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Polymer Chemistry

Guangxi University School of Chemistry amp Chemical Engineerin

g

Li Guang Hua (李光华)

Lab材料楼mdash409321 E-mail lighuagmailcomCell phone 15978133590

CHAPTER 3

1 Introduction

2 Radical and Ionic Polymerization

3 Free Radical Initiators

4 Mechanism and Kinetics of Polymerization

Free Radical Polymerization

Guangxi University School of Chemistry amp Chemical Engineeri

ng

5 Living Radical Polymerization

6 Monomer Reactivity

7 Copolymerization

8 Techniques of Polymer Preparation

(1)

1 INTRODUCTION (I)

Chain PZN

R R CH2 C

H

Y

R CH2 C

H

Y

CH2 C

H

Ym

CH2 C

H

ICH2=CHY

termination

CH2=CHYm

R CH2 C

H

CH2 C

H


ng(2)

CH2 C

Y n

Oslash have reactive center (R+ R- R∙)

Elementary reactionOslash

Growth occurs by successive addition of monomer to limited number of growing chains

Oslash

Chain initiation chain propagationChain transfer reaction chain termination

R CH2 C

Y

CH2 C

Ym

Mol

ecul

ar w

eigh

t Chain PZN

Reaction system monomer polymer initiatorOslash

1 INTRODUCTION (II)

The reaction rate and activation energy of every elementary reactions have relatively large differences

Oslash


ng(3)

Most addition PZN belong to chain PZN

0 20 40 60 80 100 Conversion

Mol

ecul

ar w

eigh

t

(a)

(c)

2 RADICAL amp IONIC PZN (I)

C C C C C Chomolysisheterolysis

R+ R- PZN R∙ PZN

CH2 CH

YPolymerized by which kinds of PZN


ng(4)

Stabilization of Y group for reactive center R+ R- and R∙ PZN

Electronic effect

Inductive effect (诱导效应)

Resonance effect (共轭效应)

Y electron withdrawing groupR- or R∙ PZN

Y electron donating group R+ PZN

R+ R- and R∙ PZN

2 RADICAL amp IONIC PZN (II)

Oslash For conjugated monomer

R+ R- and R∙ PZN

CH2 CH CH2 CH CH CH2 CH2 C CH CH2

CH3

Resonance effect


ng(5)

CH2

H

CH2

H

C CH2

H

C CH2

H

CC

Ex

2 RADICAL amp IONIC PZN (III)

Oslash For the monomers containing e- withdrawing groups

R- and R∙ PZN Resonance effect

CH2 CH

CN

CH2 CH

C O

R

CH2 CH

C O

OR

Inductive effect


ng(6)

Resonance effect

Ex

R + CH2

CN

N

δ δR CH2

C

C

H

CH

N

R CH2

C

C

H

2 RADICAL amp IONIC PZN (IV)

CH2 CH

Cl

Resonance effect (e- donating)

e- withdrawing of Cl atom

Relatively weak e- withdrawing R∙ PZN

CH2

Cl

C

H

CH2

Cl

C

H


ng(7)


CH2 CH

NO2

CH2 C

CN

CN Strong e- withdrawing R- PZN

2 RADICAL amp IONIC PZN (V)

Oslash For the monomers containing e- donating groups

R+ PZN Resonance effect

Inductive effectCH2 CH

OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3

hyperconjugation effect

Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN

2 RADICAL amp IONIC PZN (VI)

For radical PZN

Chain transfer to monomer

Weak e- donatingCoordination PZN

CH2 CH

CH3

FCH2 CH

Ye- withdrawing group


ng(9)

2

Y Y (in most cases)e withdrawing groupresonance effect

Most vinyl monomers can be polymerized by R∙ PZN

not In modern polymer industries more than 70 of polymeric materials were prepared by radical polymerization

2 RADICAL amp IONIC PZN (VII)

Monomer Type of InitiationRadical Cationic Anionic Coordination

Ethylene (CH2 = CH2)

Propylene (CH2 = CHCH3)

Isobutylene (CH2 = C(CH3)2)

Butadiene (CH2 = CHCH= CH2) +

Isoprene (CH2 = C(CH3)CH= CH2) + +

2-Chlorobutadiene (CH2= CClCH= CH2)


ng(10)

Styrene (CH2 = CHC6H5) + + +

Vinyl chloride (CH2 = CHCl) +

Vinylidene chloride (CH2 = CCl2) +

Vinyl fluoride (CH2 = CHF)

Tetrafluoroethylene (CF2 = CF2)

Vinyl ethers (CH2 = CHndashOR) +

Vinyl esters (CH2 = CHOCOR)

Methyl acrylate (CH2 = CHCOOCH3) + +

Methyl methacrylate (CH2 =C(CH3)COOCH3) + +

Acrylonitrile (CH2 = CHCN) + +

―commercialized + ―polymerized

3 FREE RADICAL INITIATORS (I)

R CH2 C

H

Y

H H

CH2=CHY∆ or hvI Chain initiation

Initiator Primary radical Monomer radical

H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation

Styrene Donrsquot add initiator Thermal PZN

PZN of most monomers require initiators

sup1

Peroxide amp hydroperoxide

3 FREE RADICAL INITIATORS (II)

FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph

Benzoyl peroxide (BPO)

60 - 80 oC

O O(CH ) COOC(CH )


ng(12)

sup1 Hydroperoxide ROOH

CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3

diacetyl peroxide di-t-butyl peroxide

gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide

3 FREE RADICAL INITIATORS (III)

Oslash Initiator efficiency f

initiatorfromformedradicalschainpolymerainitiatethatradicals

=f = 03 ~ 08 lt 1 ()

sup1 Cage effect (笼蔽效应)Some secondary reactions occur because of the confining effect of

solvent molecules and as a result the concentration of initiator

f


ng(13)

solvent molecules and as a result the concentration of initiator radicals is depleted

Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O

3 FREE RADICAL INITIATORS (IV)

Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh

sup1 Induced decomposition (诱导分解)

Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH

RO CH2CH CH2CH + ROOH

R Rn

2ROO

RO + OH

RO CH2CH CH2CH2 + ROO

R Rn

[ ROO OOR ] 2RO + O2

3 FREE RADICAL INITIATORS (V)

Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2

NN-dimethylaniline promoter


ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt

Azo compounds (偶氮化合物)

3 FREE RADICAL INITIATORS (VI)

F

ααrsquo-azobis(isobutyronitrile)(AIBN)

(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC

Resonance stabilization


ng(16)

Driving forceResonance stabilizationProduction of N2 gas

2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f

Redox initiators (氧化-还原引发剂)

3 FREE RADICAL INITIATORS (VII)

Freduction―oxidation

Thermal decomposition initiators Redox initiators

Activation energy Ea 80 ~ 140 kJmol 40 ~ 60 kJmol

Temp of initiating PZN 50 ~ 100 oC ~ 5 oC


ng(17)

Temp of initiating PZN 50 ~ 100 C ~ 5 C

Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxideFe2+

~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+

3 FREE RADICAL INITIATORS (VIII)

HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3

Initiate PZNpersulfate thiosulfate

Photoinitiators (光敏引发剂) F

Initiate PZN


ng(18)


PeroxidesAzo compounds

R∙

Remove light source

∆

hvR∙

PZN stopPZN is independent of temperature

Photoinitiation

3 FREE RADICAL INITIATORS (IX)

Photolabile compounds (光不稳定化合物)Oslash

RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv

Benzoin (苯偶姻 or 安息香)

hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN

3 FREE RADICAL INITIATORS (X)

Thermal PZN (热聚合) FStyrene methyl methacrylate (MMA)

Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN

29 oC 127 oC 167 oCTime for reaching 50 of conversion 400 days 235 days 16 min

3 FREE RADICAL INITIATORS (XI)

Electrochemical PZN (电化学聚合) F

e-e-

Cathode AnodeCathode

RCH + e RCH CH2CH2

Anode

radical anion


ng(21)

(Monomer + electrolyte)

RCH + eRCH CH2CH2

Anode

radical cation

radical anion

radical cationInitiate radical or ionic PZN

Useful for coating metal surfaces with polymer films

Mechanism of Radical PZN

4 MECHANISM amp KINETICS OF PZN (I)

R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail

4 MECHANISM amp KINETICS OF PZN (II)

CH2 CH

Y

+ CH CH2

Y

TerminationF

Disproportionation (歧化)

Coupling or combination(偶合)

α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y

Whether termination occurs by coupling or by disproportionation depends in large measure on monomer structure or more exactly on the structure of the chain-end radical

Steric repulsionElectrostatic repulsion of polar groupsAmount of α-H for hydrogen transfer

4 MECHANISM amp KINETICS OF PZN (III)

CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3

Undergo mainly disproportionation

Ex

CH2 CH + CH CH2

OCOCH3 OCOCH3Undergo disproportionation


ng(24)

Generally both coupling and disproportionation processes occur

CH2 CH + CH CH2 Undergo coupling almost exclusively at low temp

CH2 CH + CH CH2

CN CNUndergo coupling

exclusively at 60oC

4 MECHANISM amp KINETICS OF PZN (IV)

Kinetics of Radical PZN

R

M1

I

MR +

InitiationF

2kd

ki

k rate constant for the initiator decomposition

Rate determining step


ng(25)

kd rate constant for the initiator decompositionki rate constant for the initiation step

ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=

4 MECHANISM amp KINETICS OF PZN (V)

M2MM1 +

PropagationF

kp kp rate constant for propagation

M3MM2 +kp

MMM +kp

Assumption 1 the equal reactivity of chain radicals


ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][

Assumption 2 the rate of PZN is equivalent to the rate of propagation

]][[][sdot==

minus MMkRdt

Mdpp

4 MECHANISM amp KINETICS OF PZN (VI)

MyMx +

TerminationF

ktc

ktc rate constant for termination by coupling

ktd

M(x+y)

MyMx + MyMx +

k rate constant for termination by disproportination


ng(27)

Rate of termination Rt

ktd rate constant for termination by disproportination

kt = ktc + ktd

The rate constant for termination kt

2][2][sdot=

sdotminus= Mk

dtMdR tt (consume two radicals)

4 MECHANISM amp KINETICS OF PZN (VII)

Assumption 3 (steady-state assumption稳定态假定)Shortly after the reaction begins the formation and destruction

of radicals occur at the same rates hence the concentration of radicals [M] remains constant

Ri = Rt2][2][2 sdot= MkIfk td

t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop

4 MECHANISM amp KINETICS OF PZN (VIII)

Average Kinetic Chain Length ( v 平均动力学链长)

The average number of monomer units polymerized per chain initiated

t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p

While donrsquot consider chain transfer reaction


ng(29)

ti RR ][2][2 sdotsdot MkMk tt

21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling

For disproportionation

DP = 2v

DP = v

4 MECHANISM amp KINETICS OF PZN (IX)

While these kinetics expressions (Rp v) apply to a great many vinyl PZNs deviations are common ()

Gel effect (Trommsdorff effect)Oslash

Bulk PZNPrecipitation PZN

viscosity Chain mobility Rt

[Mbull] Rp (autoacceleration)


ng(30)

Chain transfer reactions Oslash


MW

CH2 CH

R

+ T CH2 CH2

R

+ T

T Monomer Initiator Solvent

MW

4 MECHANISM amp KINETICS OF PZN (X)

Chain Transfer reaction (链转移反应 )

To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY

Intermolecular chain transfer


ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3

5- or 6-membered rings

CH2=CH2Backbiting (回咬)

Bu-

Intramolecular chain transfer

4 MECHANISM amp KINETICS OF PZN (XI)

CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-

To initiator or monomer or solvent FROOR


ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex

Canrsquot obtain high MW PP Coordination PZN

4 MECHANISM amp KINETICS OF PZN (XII)

CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)

To chain transfer agent FCH2CH

Y

+ RSH CH2CH2

Y

+ RS

Control molecular weightLead into functional groups at chain end such as ndashSH etc

4 MECHANISM amp KINETICS OF PZN (XIII)


While consider chain transfer reaction

t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=

Rtr = RtrM + RtrI + RtrS + RtrT

sum sdot= ]][[trtr TMkR

sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p

(ktr chain transfer rate constant)General formula


][][11 tr

tr MkTk

vv p

sum+=

Leading into chain transfer constant CT

pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC

vvTsum+= Mayo equation

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


sup1 CM CI [I] are very small

sup1 Donrsquot add chain transfer agent ][][11

tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv

sup1 Add chain transfer agent

Large CT CS amp increase [T] and [S] vtr

Control MW

][][11

tr MTC

vv T+=


Application of chain transfer reactions

Control molecular weight Oslash

Synthesize telomer (telomerization 调聚反应) Oslash

I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation

Chain transferTelomer (n lt 100)

Termination

Telogen


Inhibit the PZN of monomers Oslash

Inhibitor (阻聚剂 )The substances act by reacting with the initiating amp propagating

radicals and converting them to either nonradical species or radicals of reactivity too low to undergo propagation

Ex benzoquinone phenols anilines nitrobenzene O2 etc


ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR

Mx O2+ Mx OOunreactive

RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH

5 CONTROLLEDLIVING RADICAL PZN (I)

In 1956 Szwarc (US) discovered living anionic PZN and pioneered the precedent of polymer design

+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M

Characteristics Oslash

Living polymer


ng(39)


sup1 Ri ge RP

sup1 No terminationsup1 No chain transfer reaction

MW

M1

M2

Conversion 100

Living PZN

Radical PZN Living radical PZN

5 CONTROLLEDLIVING RADICAL PZN (II)

Characteristics of radical PZNOslash

sup1 Slow initiation kd = 10-4 ~ -6 s-1 Ri = 10-8 ~ -10 molLmiddots

sup1 Fast propagation kP = 104 ~ 2 Lmolmiddots RP= 10-4 ~ -6 molLmiddots

sup1 Quick termination k = 108 ~ 6 Lmol s R = 10-8 ~ -10 molL s


ng(40)

Ri ge RP（similar structures of initiator and monomer）

Living radical polymerization (MwMn lt 15)

kt = 108 ~ 6 Lmolmiddots Rt= 10-8 ~ -10 molLmiddotssup1 Chain transfer reaction

Restrain termination and chain transfer (decrease [R]）

Monomer conversion le 70

5 CONTROLLEDLIVING RADICAL PZN (III)

Stable free radical PZN (SFRP) (1993 Geoges)F

BPO

Dormant(休眠种)

Active species(活性种)

R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)

TEMPO 2266-tetramethyl-1-piperidinoxyl

2266-四甲基哌啶-1-氧基O N

R M O N

initiator

()conversion][][

DP0

0 times=I

M

5 CONTROLLEDLIVING RADICAL PZN (IV)

Atom transfer radical PZN (ATRP) (1995)F

CCl4RuCl2(PPh3)3MeAl(ODBP)2 MMA toluene(80) 60oC

PMMA Mn GPC = 5200 MwMn = 132

Oslash M Sawamoto (Depart of Polymer Chemistry Kyoto University Japan)

RuCl2(PPh3)3 dichlorotris(triphenylphosphine)ruthenium

Macromolecules 28 1721 (1995)mdash


ng(42)

1-PEClCuClbpy St 130oC PS Mn GPC = 3800 ~ 105000 MwMn = 130 ~ 145

K Matyjaszewski (Depart of Chemistry Carnegie-Mellon University USA)Oslash

RuCl2(PPh3)3 dichlorotris(triphenylphosphine)ruthenium MeAl(ODBP) methylaluminium bis(26-di-tert-butylphenoxide)

1-PECl 1-phenylethyl chloride bpy 22rsquo-bipyridine

J Am Chem Sci 117 5614 (1995)mdash

5 CONTROLLEDLIVING RADICAL PZN (V)

R Mn +

+ M

kpkt

termination

CuX2 (bpy) R Mn X + CuX (bpy)

R X + CuX (bpy) R + CuX2 (bpy)

nMinitiator


ng(43)

+ M termination

Dormant (休眠种)Active species (活性种)

()conversion][][

DP0

0 times=I

M

5 CONTROLLEDLIVING RADICAL PZN (VI)

Reversible Addition-Fragmentation Transfer Radical PZN (RAFT)(1998 G Moad)

F

S

CSZ

R

RAFT agent dithioesters （双硫酯）

Z活化C=S基团的自由基加成Ph CH3

R活泼的自由基离去基团CH2Ph CH2CN


ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp

6 MONOMER REACTIVITY (I)

For almost any monomer containing a double bond

ΔGP = ΔHP ndash TΔSP lt 0enthalpy entropy

Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y

sup1 The propensity for chain transfer sup1 Polarity amp size of Y group (polar amp steric effect)

CH2 CH

Y

CH CH

YX

CH2 CH

Y

X

Polymerizable Polymerizableunless X=Y=Ph

Fail to polymerizeunless X=Y=F

(46)

6 MONOMER REACTIVITY (II)

sup1 For the initiation of radical PZN

R + CH2 CH CH2 CHR CH2 CHR

Alkyl radical


C N

Stability of monomer radical


ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

Monomer reactivity gt gt

(47)

6 MONOMER REACTIVITY (III)

BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM

Monomer reactivity M1 gt M2


ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)

sup1 For the propagation of radical PZN

The inverse relationship between monomer stability and Rp

(48)

Monomer stability prop 1monomer reactivity

6 MONOMER REACTIVITY (IV)

Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt

(Polar and steric effect)kp (Lmolmiddots 60oC) 2640 (50oC) 1960 176


ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3

Hyperconjugation andor steric effect

(49)

kp (Lmolmiddots 60oC) 2090 515

RS + M R + MSltRp

6 MONOMER REACTIVITY (V)

Ceiling Temperature (Tc 聚合上限温度)F

Mx + M Mx+1

kP

kdP

kp rate constant for propagationkdp rate constant for depropagation

H∆


ng

ΔGP = ΔHP ndash TΔSP = 0SHTc ∆

∆=

With most common vinyl monomer ceiling temperatures are sufficiently high

sup1 Steric effect

sup1 The relative stability of radicalsTc

(50)

Tc M reactivity

7 COPOLYMERIZATION (I)

sup1 The mechanism of co-PZN is analogous to that of homo-PZN

sup1 CH CH

YX

fail to homopolymerize yet enter into co-PZN with

CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y

The significance of co-PZN Oslash

sup1 Increase the variety of polymers

sup1 Modify polymers to endow new functions

(51)

7 COPOLYMERIZATION (II)

Consider the case where two monomers M1 and M2 copolymerize

+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate

[ ][ ]1111 middot MMk



ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation



Steady-state assumption for [M1middot] [M2middot]

[ ][ ] [ ][ ]12212112 middotmiddot MMkMMk =][][

][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)

7 COPOLYMERIZATION (III)

[ ] [ ][ ] [ ][ ]122111111 middotmiddot MMkMMk

dtMd

+=minus


dtMd

+=minus

sdot+sdot

The rate of disappearance of M1 and M2


ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd

Monomer reactivity ratios (r 竟聚率)

12

111 k

kr =21

222 k

kr =and

(53)

7 COPOLYMERIZATION (IV)

12

111 k

kr =21

222 k

kr =and

The relative tendencies of the monomers to self-propagateor cross-propagate

If 0 lt r1 lt 1 Copolymerization is preferredIf r1 = 0 M1 would exhibit a tendency to copolymerize


ng

The relative reactivities of two monomers

+ M1M1 M1k11

+ M2M1 M2k12

If r1 gt 1 M1 tends to self-propagationIf 0 lt r1 lt 1 Copolymerization is preferred

If r1 rarrinfin M1 would exhibit a tendency to homopolymerize

(54)

7 COPOLYMERIZATION (V)

r1 r2 and [M1middot][M2middot] combine into the above formula

+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd

Copolymer instantaneous composition equation

d[M ]d[M ] The molar ratio of two monomer units in copolymer


ng

d[M1]d[M2] The molar ratio of two monomer units in copolymer

[M1][M2] The molar ratio of two monomers in the feed

f1 f2 The mole fractions of monomer M1 and M2 in the feed

Assumption

F1 F2 The mole fractions of M1 and M2 in the copolymer

(55)

7 COPOLYMERIZATION (VI)

Above copolymer instantaneous composition equationchanges into

212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=

If we know r1 and r2 we can calculate the initial molar ratio of monomers needed to give a desired ratio of monomeric units in the copolymer

Copolymer composition equation

(56)

7 COPOLYMERIZATION (VII)

Copolymer composition curvesFOslash r1 = r2 = 10

The tendency to homopolymerize is equal to that to copolymerize

Random copolymer

The copolymer equation reduces to F1 = f1


ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)

7 COPOLYMERIZATION (VIII)

Oslash r1 = r2 = 0

Neither monomer would exhibit a tendency to homopolymerize

Alternating copolymer

The copolymer equation reduces to F1 = 05

10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)

7 COPOLYMERIZATION (IX)

Oslash 0 lt r1 lt 1 0 lt r2 lt 1The curve crosses the diagonal At this intersection either feed ratio

or copolymer composition donrsquot change

Azeotropic PZN (恒比聚合)

At azeotropic point ][][

][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=

The copolymer equation reduces to

MMA + Styrene

(59)

7 COPOLYMERIZATION (X)

Oslash r1 gt 1 r2 lt 1Such cases lead to incorporation of monomer M1 almost exclusively

in the early stages of PZN

When r1 is very high and r2 is close to 0 one obtains essentially a homopolymer of M1

10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)

7 COPOLYMERIZATION (XI)

Oslash r1 middot r2 = 1It is common among polymer chemists to refer to as ideal co-PZN

following a parallel with vapor-liquid equilibria

Random copolymer

The copolymer equation reduces to ][][

][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)

7 COPOLYMERIZATION (XII)

Q-e SchemeFr is a important parameter for co-PZN but it is difficult for it to

determine totally

Q-e scheme was suggested by Alfrey-Price in 1947

+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1

+ M2M1 M2k12 )exp( 212112 eeQPk minus=

)exp( 11111 eQPk minus=

P1 the intrinsic reactivity of M1middotQ1 Q2 the intrinsic reactivities of M1 and M2 respectively

e1 the polarities of M1middot and M1


(62)

7 COPOLYMERIZATION (XIII)

)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk

Q1 Q2 the measures of the reactivity of M1 and M2

e1 e2 the measures of the polarity of M1 and M2

Resonance stabilization Q value of M

M with e- withdrawing group e positive (+)M with e- donating group e negative (-)

(63)


Styrene was chosen as the standard and assigned values of Q = 100 and e = -080

Monomer Q e

1-Vinylnaphthalene 194 -112p-nitrostyrene 163 039p-methoxystyrene 136 -111


ng

p-methoxystyrene 136 -111styrene 100 -080Methyl methacrylate 074 040Acrylonitrile 060 120Methyl acrylate 042 060Vinyl chloride 0044 020Vinyl acetate 0026 -022

(64)


Reactivity ratio r steric resonance and polar effects

The values of r1 r2 calculated by Q-e Scheme are deviations from those obtained by experiments(not considered steric effect)

Oslash Applications of Q-e Schemesup1 Predict the reactivity ratios of monomerssup1 Discriminate the behavior of co-PZNs


ng

sup1 Discriminate the behavior of co-PZNs

(1) The difference of Q value is large difficult to co-PZN

Ex StyreneVAc Q1 = 10 Q2 = 0026 (r1 = 55 r2 = 001)

(2) The monomers with similar value of Q e are easy to take place co-PZN

Ex StyreneMMA Q1 = 10 Q2 = 074 e1 = -080 e2 = 040 (r1 = 052 r2 = 046)

(65)


(3) The differences of e value are large easy to take place alternating co-PZN

CHHCC

OC OO

+CH2 CH

PhAlternating copolymer

cannot homopolymerize

Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2

By Q-e Scheme 0032 54times10-8

By experiment (60oC) 0041 001

(66)

8 TECHNIQUES OF RADICAL PZN (I)

Techniques of Step PZN

Melt polycondensation

Solution polycondensation

Interfacial polycondensation

Solid-phase polycondensation


ng

Techniques of Radical PZNF

Homogeneous PZN

Heterogeneous PZN

Bulk PZN (本体聚合)

Solution PZN (溶液聚合)

Suspension PZN (悬浮聚合)

Emulsion PZN (乳液聚合)

(67)

8 TECHNIQUES OF RADICAL PZN (II)

Bulk PZN

Components M + I (monomer + initiator)

Place of PZN Bulk

Mechanism 21][][ IMRp prop 21][1][

IMv prop

Oslash Bulk PZN (本体聚合)


ng

Mechanism

Advantages Simple no contaminants added

DisadvantagesReaction exotherm difficult to control

high viscosity

Industrial applications

Poly(methyl methacrylate) (PMMA)Polystyrene (PS)

Polyethylene (PE)Poly(vinyl chloride) (PVC)

][][ IMRp prop 21][][

IMv prop

(68)

8 TECHNIQUES OF RADICAL PZN (III)

Solution PZNComponents M + I + S (monomer + initiator + solvent)Place of PZN Solution

MechanismChain transfer to solvent

21][][ IMRp prop 21][1][

IMv prop

Oslash Solution PZN (溶液聚合)


ng

Chain transfer to solvent

Advantages Heat readily dispersed low viscosity may be used directly as solution

DisadvantagesAdded cost of solvent solvent difficult to remove

possible chain transfer with solvent possible environmental pollution


Poly(acrylic ester) (PMMA)Polyacrylonitrile (PAN)

Poly(vinyl acetate) (PVAc)

(69)

8 TECHNIQUES OF RADICAL PZN (IV)

Suspension PZN

ComponentsM + I + H2O + stabilizer (dispersant)

(I soluble in monomer)Place of PZN Monomer droplet

Mechanism 21][][ IMR prop1][Mv prop

Oslash Suspension PZN (悬浮聚合)


ng

Mechanism

AdvantagesHeat readily dispersed low viscosity polymer obtained

in granular form and may be used directly

DisadvantagesWashing andor drying required agglomeration may

occur contamination by stabilizer


Poly(vinyl chloride) (PVC)Polystyrene (PS)

21][][ IMRp prop 21][][

IMv prop

(70)

8 TECHNIQUES OF RADICAL PZN (V)


M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion

aggregationcoagulation

coagulation

(71)

8 TECHNIQUES OF RADICAL PZN (VI)

Emulsion PZN

ComponentsM + I + H2O + emulsifier

(I soluble in water)Place of PZN Emulsion particle amp micelle

Mechanism Increasing rates of emulsion PZN usually lead to higher MW

Oslash Emulsion PZN (乳液聚合)


ng


AdvantagesHeat readily dispersed low viscosity high MW obtainable

may be used directly as emulsion works on tacky polymers

DisadvantagesContamination by emulsifier and other ingredients chain

transfer agents often needed to control DP washing and drying necessary for bulk polymer


Styrene-Butadiene Rubber (SBR)Poly(acrylic ester) (coatings adhesives)

(72)

8 TECHNIQUES OF RADICAL PZN (VII)

polymerM

I R

Micelle(4 ndash5nm)

M-swollen micelle(10 nm)

Polymer particleswollen with M

Increasing rates of emulsion PZN usually lead to higher MW


ng

Micelle Monomer droplet

concentration ml-1 1018 1012

Surface area cm2middotml-1 3times106 3times104

M droplet1000nm

Aqueous phase

(73)

8 TECHNIQUES OF RADICAL PZN (VIII)

]][[ sdot= MMkR pp

[M] The concentration of monomer in micelles plus particlesN The concentration of micelles plus particles (ml-1)

The average number of radicals per micelles plus particles n

21=n


ng

2=n

ANNM

210][

3

=sdot

Then

NA Avogadro constant

A

pp N

MNkR

2][103

= NMRp ][prop

(74)

8 TECHNIQUES OF RADICAL PZN (IX)

Ri The overall rates of initiator radical formation

For a emulsion particle

NR

r ii =Initiation rate ri

Propagation rate rp ][Mkr pp =


ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then

The molecular weight Increases with PZN rate

(75)

Hermann Staudinger (1881mdash1965)


ng

HW

Review exercises 1 (a) (b) (c) (g) (m) (p)2 (a) (d) (e)3 8 9 11 16

(76)

CHAPTER 3

1 Introduction

2 Radical and Ionic Polymerization

3 Free Radical Initiators

4 Mechanism and Kinetics of Polymerization

Free Radical Polymerization


ng

5 Living Radical Polymerization

6 Monomer Reactivity

7 Copolymerization

8 Techniques of Polymer Preparation

(1)

1 INTRODUCTION (I)

Chain PZN

R R CH2 C

H

Y

R CH2 C

H

Y

CH2 C

H

Ym

CH2 C

H

ICH2=CHY

termination

CH2=CHYm

R CH2 C

H

CH2 C

H


ng(2)

CH2 C

Y n




Oslash


R CH2 C

Y

CH2 C

Ym

Mol

ecul

ar w

eigh

t Chain PZN


1 INTRODUCTION (II)


Oslash


ng(3)


0 20 40 60 80 100 Conversion

Mol

ecul

ar w

eigh

t

(a)

(c)



R+ R- PZN R∙ PZN

CH2 CH



ng(4)


Electronic effect





R+ R- and R∙ PZN



R+ R- and R∙ PZN


CH3

Resonance effect


ng(5)

CH2

H

CH2

H

C CH2

H

C CH2

H

CC

Ex




CH2 CH

CN

CH2 CH

C O

R

CH2 CH

C O

OR

Inductive effect


ng(6)

Resonance effect

Ex

R + CH2

CN

N

δ δR CH2

C

C

H

CH

N

R CH2

C

C

H


CH2 CH

Cl




CH2

Cl

C

H

CH2

Cl

C

H


ng(7)


CH2 CH

NO2

CH2 C

CN






OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3


Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)

1 INTRODUCTION (I)

Chain PZN

R R CH2 C

H

Y

R CH2 C

H

Y

CH2 C

H

Ym

CH2 C

H

ICH2=CHY

termination

CH2=CHYm

R CH2 C

H

CH2 C

H


ng(2)

CH2 C

Y n




Oslash


R CH2 C

Y

CH2 C

Ym

Mol

ecul

ar w

eigh

t Chain PZN


1 INTRODUCTION (II)


Oslash


ng(3)


0 20 40 60 80 100 Conversion

Mol

ecul

ar w

eigh

t

(a)

(c)



R+ R- PZN R∙ PZN

CH2 CH



ng(4)


Electronic effect





R+ R- and R∙ PZN



R+ R- and R∙ PZN


CH3

Resonance effect


ng(5)

CH2

H

CH2

H

C CH2

H

C CH2

H

CC

Ex




CH2 CH

CN

CH2 CH

C O

R

CH2 CH

C O

OR

Inductive effect


ng(6)

Resonance effect

Ex

R + CH2

CN

N

δ δR CH2

C

C

H

CH

N

R CH2

C

C

H


CH2 CH

Cl




CH2

Cl

C

H

CH2

Cl

C

H


ng(7)


CH2 CH

NO2

CH2 C

CN






OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3


Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)

Mol

ecul

ar w

eigh

t Chain PZN


1 INTRODUCTION (II)


Oslash


ng(3)


0 20 40 60 80 100 Conversion

Mol

ecul

ar w

eigh

t

(a)

(c)



R+ R- PZN R∙ PZN

CH2 CH



ng(4)


Electronic effect





R+ R- and R∙ PZN



R+ R- and R∙ PZN


CH3

Resonance effect


ng(5)

CH2

H

CH2

H

C CH2

H

C CH2

H

CC

Ex




CH2 CH

CN

CH2 CH

C O

R

CH2 CH

C O

OR

Inductive effect


ng(6)

Resonance effect

Ex

R + CH2

CN

N

δ δR CH2

C

C

H

CH

N

R CH2

C

C

H


CH2 CH

Cl




CH2

Cl

C

H

CH2

Cl

C

H


ng(7)


CH2 CH

NO2

CH2 C

CN






OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3


Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



R+ R- PZN R∙ PZN

CH2 CH



ng(4)


Electronic effect





R+ R- and R∙ PZN



R+ R- and R∙ PZN


CH3

Resonance effect


ng(5)

CH2

H

CH2

H

C CH2

H

C CH2

H

CC

Ex




CH2 CH

CN

CH2 CH

C O

R

CH2 CH

C O

OR

Inductive effect


ng(6)

Resonance effect

Ex

R + CH2

CN

N

δ δR CH2

C

C

H

CH

N

R CH2

C

C

H


CH2 CH

Cl




CH2

Cl

C

H

CH2

Cl

C

H


ng(7)


CH2 CH

NO2

CH2 C

CN






OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3


Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



R+ R- and R∙ PZN


CH3

Resonance effect


ng(5)

CH2

H

CH2

H

C CH2

H

C CH2

H

CC

Ex




CH2 CH

CN

CH2 CH

C O

R

CH2 CH

C O

OR

Inductive effect


ng(6)

Resonance effect

Ex

R + CH2

CN

N

δ δR CH2

C

C

H

CH

N

R CH2

C

C

H


CH2 CH

Cl




CH2

Cl

C

H

CH2

Cl

C

H


ng(7)


CH2 CH

NO2

CH2 C

CN






OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3


Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




CH2 CH

CN

CH2 CH

C O

R

CH2 CH

C O

OR

Inductive effect


ng(6)

Resonance effect

Ex

R + CH2

CN

N

δ δR CH2

C

C

H

CH

N

R CH2

C

C

H


CH2 CH

Cl




CH2

Cl

C

H

CH2

Cl

C

H


ng(7)


CH2 CH

NO2

CH2 C

CN






OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3


Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


CH2 CH

Cl




CH2

Cl

C

H

CH2

Cl

C

H


ng(7)


CH2 CH

NO2

CH2 C

CN






OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3


Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)





OR

H H

CH2

O

C

R

H


ng(8)

CH2 C

CH3

CH3


Inductive effect

R

CH2

O

C

R

CH2

O

C

R+ PZN


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


For radical PZN



CH2 CH

CH3

FCH2 CH



ng(9)

2













ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)










ng(10)













R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


R CH2 C

H

Y

H H



H

decompositionR2


ng(11)

R CH2 C

H

Y

CH2 C

H

Yn

CH2=CHYnR CH2 C

H

Y

Chain propagation



sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)

sup1



FPeroxide ROOR

Ph C O O C Ph

O OC O

O

2Ph


60 - 80 oC

O O(CH ) COOC(CH )


ng(12)


CH3COOCCH3

Ph C OOH

CH3

CH3

(CH3)3COOC(CH3)3


gt 100 oCPh C O

CH3

CH3

OH+

cumyl hydroperoxide




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




=f = 03 ~ 08 lt 1 ()



f


ng(13)


Ph C O O C Ph

O OC O

O

2Ph∆

Ph + CO2

M Initiate PZN

2Ph Ph Ph

C O

O

Ph Ph+ Ph C O Ph

O


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


Ph C O O C Ph

O O

Ph+ Ph C O O C Ph

O OPh


Ph C O Ph

O

O C Ph

O

+

I

I

f


ng(14)

ROOH


R Rn

2ROO

RO + OH


R Rn



Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


Ph C O O C Ph

O O

+ Ph N(CH3)2

Ph N O C Ph

CH3 O+ Ph CO2



ng(15)

CH3

Ph N O C Ph

CH3 O

CH3

Ph NH2(CH3)2 C OO

Ph+

Initiate PZN

rt



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



F


(CH3)2C N N C(CH3)2

CN CN

2(CH3)2C

CN

+ N2gt 40 oC



ng(16)


2(CH3)2C

CN(CH3)2C C(CH3)2

CN CN

(CH3)2C C N C(CH3)2

CNCage effect

f








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)








ng(17)


Ex

Ph C OOH

CH3

CH3

gt 100 oCPh C O

CH3

CH3

OH+


~ 5 oCPh C O

CH3

CH3

OH+ + Fe3+


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


HOOH + Fe2+

O3SOOSO3 + S2O32

+ OH Fe3++HO

SO4+SO42 + S2O3



Initiate PZN


ng(18)



R∙

Remove light source

∆

hvR∙


Photoinitiation



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



RS SR

Ph C CH Ph

O OH

2RS

O OH

hv

disulfide

hv

Initiate PZN


ng(19)

Ph C CH Ph

Ph C C Ph

O O

+Ph C CH Ph

C

O

2Ph

hv


hv

Benzil (苯偶酰)

Initiate PZN

Initiate PZN



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



Ph PhH

CH2 CH

PhDiels-Alder


ng(20)

Ph

CH3 CH

Ph

+

Ph

Initiate PZN




e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



e-e-


RCH + e RCH CH2CH2

Anode

radical anion


ng(21)


RCH + eRCH CH2CH2

Anode

radical cation

radical anion





R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



R

R CH2 CH

Y

I

CH2 CH

Y

R +

InitiationF

2 Primary radical

Monomer radical

∆ or hv


ng(22)

R CH2 CH

Y

CH2 CH

Y

CH2 CH

Yn

CH2=CHYn

PropagationFCH2 CH

Y

+R CH2 CH

Y

CH2 CH

Y

R CH2 CH

Y

head-to-tail


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


CH2 CH

Y

+ CH CH2

Y

TerminationF



α α


ng(23)

CH2 CH

Y

CH CH2

Y

CH CH

Y

+ CH2 CH2

Y




CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


CH2 C

COOCH3

+ C CH2

CH3 CH3

COOCH3


Ex

CH2 CH + CH CH2



ng(24)



CH2 CH + CH CH2


exclusively at 60oC



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



R

M1

I

MR +

InitiationF

2kd

ki




ng(25)


ki gtgt kd

Initiation rate Ri

][2][

IfkdtMd

R di =sdot

=


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


M2MM1 +

PropagationF


M3MM2 +kp

MMM +kp



ng(26)

Rate of PZN R

M(x+1)MMx +

pi RRdt

MdR +=minus

=][


]][[][sdot==

minus MMkRdt

Mdpp


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


MyMx +

TerminationF

ktc


ktd

M(x+y)

MyMx + MyMx +



ng(27)



kt = ktc + ktd


2][2][sdot=

sdotminus= Mk






t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)





t

d

kIfk

M][

][ =sdot


ng(28)

t

t

dppp k

IfkMkMMkdt

MdR ][][]][[][=sdot=

minus=

21][][ IMRp prop




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




t

p

i

p

RR

RR

v ==][2

][][2

]][[2 sdot

=sdot

sdot=

MkMk

MkMMk

vt

p

t

p



ng(29)


21])[(2][

IkfkMk

vdt

p= 21][1][

IMv prop

For coupling


DP = 2v

DP = v








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)








ng(30)



MW

CH2 CH

R

+ T CH2 CH2

R

+ T


MW



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



To polymer F

CH

Y

+ CH2CH

Y

CH2

Y

+ CH2C

Y CH2=CHY

CH2CHY



ng(31)

CH2C

Y(branching)

CH

CH2 CH2

CH2

CH2H

CH

CH2 CH2

CH2

CH3



Bu-



CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


CH

CH2

CH CH2CH3

CH2

CH2 H

CH

CH2

CH CH2CH3

CH3

CH2

CH2=CH2

Et-



ng(32)

CH2CH

Y

CH2CHOR

Y

+ RO

CH2CH2

Y

+ CH2 CYCH2=CHY

ROOR

CH2CH

CH3

+ CH3CH CH2 CH2CH2

CH3

+ CH CH2CH2

Ex



CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


CH2CH

Ph

+ CCl4

CH2

Ph

CH+CCl3 Cl3CCH2CH

Ph

etc

CH2CHCl

Ph

+ CCl3

solvent


ng(33)


Y

+ RSH CH2CH2

Y

+ RS





t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




t

p

i

p

RR

RR

v ==

trR

v p

+=

][2][

][2]][[

2 sdot=

sdot

sdot=

MkMk

MkMMk

vt

p

t

p


ng(34)

tr

trRR

vt +

=



sum+sdot=

sum sdot+sdot

sdot=

][][2][

]][[][2]][[

trtr2tr

TkMkMk

TMkMkMMk

vt

p

t

p



][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


][][11 tr

tr MkTk

vv p

sum+=


pT k

kC tr= CH

R

M kp

Tktr


ng(35)

pk R ktr

][][11

tr MTC


][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




tr MSC

vv S+=

][][

][][

][][11

tr MTC

MSC

MICC

vv TSIM ++++=


ng(36)

][tr Mvv



Control MW

][][11

tr MTC

vv T+=





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)





I+ YZR+ MY

hvor 2R

RZ + YYM

Initiation


ng(37)

+ MYMn

+ MY

+ YZYMn

+Y Y

YM

YMn+1

YMnZ + Y

Dead polymer

Y2

+YMn YMn

Propagation


Termination

Telogen







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)







ng(38)

R +R R

R

OH

RRH +R R

R

OR R

R

OR


RH

Mx

MxOOH

MxOOMx

gt100oC MxO and OH



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn

n M


Living polymer


ng(39)


sup1 Ri ge RP


MW

M1

M2

Conversion 100

Living PZN








ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)







ng(40)








BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



BPO

Dormant(休眠种)


R Mn + O N

+ M

kpkt

termination

R R Mn O NnM


ng(41)



R M O N

initiator

()conversion][][

DP0

0 times=I

M









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)









ng(42)







R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


R Mn +

+ M

kpkt

termination



nMinitiator


ng(43)

+ M termination


()conversion][][

DP0

0 times=I

M



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



F

S

CSZ

R





ng(44)

+ S CZ

S RI + nM Mn S C

Z

SR

RAFT agent

()conversion][

][DP0

0 times=RAFT

M


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


I R

Pn + S CZ

S RPn S C

Z

S RPn S C

Z

SR+

Pm

nM

mM


ng(45)

Pm + S CZ

S PnPm S C

Z

S PnPm S C

Z

SPn+

+ M

kp

+ M

kp




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




Thermodynamics

Kinetics

Oslash

Oslash

Monomer reactivityF


ng

CH2 CH

Y


CH2 CH

Y

CH CH

YX

CH2 CH

Y

X



(46)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




Alkyl radical


C N



ng

CN CN C N

R + CH2 CH

OCCH3

O

CH2 CHR

OCCH3

O

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3


(47)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


BPOΔ Ph14CO2

Ph14CO2M

Ph + 14CO2

M2

M1PhM



ng

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt (Polar effect)



(48)



Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


Monomer reactivity

Monomer reactivity

CH2 CH

Ph

CH2 CH

CN

CH2 CH

OCOCH3

gtgt



ng

Monomer reactivity

CH2 C

COOCH3

CH3

gtCH2 CH

COOCH3


(49)


RS + M R + MSltRp



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



Mx + M Mx+1

kP

kdP


H∆


ng


∆=


sup1 Steric effect


(50)

Tc M reactivity



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



sup1 CH CH

YX


CH2 CH

Y

CH2 CH

Y

X

or


ng

Y Y




(51)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



+ M1M1 M1k11

+ M2M1 M2k12

Self-propagation

Cross-propagation

Rate




ng

+ M1M2 M1k21

+ M2M2 M2k22

Cross-propagation





][][

212

121

2

1

MkMk

MM

=sdotsdot

(52)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



dtMd

+=minus


dtMd

+=minus

sdot+sdot



ng

sdot+sdotsdot+sdot

=][][][][

][][

][][

222112

221111

2

1

2

1

MkMkMkMk

MM

MdMd


12

111 k

kr =21

222 k

kr =and

(53)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


12

111 k

kr =21

222 k

kr =and




ng


+ M1M1 M1k11

+ M2M1 M2k12



(54)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



+

+=

][][][][

][][

][][

221

211

2

1

2

1

MrMMMr

MM

MdMd




ng




Assumption


(55)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



212

11 fffrF

+=

][][][

121

121 MM

Mff

+=minus=

][][][

121

121 MdMd

MdFF

+=minus=


ng

22221

211

21111

2 frfffrfffr

F++

+=



(56)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




Random copolymer



ng

F1

f1

0 05 10

10

05CH2 CH2 CH2 CH

OCOCH3

+

r1 = 097 r2 = 102

Ex

(57)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


Oslash r1 = r2 = 0




10


ng

F1

f1

0 05 10

10

05

r1 = 0041 r2 = 001

Ex

HC CH

C O

CH2 CH

Ph COO

+

(58)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)






][][

2

1

2

1

MM

MdMd

=


ng

r1 = 052 r2 = 046

ExF1

f1

0 05 10

10

05

Azeotropic point

22

1

2

2

1

11

][][

rr

MM

minusminus

=


MMA + Styrene

(59)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)





10


ng

F1

f1

0 05 10

10

05

r1 = 55 r2 = 001

Ex

CH2 CHCH2 CH

Ph

+

OCOCH3

(60)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




Random copolymer


][][

2

11

2

1

MMr

MdMd

=


ng

r1 = 10 r2 = 01

Ex

CH2 CHCH2 C

COOCH3

+

Cl

CH3

r1 = 01

r1 = 10

03

3F1

f1

0 05 10

10

05

(61)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



determine totally


+ M1M1 M1k11 )exp( 2

11111 eQPk minus=


ng

+ M1M1 M1






(62)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


)](exp[ 2112

1

12

111 eee

QQ

kkr minusminus

==

)](exp[ 1221

2

21

222 eee

QQ

kkr minusminus

==

In the same way


ng

121 Qk





(63)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



Monomer Q e



ng


(64)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)






ng






(65)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



CHHCC

OC OO

+CH2 CH



Q = 10 Q = 086


ng

Q1 = 10 e1 = -080

Q2 = 086 e2 = 369

r1 r2



(66)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)








ng


Homogeneous PZN

Heterogeneous PZN





(67)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


Bulk PZN


Place of PZN Bulk


IMv prop



ng

Mechanism



high viscosity




][][ IMRp prop 21][][

IMv prop

(68)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




21][][ IMRp prop 21][1][

IMv prop



ng








(69)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


Suspension PZN






ng

Mechanism







21][][ IMRp prop 21][][

IMv prop

(70)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



M dropletM droplet

Water


ng

M

dispersant

stirring

stirring

dispersion


coagulation

(71)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


Emulsion PZN






ng








(72)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


polymerM

I R

Micelle(4 ndash5nm)





ng




M droplet1000nm

Aqueous phase

(73)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)


]][[ sdot= MMkR pp



21=n


ng

2=n

ANNM

210][

3

=sdot

Then


A

pp N

MNkR

2][103

= NMRp ][prop

(74)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)




NR




ng

NMv ][prop

][2][][

DPIfk

MNkR

MNkrr

vd

p

i

p

i

p ====

Then


(75)



ng

HW


(76)



ng

HW


(76)

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