22

Vol.2Vol.2

1.

2.

3.

4.

5.

6.

7.

2

2

3

7

11

13

18

2 3

1.

2.

1880 1928 1912 1930

1839 19301835 19311933 1939

1934 1938 PET1941 1953

1930

1930

H. Staudinger1953

19201

Staudinger

X

Staudinger a

1930 1935 Carothers

2000 K. Ziegler G. Natta 1963P. J. Flory

1974B. Merrifield19842002

3.

St

20

ESR PLP

(Rp) (1) Rp kp[M]Ri/kt0.5 1kp kt [M] Ri kp/kt0.5 kp kt Polymer Handbook2 60 kt0.5 kp 1 2

1kt0.5kp-() (CH2C(CH2X)CO2R) (CH2C(CH2CO2R)CO2R)

(CH2C(CH3)CO2R)- (CH2CHX)

((OCCHCHC(O)NR) (trans-RO2CCHCHCO2R) (CH3CHCHCO2R)

a

CH2 CH2 CH2 CH2 CH2 CH2CH CH CH CH CH CH

H

H

HH

H

H

H

HH

H

H

H

HH

H

HH

H H

HH H

HHH

H

HH

H H

HH H

HHH

H

HH

H H

HH H

HHH

H-2.00

1.0

2.0

3.0

4.0

5.0

-1.0 1.0 2.0 3.0 4.00

log[kpL/mols]

log

[kt0

.5 (L0

.5/m

ol0.5s

0.5)]

4 5

kp 2800 L/mols VAc1 0.028 L/mols2RCH2CCH33 105 kt 2x107 L/mols- 3 44 L/mols2RCH2C-

(CH3)3

2N- 456kp kt StMMA VAc - CH2C-

CH2XCO2R kp kt -3MMA7- kp 831 L/mols kt 2.1x107 L/mols kp kp 8.6 L/mols kt 2.1x107 L/mols- - -

-8-

CH2CHCO2CH32 kp kt 1kp/kt0.5 kp 4.0 L/mols kt 4x104 L/mols

-

CH2CCO2C2H53 -9-

CH2CHCO2CH32 8

Tc

Tc 1 2-52 [M]c 1 mol/L Tc H/S Tc H/S + Rln [M]c 2H S H -80 -100 kJ/molS -100 -120 J/molKMMA H -56 kJ/molS -117 J/molK 110 [M]c 0.0298 mol/L 2

-10Tc 0- 3 kp

CC

1- 11 3,5-

-1- 12 kp kt 6

1 CH2CHCH2X

b

CH2CHCHX c

2(1) - (12)

C

CHHC

CN

OO

R

N- 4

CH2 C

CH2CO2R

CO2R

5 6

CH CH

CO2R

CH3

CH2 C

CH3

CO2CH3

7

- 8

CH2 C

CH2CH

CO2CH3

CO2CH3

CO2CH3

- 9

CH2 C

CH2C

CO2CH3

CO2C2H5CO2C2H5CO2C2H5

CH2 CH

OCOCH3

1

RO2C

CH CH

CO2R

2 - 3

CH2 C

CO2R

CH2CH3

- 10

CH2 C

CH3

1- 11

CH2 C

CH3

CO2

3,5- -1- 12

CH2 C

CH3

CO2

CH3

CH3

1Tc

[M] (mol/L) Tc 0.82

8.35

1.99

9.1 x 10-4

1.8

155.5

220

82

90

120

150

310

53

61

2

2

3

4

5

2

2

2

2

MMA7

MMA7

- 3

5

- 10

- 10

- [2,2- ]-

8

b

c

P + CH2 CH2CHCH2X P CHCHXH +

CH2 CH2CHCHX + CHCH2X CH2 CH2 CHCHCH

X CH2X

6 7

CH2CHCH3 -

CH2CCO2CH3CH3 MMA7

CH2CCO2CH3CH2

1

6

- --- 13

7-10

-14 8 3

9-11

-

-

1963-1964 12,13

-

MMA

14-

- 20

- CH2CCH2OHCO2R

1980 15

1990

16

- -

- 17

d

e18,19 2

4.

4 2,2- MAIB

St

20

3

C

CO

CH2

CH2 CH2

O

CH2 CH2CH2 C

CC

- -- 13 - 14

d

e

CO2R

O

CO2RCO2R CO2R CO2R CO2R

OO

+

NC CNRO2C CO2R

CO2R CO2R CO2R CO2R

NC CNNC CN

+

5

10

15

0

min

0 100 200 300 400 500

%

Rp x

10

4 (m

ol/L

s)

20

40

60

80

100

0

:

: FT-NIR

4St70FT-NIR

Rp [MAIB]0.01 mol/L

8 9

MMA 60 20%

FT-NIR

1H-NMR HCC

ESR

ESR

ESR FT-NIR Rp 21,22

5 St 20,23

MAIB Ri RtRp

Rp 100%

6

kp kt 7 8 90%

5St70

7St70DVBkp

[St

] x1

07

mol/L

0

30

20

10

0

200 400 600

min

[MAIB]0.2 mol/L

0.1 mol/L

0.05 mol/L

0.02 mol/L

A B

3

2

1

0

-10 20 40 60 80 100

%

log

[kp

L/m

ols

]

[DVB]00.20, 0mol/L,

6

(A)

(B)

10 11

Ri

0% 9

St 20

9

7 8 5 Rp 4Mn Mw/Mn 9 St RpMn Mw/Mn

5.

M1 M2M1 M2

102

2

M1 M2

34

d[M1]/dt k11[M1][M1] + k21[M2][M1] 3 d[M2]/dt k12[M1][M2] + k22[M2][M2] 4 [M1] [M2] M1 M2 k11 M1 M1 M1 k21 M2 M2 M1 k12 k22 f g hi

M1M1 M2M1 M1M2 M2M2

[M1] [M2] 24

M1 M25 M2M1

M1M2

k12[M1][M2] k21[M2][M1] 5345 [M1] [M2] 6

d[M1]/d[M2] ([M1]0/[M2]0){(k11/k12)[M1]0 + [M2]0}/{[M1]0 + (k22/k21) [M2]0} ([M1]0/[M2]0){r1[M1]0 + [M2]0}/{[M1]0 + r2[M2]0} 6

8St70DVBkt 10M1M2

9St (a) 03.3% (010 min); (b) 3.36.8% (1020 min); (c) 9.8~19.5% (3060 min); (d) 34.4~48.4% (120180 min); (e) 60.3~89.9% (240300 min)

%

log

[kt

L/m

ols

]

[DVB]00.20, 0.10, 0 mol/L

0 20 40 60 80 100

6

4

2

8

log Mn

a

c d

e

b

4 5 63 7

M2 M2

M2M2

M2M2 M2

M2 M2 M2

M1M1

M1

M1 M1

M1M1

M1M1

M1

M1M2

+

M2M1

M1 M1M1+k11

f

M2 M1M1+k21

h

M1 M2M2+k12

g

M2 M2M2+k22

i

12 13

6.

1 2

3

13

k11/k12 k22/k21 r1 r2 2

r1 x r21 r1 x r21 6[M1]0/[M2]0d[M1]/d[M2]M1 M2 (3) (4)r1 r2 1 r1 r2 0 [M1]/[M2] r1 r2 (6)

MMAM1 StM2

6 11 rMMA 0.46rSt 0.52MMA St r1 r2 1

St VAc

11VAc St

St St VAc rVAc 0rSt 42 St VAc St

12VAc-St

St-MMA

100

80

60

40

20

00 20 40 60 80 100

[St

]

mol%

[St]mol%

St-VAc

St-MMA

r1r21

r1 r20

11St-VAc () St-MMA () r1r21r1r20

12St-VAc () St-MMA ()

13

0 20 40 60 80 100

20

16

12

8

4

00

10

20

30

40

50

60

VAc-

St

x10

5 m

ol/L

s

MM

A-S

t

x10

5 m

ol/L

s

[VAc] [MMA]mol%

Z

ZZ

Z

Z

X

CH2

CH2

C

X

Z

C

14 15

14 CH2CH-C6H4-CHCH2, DVB

St [DVB]0 0.10 0.20 mol/L 20 10%

FT-NIR St

[DVB] 0 DVB

25

15 DVB

DVB Rt DVB

DVB

7 DVB St kp kp 80% kp DVB 90%DVB

kt DVB 8 90% kt 1/100,000 7 8 kp kt kp/kt0.5 kp 150 L/mols[DVB] 0.20 mol/L 90% kp 1 L/mols kt 3x106 5x107 L/mols 90% kt 2900 L/mols kp/kt0.5 0.02 0.08 L0.5/mol0.5s0.5 90% 0.02 L0.5/mol0.5s0.5

90% 1/10 kp/kt0.5 1/10kp/kt0.5 Mn [DVB] 0 Mn Mw/Mn 2 16Mn DVB Mn Mw/Mn 2 DVB Mw/Mn 16Mn

14DVBSt70[MAIB] 0.10 mol/L

15DVBSt70

[MAIB] 0.10 mol/L

16DVBSt70MnMw/Mn[DVB]0 0.20 (), 0.10 (), 0.05 (), 0 () mol/L, [MAIB] 0.10 mol/L

[DVB]00.20 mol/L

[DVB]00.10 mol/L

[DVB]00 mol/L

0 100 200 300 400

100

80

60

40

20

0

min

%

min

[St

] x1

07

mol/L

20

0

60

40

0 400 800 1200

[DVB]0.2 mol/L

[DVB]0 mol/L

Mn x

10

-4M

w/M

n

[DVB]

[DVB]

6

5

4

3

2

10 10 20 30 40 50

%

4

3

2

1

16 17

7Flory-Stockmayer

261

2

c1/(Pw -17c Pw

1 Pw 11 c 0.1 Pw 101 c 0.01 10% 1%

26,27

17

7

18

MMAEGDMA

EGDMA

1H-NMR

1/2 28

2 MMA EGDMA 291%

EGDMA 5.7%EGDMA

7

EGDMA EGDMA

EGDMA

17

18

2MMA-EGDMA(7)

[EGDMA]mol%

Pw x10-3%

2.94

3.80

4.85

56.6

13.2

1.05

72.5

35.8

5.7

0.03

0.1

1

18

MMA

EGDMA

1/85 1/16 0%

6.5 30EGDMA MMA

Flory-Stockmayer 7

Flory-Stockmayer

7.

) , , , , 1966.

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193

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Vol.2 220102

2010225