rh r･＋o roo･＋rh ro･＋rh 2r･ - nedo:国立研 …...
TRANSCRIPT
-
95
.2.1.1(3)-1
1) P, ,,
(1998),p.16
2) M. Kakugo, H. Sadatoshi, M. Yokoyama, K. Kojima, Macromolecules, 22222222, 547 (1989)
3) L. Norosti, E. Marchetti, G. Baruzzi, P. Sgarzi, J. Polym. Sci. Part A : Polym. Chem., 32323232,
3047 (1994)
4) G. Cecchin, E. Marchetti, G. Baruzzi, Macromol. Phys., 202202202202, 1987 (2001)
5) G. Weickert, G. B. Meier, J. T. M. Pater, K. R. Westerterp, Chem. Engng, Sci., 54545454, 3291
(1999)
6) T. MaKenna, V. Mattioli, Macromol. Symp., 173173173173, 149 (2001)
7) J. B. P. Soares, A.E. Hamielec, Macromol. Theory Simul., 4444, 1085 (1995)
8) P. Galli, J.Macromol. Sci., Pure Appl. Chem., A36A36A36A36, 1561 (1999)
9) J. Pater, G. Weickert, W. Swaaij, J. Appl. Polym. Sci., 87878787, 1421 (2003)
10) , , 81818181, 1024 (1965)
11) Basell Polyolefins, W0 00/63261(2000)
12) Basell Polyolefins, W0 01/57099(2001)
13) Basell Polyolefins, W0 02/30998(2002)
14) J. C. Chadwick, F. P. T. J. van der Burgt, S. Rastogi, V. Busico, R. Cipullo, G. Talarico,
Macromolecules, 37373737, 9722 (2004)
15) G. Cecchin, G. Morini, A. Pelliconi, Macromol. Symp., 173173173173, 195 (2001)
16) , 2004-204071
-
96
2.1.22.1.22.1.22.1.2
PPPP
3
PP
PP
PP
PP.2.1.2-1
31,2)
C-H
(R)(())R
(ROO)(())
R108109 mol-1s-13)ROO
(ROOH) R
(()) ROOH (RO)(HO)
(())ROOH-O-O-3040kcalmol
PP
.2.1.2-2RO
RH
RO2ROORH ROOH RORHOHRH
2RRROO
RH
ROO ROOHR ROOH ROH+R H2O+R
R-R ROOR
()
()() () ()()
()()
.2.1.2-1 PP
-
97
()()
PPPP
.2.1.2-3
.2.1.2-1
(UVA)
PP ROOH
UVA
RROO
(HALS)
CCH3
OCH2CH2
CO
CH2CH2
CO
CH3CH2
+
+
CH3
CH2
.2.1.2-2
Polymer RRRR----HHHH
ROOROOROOROO
RRRROOOO2222
OOOO2222RORORORO
,,etc.
RRRR----HHHH
ROOHROOHROOHROOH HALSHALS
UVAUVA
.2.1.2-3 PP
-
98
.2.1.2-4ROO
ROO12
2ROO
12
>>
>>
.2.1.2-1
HALS
etc.
HALS
etc.
OH
R
ROO ROOH
OH
R
O
R
CH3OH
R
O
R
OH
RCH3
ROOO
R OOR
.2.1.2-4
-
99
HALS
100
.2.1.2-5 2,2,6,6-
4,5)
ROOH
ROOH
ROOH
.2.1.2-6
1/100
6,7)
ROOH
ROOH
PPPP
PP
.2.1.2-7
NR
.2.1.2-5 HALS
P O R
P O R
P O R
P O RO
P O RO
P O R'O
RO
+ R'OOH + R'OH
+ R'OO + R'O
+ R'O +
ROOH
.2.1.2-6
RH R ROO R ROOHO2 RH
RO P3
ROOH
RO P3
O
ROH
AOAO
AOAO
O
HO
RH R ROO R ROOHO2 RH
RO P3
RO P3
ROOH
RO P3
ORO P3
O
ROH
AOAO
AOAO
AOAO
AOAO
OO
HOHO
.2.1.2-7
-
100
ROOROOH ROH
PP
()
()
PP()
PP()
PP
2
8
HALS
9
PP
10%
10)
PP PP
PP
/
100
11,12
/
-
101
()
SPM
-
102
(1)(1)(1)(1)
[]
PP
13)
(
)
[]
(EspecST-120BI)
(MFR)23062.16kgf(JIS K 7210)
PPMFR
MFT-2000 ()
FTIR
4000650cm-1
MCT
ATOS(Aperture Though Optical System)
PP1720cm-1
Gel Permeation Chromatography(GPC)
alliance GPC 2000 (Waters)
P/N WST044218 Styragel HT6E (7.8 x 300mm, 10mm) x 2 (Waters)
P/N WST044218 Styragel HT2 (7.8 x 300mm, 10mm) x 1 (Waters)
145
-
103
o-2,6--t--4-(250ppm) 400ppm1451
(RI)
1.0ml/min
6080100120()GPC
[]
()
()
(.2.1.2(1)-1)
.2.1.2(1)-1
MFR
PPMFRPP
PP
.2.1.2(1)-2 MFR
MFR MFR
MFRMFRMFR
(
) 80 26h
MFR
5g
-
104
()(65h)
.2.1.2(1)-3.2.1.2(1)-465h
1720cm-1
MFR
(MFR 2.0g/10min 3.0g/10min )
(h)
10.0
0 25 75 10050
80
MFR(g/10min)
20.0
30.0
(h)
10.0
0 25 75 10050
80
MFR(g/10min)
20.0
30.0
.2.1.2(1)-2 MFR
.2.1.2(1)-3
-
105
.2.1.2(1)-4
()
.2.1.2(1)-5 GPC
MFR GPC
.2.1.2(1)-5
80 GPC
26hMFR
.2.1(1)-6(90h)
2GPC
(h)
1x103
1x105
1x106
0 25 75 100
2x105
5x105
2x104
5x104
50
80
(Mw )
(h)
1x103
1x105
1x106
0 25 75 100
2x105
5x105
2x104
5x104
50
80
(Mw )
.2.1.2(1)-5
-
106
(.2.1.2(1)-6)
.2.1(1)-7 60120
MFR GPC .2.1.2(1)-1 GPC
GPC
0
1
2
3
4
5
6
17 22 27
min
RI
800
1
2
3
4
5
6
17 22 27
min
RI
80
.2.1.2(1)-6
120
100
80
60
(h)
1x103
1x105
1x106
0 25 75 100
2x105
5x105
2x104
5x104
50
,Mw
120
100
80
60
(h)
1x103
1x105
1x106
0 25 75 100
2x105
5x105
2x104
5x104
50
,Mw
(h)
1x103
1x105
1x106
0 25 75 100
2x105
5x105
2x104
5x104
50
,Mw
.2.1.2(1)-7
-
107
()
()()
(1/T)(.2.1.2(1)-8)
()
Ln(t)=A+(E/R)1/T t : T A : E : R : T :
12060GPC(t)
(40)
.2.1(1)-8120604()()
.2.1.2(1)-1
GPC
MFR
GPC
MFR
-
108
.2.1.2(1)-8
401990h(83)
2
40402
[]
GPC
[]
SPM
()
0
1
2
3
4
5
6
7
2.4 2.6 2.8 3.0 3.2
1/T
ln(1/t)
60
80
100
120
10-3
40
60
80
100
120
1990
180
26
4
0.8
T/oC t/h
3.4
-1
-2 40
0
1
2
3
4
5
6
7
2.4 2.6 2.8 3.0 3.2
1/T
ln(1/t)
60
80
100
120
10-3
40
60
80
100
120
1990
180
26
4
0.8
T/oC t/h
3.4
-1
-2 40
.2.1.2(1)-8
-
109
[]
(60) SPM
GPC
SPM6mm2mm
(80)
( CM1100)(.2.1.2(1)
-1)
20m
-20
= 1720cm-12840cm-1
[]
.2.1.2(1)-2
.2.1.2(1)-?
6mm1.2mm2mm0.4mm
6mm1.2mm2mm0.4mm
6mm1.2mm2mm0.4mm
6mm1.2mm2mm0.4mm
6mm1.2mm2mm0.4mm
6mm1.2mm2mm0.4mm
.2.1.2(1)-1
1x103
1x105
1x106
0 100 300 400
2x105
5x105
2x104
5x104
200
60
(h)
,Mw
1x103
1x105
1x106
0 100 300 400
2x105
5x105
2x104
5x104
200
60
(h)
,Mw
.2.1.2(1)-2
-
110
2mm6mm80
.2.1.2(1)-3.2.1.2(1)-4
[]
0 50 100 150
0.2
0.5
0.3
0.4
0.0
0.1
(h)
80
0 50 100 150
0.2
0.5
0.3
0.4
0.0
0.1
(h)
80
.2.1.2(1)-3 (2mm)
(h)
0 50 100 150
0.2
0.5
0.3
0.4
0.0
0.1
80
(h)
0 50 100 150
0.2
0.5
0.3
0.4
0.0
0.1
80
.2.1.2(1)-4 (6mm)
-
111
[]
()
[]
Nile Bule A(5-amino-9H-benzo(a)phenoxazin-9-ylidene)diethylanmonium chloride20mg
20ml150m 10.0g
1
Nile Bule A 20mg 20ml
10g2530
1
(Nile Bule A/) 1mg/ml5mg/ml
2550
1103060
3-(3',5'--t--4'-)-N-(AO-50) 3-(3,5--t--4-
-
112
)-(AO-50(Me))3-(3',5'--t--4'-)-(AO-50(iso-Octyl))[-3-(3',5'--t--4'--)](AO-60) 4
200mg 80ml
TEM V-1000N100g(
1h)
100ml4h
()
100ml100ml4h
(2)12
8024h
(100)
= 1720cm-12840cm-1
[]
.2.1.2(1)-1
.2.1.2(1)-1
-
113
.2.1.2(1)-2.2.1.2(1)-3
.2.1.2(1)-2
.2.1.2(1)-3
30
30
()
.2.1.2(1)-4
0min 1min 10min 30min 60min
1mg/ml25
0min 1min 10min 30min 60min
1mg/ml25
.2.1.2(1)-2
0min 1min 10min 30min 60min
1mg/ml25
5mg/ml25
5mg/ml50
0min 1min 10min 30min 60min
0min 1min 10min 30min 60min
0min 1min 10min 30min 60min
1mg/ml25
5mg/ml25
5mg/ml50
0min 1min 10min 30min 60min
0min 1min 10min 30min 60min
.2.1.2(1)-3
-
114
3-(3',5'--t--4'-)AO-50 type
3-(3',5'--t--4'-)4AO-60AO-50 type
21.314)
.2.1.2(1)-5AO-50 typeAO-50
type()AO-50 type()AO-50
AO-50 type(Me)
AO-50 type(iso-Octyl)
AO-50 AO-60
4
10
6
8
0
2
AO(mg)
6.06.1
7.2
3.8
AO-50 type(Me)
AO-50 type(iso-Octyl)
AO-50 AO-60
4
10
6
8
0
2
AO(mg)
6.06.1
7.2
3.8
.2.1.2(1)-5
O
OCH3HO
AO-50type(Me)
292.4
O
O
HO
AO-60
4
1178.0
O
OC18H37HO
AO-50
530.9 21.3 4.8
O
OC8H17HO
AO-50 type(iso-Octyl)
390.6
O
OCH3HO
AO-50type(Me)
292.4
O
O
HO
AO-60
4
1178.0
O
OC18H37HO
AO-50
530.9 21.3 4.8
O
OC8H17HO
AO-50 type(iso-Octyl)
390.6
.2.1.2(1)-4
-
115
(>>)AO-60
AO-60AO-50 type
AO-50
.2.1.2(1)-6.2.1.2(1)-7AO-50AO-60
AO-60AO-50
AO-50AO-60AO-50
AO-50AO-60
(h)
0.4
1.0
0 50 150 200
0.6
0.8
0.0
0.2
100
100
(h)
0.4
1.0
0 50 150 200
0.6
0.8
0.0
0.2
100
100
.2.1.2(1)-6 AO-50
100
(h)
0.4
1.0
0 50 150 200
0.6
0.8
0.0
0.2
100
100
(h)
0.4
1.0
0 50 150 200
0.6
0.8
0.0
0.2
100
.2.1.2(1)-7 AO-60
-
116
[]
AO-50
AO-50
-
117
(2)(2)(2)(2)
2
2
SPM
8-12,15,16)
8-10,15)/
11,16)
12)
PP
PP
SPM
-
118
[]
.2.1.2(1)
[]
AO-50 200mg80ml100g
1h
150m3.0g AO-50/(1.2 wt%)
( PET No.50A )
100ml 4h
100ml
100ml 4h
24hHPLC
(10080)GPC
[]
2.1.2(1) AO-50
.2.1.2(2)-1
-
119
(h)
1x103
1x105
1x106
0 20 60 80
2x105
5x105
2x104
5x104
40
100
, M w
(h)
1x103
1x105
1x106
0 20 60 80
2x105
5x105
2x104
5x104
40
100
, M w
240ppm409.0
1000ppm406.6
/402
.2.1.2(2)-1
205kWh/MT
250kWh/MT(35wt.%3080
)
80kWh/MT( 5wt.%30 80
)SPM
.2.1.2(2)-1
.2.1.2(2)-1
150
80
250
(kWh/MT)
205
80
250
(kWh/MT)
-
120
[]
SPM
[]
2.1.2(1)
(DEHA)DEHA
[]
17) 2.6 wt%
(1 dm3) 0.4 dm3
TEAL 5 cm3
(DCPDMS)(0.1 moldm-3) 5 cm3
(1.9 mgcm-3) 2.5 cm3
0.1 MPaG()3550300 s-110 min
0.15 dm3(
)0.5 MPaG70600 s-1
0.5 MPaG 1h
5cm3
DEHA
(DEHA)300ml500ml(3cm
)100ml/DEHADEHA
( 50g) 1
DEHA
-
121
(100)GPC
[]
DEHA .2.1.2(2)-1 DEHA
DEHA 10000ppm409.5
10000ppm DEHA
9.5(1000ppm406.6)
DEHA
4kWh/MT( 5wt%
)
[]
DEHA
(h)
1x103
1x105
1x106
0 100 300 400
2x105
5x105
2x104
5x104
200
80
, M w
(h)
1x103
1x105
1x106
0 100 300 400
2x105
5x105
2x104
5x104
200
80
, M w
.2.1.2(2)-1
-
122
a.
[]
Retrofitable
/
PP
Ti
MgCl2TiTiCl4(
)
Ti Ti 1.5
3.0%
PP
Ti
Ti
18)PP
PPPP/
(TEAL)
2,6--t--4-(BHT)
19-23)
TEAL
TEAL Et2AlOHO TEAL Et2AlOHO
.2.1.2(2)-1 TEAL
-
123
()
24)
()TEAL
[]
AO-330(1,3,5--2,4,6-(3',5'--t--4'-)) 0.1g() 20
cm3 TEAL (1moldm-3) 0.4 cm3
1H-NMR(R-1900 FT-NMR)
17) 2.6 wt%
(1 dm3)
0.4 dm3 TEAL 5cm3 DCPDMS
(0.1 moldm-3) 5cm3 (1.9 mg
cm-3) 2.5cm3AO-330
40mg
0.1MPaG() 3550
300 s-1 10 min
0.15dm3() 0.5 MPaG
70 600 s-1 0.5 MPaG
1h5cm3
6024h
PP
PP GPC(Waters 2000135 o-) meso pentad [mmmm] 13C-NMR(JEOL EX-400 FT-NMR130
o-)Tm(Perkin Elmer Diamond DSC10min-1)
(100)GPC
-
124
()(Yellowness indexY.I.)
[]
AO-330
AO-330.2.1.2(2)-2
AO-330TEAL
AO-330
TEALTEAL AO-330
1H-NMR.2.1.2(2)-3
AO-330 TEAL (4.93ppm)
AO-330 TEAL
.2.1.2(2)-1
PP
OH
HO
OH
OH
HO
OH
.2.1.2(2)-2
ADK STAB AO-330
AO-330 AO-330TEALAO-330 AO-330TEAL
.2.1.2(2)-3
-
125
AO-330
8000 g-PPg-cat-1 (PP) 85%
AO-330 TEAL
TEAL
/AO-330
AO-330
Tm[mmmm] AO-330 AO-330
AO-330
AO-330
9200 g-PPg-cat-1
/TmPPI.I.[mmmm]
AO-3301020wt-ppm
.2.1.2(2)-4100
24 h 10 1AO-330750hAO-330
(Yellowness
indexY.I.)Y.I.=5.375hY.I.=15.2AO-330
Y.I.
.2.1.2(2)-5
.2.1.2(2)-1 AO-330
a)
AO-330
AO-330
g-PP/g-cat.
940080009200
Mw10-5 b)
4.04.24.1
Mw/Mn b)
5.14.85.1
I.I. c)
wt%
98.597.297.4
[mmmm] d)
%
97.197.396.5
Tm e)
163.7163.4163.2
AO-330
AO-330
g-PP/g-cat.
940080009200
Mw10-5 b)
4.04.24.1
Mw/Mn b)
5.14.85.1
I.I. c)
wt%
98.597.297.4
[mmmm] d)
%
97.197.396.5
Tm e)
163.7163.4163.2
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
-
126
AO-330230
25)
AO-330AO-330
.2.1.2(2)-2
(h)
1x103
1x105
1x106
0 500 1000 1500
2x105
5x105
2x104
5x104
100
, M w
(h)
1x103
1x105
1x106
0 500 1000 1500
2x105
5x105
2x104
5x104
100
, M w
.2.1.2(2)-4 AO-330
.2.1.2(2)-2
CH2
H2CCH2
OHt-But-Bu
t-Bu
t-But-Bu
HOt-Bu
OH
CH
HCCH
Ot-But-Bu
t-Bu
t-But-Bu
Ot-Bu
O
230, Air
.2.1.2(2)-5 AO-330
-
127
[]
(AO-330)
TEAL
PP
b.
[]
PP
//
()
AO-330
[]
AO-1
-
128
3-(3',5'--t--4'-) 60.1g 66.3g 0.5 dm3 60(28 wt%) 4.6cm3
1506h 0.2dm3(85wt%) 1.9cm3
79.5g73wt%99wt%
PP (
250)(2mm)(150)
ADK STAB 2112Ca-St
VG-800-TAO-20AO-30AO-40AO-50AO-330(
)Irganox 1098()0.5g
TEAL (1moldm-3) 2.5cm3 AO-1
AO-20((3,5--t--4-))AO-30(1,1,3-(2'--4'--5'-t-))AO-40(4,4- (6-t--3- ))AO-50AO-330Irganox 1098 20mg () 20cm3 TEAL (1moldm-3
)1.5cm3 AO-1 TEAL 1.5cm3
5cm3GPC(GC) 1H-NMR
AO-1 0.1 g() 20 cm3TEAL(1mol
dm-3 ) 0.6 cm3
1H-NMR(R-1900 FT-NMR)
17) 2.6 wt%
(1 dm3)
0.4 dm3 TEAL 5cm3 DCPDMS
(0.1 moldm-3) 5cm3 (1.9 mg
cm-3) 2.5cm3AO-1
-
129
40mg
0.1MPaG() 3550
300 s-1 10 min
0.15dm3() 0.5 MPaG
70 600 s-1 0.5 MPaG
1h5cm3
6024h
PP
PP GPC(Waters 2000145 o-) meso pentad [mmmm] 13C-NMR(JEOL EX-400 FT-NMR130
o-)Tm(Perkin Elmer Diamond DSC10min-1)
(100)GPC
()(Yellowness indexY.I.)
[]
.2.1.2(2)-6
N
N
N
O
O OHO
OH
OH
HO
OH
OH HO OH
HO
OC18H37
O
HO
O
O
4
HO
OH
OH
HO
NH
O OHHN
O
ADK STAB AO-20
ADK STAB AO-30
ADK STAB AO-40
ADK STAB AO-50
ADK STAB AO-60
ADK STAB AO-330
Irganox 1098
N
N
N
O
O OHO
OH
OH
HO
OH
OH HO OH
HO
OC18H37
O
HO
O
O
4
HO
OH
OH
HO
NH
O OHHN
O
ADK STAB AO-20
ADK STAB AO-30
ADK STAB AO-40
ADK STAB AO-50
ADK STAB AO-60
ADK STAB AO-330
Irganox 1098
.2.1.2(2)-6
-
130
AO-20 PPPE
AO-30AO-40
ABS
AO-40 PP
AO-50AO-60
Irganox
1098AO-330
TEAL/
.2.1.2(2)-3
AO-50AO-330TEAL/AO-20
AO-30AO-40IRGANOX 1098
AO-50
TEAL
AO-330
AO-20AO-30AO-40AO-60Irganox 1098AO-50AO-330
AO-20
AO-30AO-40TEAL
AO-30TEAL
AO-60Irganox1098
TEAL/
.2.1.2(2)-4
.2.1.2(2)-3 TEAL/ a)
a)1.0mol/L TEAL/hexane(25wt%), =, =
a)
AO-20 AO-30 AO-40 Irg 1098
AO-50 AO-330
AO-60
a)1.0mol/L TEAL/hexane(25wt%), =, =
a)
AO-20 AO-30 AO-40 Irg 1098
AO-50 AO-330
AO-60
-
131
AO-20 AO-50 AO-60
AO-20 AO-50 AO-60
TEAL
AO-30AO-40Irganox1098AO-330
AO-30AO-40 AO-330
Irganox1098
.2.1.2(2)-7
1)2)
3)
3-(3',5'--t--4'-)1
AO-50
(>>
>)
.2.1.2(2)-4 TEAL/a)
a)
AO-20 AO-30 AO-40 Irg 1098AO-50 AO-330AO-60
a)1.0mol/L TEAL/hexane(25wt%), =, =
a)
AO-20 AO-30 AO-40 Irg 1098AO-50 AO-330AO-60
a)1.0mol/L TEAL/hexane(25wt%), =, =
HOR2
R1 X R3
HOR2
R1 X R3
.2.1.2(2)-7
-
132
Irganox1098
3-(3',5'--t--4'-)-N-
(AO-1).2.1.2(2)-8AO-1
(
)PP
AO-50
3-(3',5'--t--4'-)1
(AO-1)
AO-1.2.1.2(2)-5
AO-1
AO-1
AO-1
PP
(2mm)150
()
.2.1.2(2)-9
O
NH
HO
C18H37
.2.1.2(2)-8 AO-1
.2.1.2(2)-5 TEAL/AO-1a)
a)
AO-1
a)1.0mol/L TEAL/hexane(25wt%), =, =
a) a)
AO-1
a)1.0mol/L TEAL/hexane(25wt%), =, =
a)
-
133
AO-1AO-330AO-50
AO-1
AO-1
AO-1
AO-1 TEAL 1H-NMR
AO-1TEAL
AO-13TEAL
1H-NMR .2.1.2(2)-10 1H-NMR
5.04 ppm 5.30 ppmTEAL
TEAL
1H-NMR
AO-1
AO-1 AO-1TEALAO-1 AO-1TEAL
.2.1.2(2)-10
non AO-330
200
500
300
400
0
100
(h)
AO-50 AO-1non AO-330
200
500
300
400
0
100
(h)
AO-50 AO-1
.2.1.2(2)-9 PP
-
134
/
AO-1.2.1.2(2)-6
AO-17100 g-PP/g-catAO-330
AO-330
0.1wt% A-330AO-1
40 mg(
1000 ppm)AO-1
/ AO-1 AO-330
AO-1
PP /[mmmm] Tm PP
[mmmm] AO-330 AO-1
AO-330
AO-1
AO-1
.2.1.2(2)-11AO-1
1030 wt-ppm
.2.1.2(2)-6 AO-1a)
NonAO-1
AO-1
g-PP/g-cat.
940071009100
Mw10-5 b)
4.03.94.0
Mw/Mn b)
5.14.85.1
I.I. c)
wt%
98.598.198.4
[mmmm] d)
%
97.197.097.2
Tm e)
163.7163.6163.4
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
NonAO-1
AO-1
g-PP/g-cat.
940071009100
Mw10-5 b)
4.03.94.0
Mw/Mn b)
5.14.85.1
I.I. c)
wt%
98.598.198.4
[mmmm] d)
%
97.197.097.2
Tm e)
163.7163.6163.4
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
-
135
AO-1 1000h AO-330PP(.2.1.2(2)-4)AO-1PP
(1000ppm)1.5(750h1000h)AO-1
Y.I.=2.6(AO-330: Y.I.=5.3)100
75 hY.I.=6.5(AO-330: Y.I.=15.2)AO-330
AO-1
[]
AO-1(3-(3',5'--t--4'-)-N-)
PP
c.
[]
PP
(h)
0 500 1000 1500
1x103
1x105
1x106
2x105
5x105
2x104
5x104
, M w
100
(h)
0 500 1000 1500
1x103
1x105
1x106
2x105
5x105
2x104
5x104
, M w
100
.2.1.2(2)-11 AO-1
-
136
2.1.2(2)a
/
PP
MFR
[]
AO-1 0.1 g() 20 cm3TEAL(1mol
dm-3 ) 0.6 cm3
1H-NMR(R-1900 FT-NMR)
ADK STAB 2112ADK STAB HP-10ADK STAB PEP-36 0.1g 20 cm3TEAL
TEAL(1moldm-3) 0.4 cm3
(CaSt) 0.1g () 20 cm3
TEAL(1moldm-3) 0.4 cm3
17) 2.6 wt%
(1 dm3)
0.4 dm3TEAL 5cm3DCPDMS(0.1
moldm-3) 5cm3(1.9
mgcm-3) 2.5cm3AO-1
40mg
20mg 12mg
0.1MPaG()
3550 300 s-1 10 min
0.15dm3()0.5 MPaG
70 600 s-1 0.5 MPaG
1h5cm3
-
137
6024h
PP
PP GPC(Waters 2000145 o-) meso pentad [mmmm] 13C-NMR(JEOL EX-400 FT-NMR130
o-)Tm(Perkin Elmer Diamond DSC10min-1)
230
23062.16kgf
MFR
[]
.2.1.2(2)-12
2112
PEP-36HP-10
TEAL
2112TEAL
.2.1.2(2)-7PP
O PO
O
OP
OOO PO
O O
O
P O
ADK STAB 2112 ADK STAB PEP-36 ADK STAB HP-10
C8H17
.2.1.2(2)-12
-
138
2112
2112
AO-1AO-1
.2.1.2(2)
-8
2112HP-10PEP-36 AO-1
(CaSt)
AO-1 2112 CaSt
.2.1.2(2)-9
.2.1.2(2)-7 a)
2112
2112+TEAL
g-PP/g-cat.
940095009500
Mw10-5 b)
4.04.04.0
Mw/Mn b)
5.15.15.1
I.I. c)
wt%
98.598.197.9
[mmmm] d)
%
97.197.097.2
Tm e)
163.7163.6163.2
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
2112
2112+TEAL
g-PP/g-cat.
940095009500
Mw10-5 b)
4.04.04.0
Mw/Mn b)
5.15.15.1
I.I. c)
wt%
98.598.197.9
[mmmm] d)
%
97.197.097.2
Tm e)
163.7163.6163.2
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
.2.1.2(2)-8 AO-1
a)
AO-1+2112AO-1+HP-10AO-1+PEP-36
g-PP/g-cat.
9400990094009400
Mw10-5 b)
4.04.04.03.8
Mw/Mn b)
5.14.94.84.7
I.I. c)
wt%
98.598.098.297.9
[mmmm] d)
%
97.197.297.397.0
Tm e)
163.7163.4163.3163.0
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
AO-1+2112AO-1+HP-10AO-1+PEP-36
g-PP/g-cat.
9400990094009400
Mw10-5 b)
4.04.04.03.8
Mw/Mn b)
5.14.94.84.7
I.I. c)
wt%
98.598.098.297.9
[mmmm] d)
%
97.197.297.397.0
Tm e)
163.7163.4163.3163.0
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
-
139
CaSt
.2.1.2(2)-13
()()(
)
MFR
AO-1AO-1/2112
AO-1/2112/CaSt
[]
//AO-1
.2.1.2(2)-9 AO-1
a)
AO-1+2112+CaSt
g-PP/g-cat.
94009800
Mw10-5 b)
4.03.8
Mw/Mn b)
5.15.0
I.I. c)
wt%
98.598.1
[mmmm] d)
%
97.197.4
Tm e)
163.7163.1
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
AO-1+2112+CaSt
g-PP/g-cat.
94009800
Mw10-5 b)
4.03.8
Mw/Mn b)
5.15.0
I.I. c)
wt%
98.598.1
[mmmm] d)
%
97.197.4
Tm e)
163.7163.1
a) , Tp=70, Pp=5MPaG, 1h, b) GPC, c) (6h), d) (13C-NMR), e) (DSC)
0
10
20
30
40
50
0 1 2 3 4
MFR (g/10m
in)
AO-1
AO-1+2112
AO-1+2112+CaSt
0 1 3 42
20
50
30
40
0
10
MFR(g/10min)
2300
10
20
30
40
50
0 1 2 3 4
MFR (g/10m
in)
AO-1
AO-1+2112
AO-1+2112+CaSt
0 1 3 42
20
50
30
40
0
10
MFR(g/10min)
230
.2.1.2(2)-13
-
140
(ADK Stab 2112)/CaSt
PP
d.
[]
/
/CaStSPM
()
SPM
SPM
[]
: (MgCl2Ti)
:
:
: 2L
500gMFRH2
701h
Al/Si/Ti=250/4/1
AO-1
(120)GPC
SPM
.2.1.2(2)-14
SPM
-
141
.2.1.2(2)-14
[]
.2.1.2(2)-15
.2.1.2(2)-10
AO-1
TEALAl/Si
3.0105
5.0105
6.0105
4.0105
, M w
3.0105
5.0105
6.0105
4.0105
, M w
.2.1.2(2)-15
BOPP
BOPP
NNNNNNNN22222222
SPMSPM
BOPP
BOPP BOPP
NNNNNNNN22222222
SPMSPM
-
142
()
TEAL
TEAL/
()
AO-1 (120)
.2.1.2(2)-16
60wt-ppm50(4010)560wt-ppm700(40
100 )
3 27000g-PP/g-cat.
9000g-PP/g-cat.1/3
60wt-ppm 10
560wt-ppm
AO-1(560ppm).2.1.2(2)
-17
.2.1.2(2)-10
AO-1(60ppm)AO-1(560ppm)
kg-PP/g-cat.
30.428.427.8
I.I.
wt%
96.796.195.9
MFR
g/10min
3.33.13.7
AO-1(60ppm)AO-1(560ppm)
kg-PP/g-cat.
30.428.427.8
I.I.
wt%
96.796.195.9
MFR
g/10min
3.33.13.7
1x103
1x105
1x106
0 250 750 1000
2x105
5x105
2x104
5x104
500
120
(560ppm)
(60ppm)
(h)
, M w
1x103
1x105
1x106
0 250 750 1000
2x105
5x105
2x104
5x104
500
120
(560ppm)
(60ppm)
(h)
, M w
.2.1.2(2)-16
-
143
.2.1.2(2)-18
AO-160ppm
560ppm ()
[]
2
(40100)
AO-1 560ppm
, Mw
(N2)
3.0105
5.0105
6.0105
4.0105
, Mw
(N2)
3.0105
5.0105
6.0105
4.0105
.2.1.2(2)-17
(N2)
3.0105
5.0105
6.0105
4.0105
(60ppm)
(560ppm)
, M w
(N2)
3.0105
5.0105
6.0105
4.0105
(60ppm)
(560ppm)
, M w
.2.1.2(2)-18
-
144
[]
PP
[]
100GPC
[]
(100).2.1.2(2)-1
100
2000h
2
PP
[]
SPM
2
(h)
1x103
1x105
1x106
0 1000 2000 3000
2x105
5x105
2x104
5x104
, M w
(h)
1x103
1x105
1x106
0 1000 2000 3000
2x105
5x105
2x104
5x104
, M w
.2.1.2(2)-1
-
145
(3)(3)(3)(3)
PPPP
3
(MB)
[]
PP
11,26-27)Basell 14mm
a.
.2.1.2(3)-1
-
146
.2.1.2(3)-1
PP
(PE)
PE
[]
PENL100PE110
PP PE
FM150J
120
GMGMZ50-32
190/200/200/200/200/200/200 () 60rpm 50kg/h
SFA-20
2101mm
KARO-
589015825m
ISK710525m
NDH2000
807
-
147
=
NDH2000
(DN600)
ASTMD189421130250mm120120mm
n=5(403)
200
(2001)
[]
PEBOPP.2.1.2(3)-1PE
PE
PE3%
.2.1.2(3)-1 PEBOPP
PE
1%
PE
3%
% 0.36 0.49 0.48
% 0.42 0.19 0.11
0.75 0.77 0.73
0.52 0.53 0.53
b.
[]
211
PEPP2
FM20C/I
FD20C/K/I
A/B/A/B900/500/200/500 (ppm)
A(9000ppm)
-
148
.2.1.2(3)-2
)
).2.1.2(3)-2
)PE120
)12030
)2050
)5015
.2.1.2(3)-2
PP
(rpm)
1 107
2 340
3
4
PE 1%
5
A
(2.0mm)
6 PE 1%
7
A
(0.6mm)
107
1.
2.
3.
4.
5. 7.
6.
AB
ABICP-AES
A1
CEM MarsX
-
149
Hewlett Packard1100 (Waters -BONDSPHERE,C4)
SX-102 (FD)
ICP-AES SPS1200A
Hewlett Packard6890
TEM
TEM
TEM H-7000 10,00030,000
JIS K0069
ROTEX GRADEX2000
JIS K6721
MT-1001
MT-1001
80MFR
[]
.2.1.2(3)-3
14
5
PP
TEM.2.1.2.(3)-2
m
TEM
-
150
.2.1.2(3)-3
(ppm)
PP
A
B
A(*1)
B
A
1 430 290 790 350
2 740 440 660 290
3 810 490 580 260
4
PE 1%
930 670 670 300 8050
(*2)
5
A
860 510 790 330 (*3)
6 PE 1% 570 430 850 410
7
A 530 390 850 330 (*4)
900 500 200 500 (9000)
*1 AMgMg
*2
*3
*4
.2.1.2(3)-2 PETEM
(PE)
-
151
PE
PE
PE
()
.2.1.2(3)-3
A A
F122AB
AMFR
2
PE
.2.1.2(3)-3
c.
[]
TEM
A(A(A(A())))
BBBBAAAA
0
20
40
60
80
100
120
0 24 48 72 96 120 144 168
((((hr)hr)hr)hr)
MFR(g/10min.)
MFR(g/10min.)
MFR(g/10min.)
MFR(g/10min.)
((((F122)F122)F122)F122)
////
80808080,,,,AirAirAirAir230230230230,10,10,10,10KgKgKgKg
A(A(A(A())))
BBBBAAAA
0
20
40
60
80
100
120
0 24 48 72 96 120 144 168
((((hr)hr)hr)hr)
MFR(g/10min.)
MFR(g/10min.)
MFR(g/10min.)
MFR(g/10min.)
((((F122)F122)F122)F122)
////
80808080,,,,AirAirAirAir230230230230,10,10,10,10KgKgKgKg
-
152
PE PP
PE
BOPP
PE
[]
.2.1.2(3)-4
) 40Kg
)
2025m/s
)
) ,
1mm
1mm
A1mm
50m
.2.1.2(3)-4
[]
.2.1.2.(3)-4
AirAir
L=30mL=30m
L=2.7mL=2.7m
AirAir
L=30mL=30m
L=2.7mL=2.7m
-
153
0.8g0.5g
A8.35.15.0g
A/0.2g0.6g
(PE)A10
PEA/
PP
PE
2.1.2(3)-4
()
(m/s)
(g)
1 19.8 8.3
2 25.5 5.1 A
3 17.7 5.0
1 19.8 0.2 A/
2 19.8 0.6
1 25.0 0.8 (F122)
2 26.7 0.5
140kg
A1mm
A/a)-2
A/B/A/B900/500/200/500 (ppm)
PEHIWAX NL100 1%
d.
[]
PE
PEPP
-
154
[]
.2.1.2(3)-5
.2.1.2(3)-5
PEPE
PE
AA/B=900/500ppm
.2.1.2.(3)-5PP4
.2.1.2(3)-5
Run PP() (*) (sec)
1 80 45
2 80 90
3 120 45
4 120 90
(*) 80PPPP
120PE
20L8L45,90sec
(80,120)
(120
(801206040)
20L8L45,90sec
(80,120)
(120
(801206040)
-
155
)107rpm
)(80120)
)120PE
)
)1,3,5,7,9min.
)
)60403
[]
5min.TEM.2.1.2.(3)-6PP
23mPP
.2.1.2.(3)-6
.2.1.2.(3)-7.2.1.2.(3)-7
.2.1.2.(3)-8
Carr
28)
.2.1.2(3)-6 TEM
1m
PEPEPEPE
PPPPPPPP
-
156
2.1.2(3)-6 HPCL
A(wt%) B(wt%)
Run.1 5min. 0.045 0.042
Run.1 9min. 0.030 0.031
Run.3 5min. 0.068 0.023
Run3. 9min. 0.062 0.021
A/B0.09/0.05 (wt%)
2.1.2(3)-7
.2.1.2(3)-7 5
Run.1 Run.2 Run.3 Run.4
(m) 1,970 2,170 2,080 2,080 1,990
(g/cc) 0.47 0.46 0.46 0.47 0.47
0
5
10
15
20
25
30
>3350 >2800 >2360 >2000 >1700 >1180 >850 >355 >180 >106
-
157
2.1.2(3)-8
Run.1 Run.2 Blank
8060 8040 8060 8040
91 88 90 90 90 88 90
PE
.2.1.2.(3)-7
PE
Run.1PE
PPPE120
Run.3
[]
PE
[]
1
-
158
[]
.2.1.2(3)-1
.2.1.2(3)-1
A12
A
) 1A2g2A4g
)
) 25MPa
) 25MPat=0(
t=010)
)
) 2
) ))
.2.1.2(3)-1
1 2
CO2
CO2
-
159
.2.1.2(3)-1
1 2 3 4
() 70 70 100 100
(MPa) 25 25 25 25
(min.) 60 30 60 30
(TOF-SIMS)
ULVAC-PHITRIT2
69Ga
15kV
0V()
200m
[]
.2.1.2.(3)-2
(100)
(60min.)
A
34
.2.1.2(3)-2
1 2 3 4
(g) 4.011 4.035 4.053 4.035
(g) 4.155 4.068 4.350 4.252
(%) 3.46 0.81 6.82 5.10
-
160
TOF-SIMS
.2.1.2.(3)-2TOF-SIMSA
AC15H23O+O-A
.2.1.2(3)-2 TOF-SIMS
[]
A
A
A
(MB)
PPBOPPPP
BOPPPP
-
161
40100
100 960
.2.1.2(3)-1
.2.1.2(3)-1 100
MB2
PP PP
MB
[]
MB(*)
MB
MB
*)SPM
MBPP%
100000
1000000
0 500 1000
(h)
-
162
SPM
()
SPM
MBBOPP
MB
BOPP
(*)
-FE
-
(*)BOPP
-BOPPFE
-
[]
()SPM(TEM-48DS)(GP)BOPP
TEM-48DS
2.1.2(3)-2
PP
FE24
-
163
.2.1.2(3)-2
PP
A
B
BF113G
)A+MB+ 200kg/h
)A+MB+ (180kg/h)
)B+MB+ 200kg/h
)B+MB+ (180kg/h)
)B+MB (180kg/h)
)B+MB+ (180kg/h)
MB
MB9wt%1,700ppm10wt%
BOPP/BOPP/ (10/80/10)
SPM
PP
MB
MB
PP
SPM
PP
MB
SPM
PP
MB
SPM
PP
MB
MB
PP
MB
PP
-
164
SPM(TEM-48DS)
C1/C2/C3/C4/C5/C6/C7 165/220/240/240/240/240/250
GP H1/1-ML1/GP/2-ML1/2-ML2/2-ML3 250/250/250/250/250/250
GP
30mgo-20ml0.45mGPC
Alliance GPC 2000
Empower
TSKgel GMH6-HT2 + TSKgel GMH6-HTL2
140
o-
1.0ml/min
500l
[] .2.1.2(3)-1B+MB
B+MB+MB
AMB
-
165
.2.1.2(3)-1
(kg/h)
371,000
368,000
368,000
377,000
369,000
356,000
357,000
355,000
352,000
BMB
354,000
363,000
348,000
349,000
347,000
339,000
349,000
344,000
345,000
344,000
343,000
345,000
344,000
BMB
343,000
345,000
[]
MB
-
166
(4)(4)(4)(4)
[]
PPBOPP
1
[]
PP
BF113G MFR=3g/10min.
ABA
SFA-20
210 (1mm)
KARO-
5890157 (25m)
10m/min.
GPCWatersGPC2000
145
o-BHT(250ppm)
400ppm1451
1.0ml/min.
BOPP
.2.1.2(4)-1
GPC
BOPP
-
167
.1.2.1(4)-1
.2.1.2(4)-1
.2.1.2(4)-1
(*)
100
(10) 10
(35) 35
(100) 100
*)100
[]
.2.1.2(4)-2
()()BOPP
(10)
(35)(100)BOPP
-
168
.2.1.2(4)-2
()()
(35)BOPP
[]
BOPP
PP
SPMBOPP
4.0E+05
4.5E+05
5.0E+05
5.5E+05
BOPP
()
()(10)
(35)(100)
-
169
(5)(5)(5)(5)
1800ppm
PE
MBBOPP
PP
-
170
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