Þ æ ?E ĵ 2 - yamakin-gold.co.jp · /feµÂ¶ l± B3e 4 : sI E /ie ... =H\Hl P 2 1 ¶ü
11
高分子技術レポート 高分子技術レポート 歯科材料開発部 歯科材料モノマーの重合ーラジカル重合の基礎 歯科材料モノマーの重合ーラジカル重合の基礎 Vol. 1 Vol. 1 匠から科学へ、そして医学への融合
Transcript of Þ æ ?E ĵ 2 - yamakin-gold.co.jp · /feµÂ¶ l± B3e 4 : sI E /ie ... =H\Hl P 2 1 ¶ü
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Vol.1Vol.1
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1.
2.
3.
4.
5.
6.
7.
8.
9.
2
2
4
5
10
10
11
12
15
-
2 3
1.
1,2)
2
2.
1) 1000
10,000
10,000 100100
90%100
(0.90)1000.00003
11)
10210 103 104 105 106 107
(g/mol)
2
( (
1
2
3
5
10
20
30
100
1000
30
58
86
143
282
562
842
2802
28001
-172
-135
-95
-30
36
81
99
106
110
-88.6
-0.5
69
174
343
241/0.3 mmHg
1 ( ( CH2CH2 )n)1)
-
4 5
50%
100%
PET
(Mn) (Mw) Mn
( ) (GPC) Mw
Mw/Mn
Mw/Mn
3.
CCCX X
O Cl
4.
0.1 mol%5060
2,2- AIBN2,2-MAIB
BPO100 -t -
CQ 2,4,6 - BPO
3
CH2 CH CH2 CH
CO2R
CH2 CH
OCOCH3
CH2 CH
Cl
CH2 C
CO2R
CH3
4
(Initiation)
2
+
(Propagation)
(P )
n
(Chain transfer)
P + +
(Termination)
+ CCH
-
6 7
(kd)
3)
50%
t1/2ln 2/kd 10 10 AIBN 65MAIB 66BPO
78 -t - 125
CH2 CXY
X Y
4)
kptI
Rif
Ri 2fkd[ I ]
Rp kp[M]
[P]
Rp kp[M][P]
CH2
Rt kt
Rt kt [P]2
6
7()
5
CH3 CH3
CH3 CH3
C CN N
CN CN
CH3 CH3
CH3 CH3
CO2CH3 CO2CH3
C CN N
CH3 CH3
CH3 CH3
CH3 CH3
C CO O
O
O
2,2-(AIBN)
(BPO)
(CQ)
2,2-(MAIB)
2,4,6-
C
O O
CO O
CH3 C OP
OCH3
CH3
t
CH2
CH2
CH2 CH2
CH2C C
CH2C
X
Y
C
X
Y
+
X
Y
X
Y
C
X
Y
C
X
Y
X, Y
7A
2.6A
CH2 CH
n
R +
2P
2R
R-M P
kd
kp
k t
-
8 9
Rp kdkp
kt kd 3)kp kt Rp [M]
[P] kp kt [P]
RiRt [P]
[P] (Ri/kt) 0.5
Ri mol/Ls kt L/mols [(mol/Ls)/(L/mols)]0.5
mol/L [P] [P]
Rp kp[M](Ri/kt) 0.5
[M] RiRp kp/kt0.5 Rp 1/2
Rp [M]
[I] 0.5
kp kt
kt
Rp
Rp kp[M](Ri/kt) 0.5 kp[M]( fIabs/kt) 0.5
Iabs fIabs
Ri
Rp Pn
Pn
PnRp/RtRp/Ri kp2[M]2/ktRp
Pn Pn
Pn+
x x x0
Pn [M] Ri
1/Pn Rp
0
kp/kt0.5 [M]
ln[M]0/[M]t kp(Ri/kt) 0.5t
t [M] ln[M]0/
[M]t t kpRi/kt0.5 t
kp Ri/kt0.5 (Ri/kt) 0.5
kt
8( p)(A)(B) n p(C)R P R
(A) (B) (C)
0 00 [ I ]0.5 [M] pR
pR
pR
n1/P
-
10 11
5.
RSH
RSH RS RSP+M
RS
ktr 1/Pn
Tktr[T] Pn
1/Pn 1/Pno + ktr[T]/kp[M] 1/Pn0 + Ctr[T]/[M]10
Pn0 Ctrktr/kp
(RSH) Ctr 10-1 101
10-5 Ctr > 1 PnCtr < 1Pn
Ctr 3)
6.
5)
pppm
7.
RiRpRt Pn 10Rp
FT-NIR H-CC C-H
6150 cm-1
10
FT-NIR 6) 1H-NMR
10706)
0
6400 6000 5600 5200 4800 4400
90
40
H-C =
(%)
(cm-1)
P + RSH
RS + M
PH + RS
P
9
C6H5 CH2
N N
N N
C6H5
C6H5
OH
OCH3
p-
OH
OH
N
O
2,2,6,6--1- (TEMPO)
N
O
OH
4--2,2,6,6--1-
-
12 13
ESR -
(CH2C(CH2CO2C4H9)CO2C4H9) 60 kp5.3 L/mols kt8.5x102 L/mols
10)CH2CXY XCHCHX
((CH3)2CHO2CCHCHCO2CH(CH3)2-trans) 30 kp0.31 L/mols kt0.84
L/mols 11)
10-4 mol/L
kp kp > Rt Rp/Rt ()
12
12,13)
13XCO2R-
kp kt
8.
Rp kp/kt0.5
ESR
ESR 11 7)100
CHCH2 C6H5
10-8
10-7 mol/L
kp kt 70
kp480 L/mols kt1.70x107 L/mols8)
ESR 9)
11
(~CH2CH( )C6H5)ESR(A) (B) 7)
10G
(A)
(B)
12t-60()(PRR) (MCR)ESR(A)(B)13)
MCR
PRR
20G
(A)
(B)
a-H 28.0G
a-H 10.3G
a-H 18.1G
a-H 28.3G
-
14 15
ESR PLP
14
L011 14)
L0i ikp[M]t011
i t0GPC
GPC15
15 i 2
i) i 15)
kp/kt PLP kp kp/kt kt 14)
Polymer
Handbook 3)
9.
[M]
[I]0.5
13(PRR)
(MCR)12)
14PLP
0t/t0
t0
1 2
[M]max
[M]
1540PLP(10 Hz)
(t-)GPC15)
100,0000 200,000 300,000
(log
)
WM
PRR
X
X
X
X X X
X
CH2C
CH2C
CH2 CH
X
CH2CH
CH2CH CH2CH2
CH2CH CH2CH
H
XX 1,5-
PRR
MCR
+CH2C CH2CH2CH2 CH
X
CH2C
X
CH2CH
X
CH2CH2
X
-
-
) , , , , 2003.
) , , , , , 2001.
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ESR
Vol.1 200910
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