Fundamental of Polymer Material Science

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??? ??????
Radical Copolymerization
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????
??
(1)???????????? (2)????????????????????
???????? (3)??????????Q-e ???
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3.1 ??
??? ?????????????????
??? ???????????????????
??????????,??????,?????
????????,???-6,6????????,????????,??????????????,?
????????
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3.1.1 ?????????
????? ?????M1?M2?????
----M1M1M2M1M2M2M2M1M2M1M1M1M1M2M2---
?????????M1?M2????????
----M1M2M1M2M1M2M1M2M1M2M1M2M1M2---
?????????M1????????M2 ????????
M1M1M1M1----M1M1M1M1M2M2M2M2----M2M2M2M2
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??????????M1??,??????
????M2???
M1M1M1M1M1M1M1------------M1M1M1M1M1M1
M2 M2
M2----M2M2M2M2M2
??
???????????,???????????????
????-??? ???-??????
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???
?-co-,-alt, -b-, -g- ???????? ????????? (random,
alternating,block, graft)
????-co-???
????-g-???
3.1.2 ??????????
?
????,?????? ??????
?
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3.2 ????????
3.2.1 ???????
????????????????????
A ??????????(?????)?
B ???(????)?????????????,??????????????????
?M2M1? , ?M1M2?
C ?????,???????
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D ????????,????????? ??????
E ??,????????????????????,?????????????,??????????
???????
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???????????????????????
???
???
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???
???????????,?????M1?M2????????????????????????
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??????????????????????(m1/m2)
?M1?? M2????????,?
?????????????? M1? ? M2??????????????????
M1????M2? ? M2? ??? M1? ??????
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?????M2? ??m1/m2? ??M1?
?
??? ??????????????,???????????
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???,?????????(???)????
?
??????????????????????????????????,???????????????
??
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?f1???????M1???????????,?
?F1????????M1?????????,?
??????? ?????????????
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3.2.2 ?????????????
????????F1?????f1???,?????????F1-f1??,????
???????????r1?r2?
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(1)r10??k110,?????????????
(2)r11??k11 k12,?????????????
(3)r18 ????,????(????????)?
(4)r1?1???????????,??????? ?????
(5)r1?1?????????
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3.2.2.1 ????(r1r21)
r1r21 ?r21/r1,?
?????????????????????r1???????????????,???????????
??
60?????(r11.39)-???(r20.78) ????????(r13.2)-???
(r20.3) ?????????
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r1?
Fig. 3-1 ?????? (r1r21)
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?? ??????
r1r21,?????????????????? ??????????,???????????
???,?F1f1,?????????????
???????-????????????- ??????????????
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3.2.2.2 ???? (r1r20)
??????????????, ?????????,????? ?????????
r1r20
r1?0,r2?0
?F1-f1???????,?f1??????????????,???????
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r1/r2
Fig. 3-2 ??????
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? r20,r1?0
?M2?????,r1M1/M21,????? 11?????M1???,?????
??
?60????(r10.01)?????(r20)?????
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3.2.2.3 r1?1,r2?1 ?r1r2?1??????(??????????)
?r1?1,r2?1?r1r2?1?,?????????????,??????????,??????
????????
????(r11.68)??????(r20.23)?
(??r1?1,r2?1,?????????? ????)
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1-???(r11.68)??????(r20.23) 2-???(r155)??????(r
20.01)
Fig. 3-3 ??????????
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3.2.2.4 r1?1,r2?1??????????
r1?1,r2?1???????????????????,???????????????,?????
???dM1/dM2M1/M2?
?
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(1)r1r2?1?
????F1f10.5,????????? ?????????
????(r10.83)??????(r20.84)???
(2)r1?1,r2?1,r1 ?r2?
?????F10.5?,?????????? ????
????(r10.41)????(r20.04)???
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Fig. 3-4 ?????????
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??
(1) r1r2?????,???????.
(2) r1r2????1,?????????
(3) 0?r1r2?1????????????(F10.5)??????(F1f1)???
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3.2.2.5 ????(r1?1,r2?1)
?????,????????????????, ???????,????????r1?r2????
????(r11.38)?????(r22.04)?
?M1? M2??????,????????????????????
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3.2.3 ????????????
(1)????
?????,?????????????,??????,????????????,??????????
????f1??????F1???????? ????????
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(i)r1?1,r2?1 (curve 1)
??????? , ??????????
gt
??????????f1?????? ??????F1????,??M1???, ????????M
2????
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(ii)r1?1,r2?1 (curve 2)
f1???????,??????????? ???,????????????
f1???????,??????????,????????F1???????f1,??f1?F1
???????????
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r1?1,r2?1
r1?1,r2?1
Fig. 3-5 ????????????
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(2)??????????
????????????
A???????????????????,?? ????,???????,???????????
????????-????????????
B????????????????????? ???,???????????.????-?????
??-?????????
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3.4 ??????????? (see P 87)
3.4.1??????
(1)?????
(2)?????
(3)?????
(4)???
?????????????????!
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3.4.2 ????????
A)?? ????,????????????? ??,?????.
B)?? ????,?????????????
??,?????? C)?? ?????????????
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3.5 ?????????
??????,?????????(kp)?????? ??????????
? kp145(St) ? kp2300 (VAc)
?,???????? ? ????????? (50-100?)
??????????? ? ????????? (100-1000?)
??????????????????????!
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3.5.1 ???????
1/r1k12/k11
??????
????????????????????? ????????????????????? ?,????
????????????(P91,Table 3-7)
?????CH2CHX????????? X C6H5-,CH2CH-?-CN,-COR
? -COOH,-COOR ?-Cl?-OCOR,-R?-OR,-H
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3.5.2 ????? (k12)
r1k11/k12
? k11kp
? k12 kp/r1
K12?? Table 3-8
??????,???????????,???? ?????
??????????,?????????
?????????,?????????????? ????,???????????
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?3-8????-?????k12?
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3.5.3 ?????????????????
????
??
??
??
????
????
???
????
(1)????
????????????,???????? ????????
????????????????,??????,????????
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???
??????????,Why?
???
????
-CN
???????????
-COOH
-COOR
(2)????
?????????????????,????? ?????????????????,????? ??
???????????
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P93,Table 3-9 ??????????r1r2??
??????????????,???????, ???????????
???
??
???????
???? ????
?????
????????
?
?????????,?r1r2???????,?? ????!
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(3)????
????????????????????
(a)?????????????,?????? ??,?????????????????
???????
(b)????????????,???????? ?????
???????,?????????2-10? ?1,2-??????????2-20??
(c)???????,????????,?? ??????????????,?????
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3.6 Q-e??
????????????100??????4950?, ????r1,r2?????
??
???????
????????
Alfrey-Price Q-e?
?????????????????????????????
k12 P1Q2 exp (- e1e2)
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k12 P1Q2 exp (- e1e2)
P1?Q2-???????????M1???M2???? e1?e2-??????M1???M2
??????
??????????e???,e1??M1?M1???,e2??M2?M2???,?
k11 P1Q1 exp (- e1e1)
k22 P2Q2 exp (- e2e2)
k21 P2Q1 exp (- e2e1)
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r1k11/ k12 Q1 / Q2 exp - e1(e1- e2)
(1)
r2k22/ k21 Q2 / Q1 exp - e2(e2- e1)
(2)
??????,?
In(r1r2) - (e1- e2)2
(3)
??????Q 1.0,e -0.8????
???(1)?(2)?(3)???????Q,e ??
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(1)Q ?????????,??????????? ?????,Q ???,????????
(2)e ?????, ????????????? ?,e??????????????,e?
???
Q ?????????????
Q ?e ???????????,?????? ???
e ?????????????,?????? ????
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P72,??19
?Ri2fkdI
fkdRi/2I4.0?10-11molL-1s-1 ? 2?0.01
molL-1 2?10-9 s-1
?Rp/Ri 1.5?10-7molL-1s-1 ? 4.0?10-11molL-1s-1 3
750
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P72,??19
P72,??19
2?2?37507500
S(1L-104g/mol?1mol/L?887g/L)?839g/L ?78g/mol9.
5 mol/L
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P72,??19
1/Xn1/7500 8.0?10-5 3.2?10-4 ?0.01/1
2.3?10-6 ?9.5/10.000243 Xn 4115