Fundamental of Polymer Material Science

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Coordination Polymerization
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6.1 ? ?
? Introduction
???????????????????,?????????????,?1938??,????????
?????
1938-1939 ??ICI??
??(180?200?C)
???
PE
??(150?300 MPa)
PE???????,????,???,????,?????????(LDPE)?
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1953?????? K. Ziegler
??????????????????PE?
PE???,????,???,????,?????????(HDPE)?
????
Ziegler???
????
1963??Nobel???!
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1954???????Natta?????? ????
1952????Frankford??Ziegler?? ??,??????
????
???PP
????
1963??Nobel???!
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6.2 ??????
1.?????????
????(????)??????,?????? ??????
1)?-???-???-?????????
2)??????????????????? ???
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????
???????????????? ?????????
????
????
????(????)
????
????C-C?????????????
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1)?????
?????(???????),?????????? ????R(?)??S(?)???
???-?????,?????R????????? ????
????C?????????,?????,C??? ?????,????????????????
?????C???????,????????
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????C?????,?????????
???? Isotactic
???? Syndiotactic
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???? Atactic
????????????????????(????????)?
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2)?????
?????????????????????? ????????????
???????,1,4-?????
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2.???????
?????????????????????,?????????????,????????
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????
???????????????,?????? ??????????????????
????
?????????????,???????? ?????????????
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????
????????????????C,???????????,??????????????????
????????,???????
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????????????
1)???????C?????
????R?S??????,???????????????????,??????
???????????,???R?S????
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2)????????C?????
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6.3 ?????????
1. ???????
??????????-?????????????????????????,???????????
???-????????????
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????????????????????????????????!
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2. ???????
1)??????????????s-? ???
2)????????
??,??????????????
3)????????????????
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4)???????????????
????????????????,???? ?????
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????????????????? ??????
??????????????????,?????????????????,????????????
??
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5)???????????
????????? ????????,????????,?????????????,???????
???????????,??????????
??????????? ??????,??????????,????????????????????
??????????Z-N???,?????,???????,???????
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3. ??????????
1)????????
a-?? ??? ???
??????
Ziegler-Natta???
???????1,4??
p-????????
???? ???
??????(??)
??????
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2)????????
(i) ?????????? (ii) ?????????
??????????????,?????????,?????????????????????????
???,???????????????
????,??????????????????
B ????????
A ??????
C ????
D ????
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4.???????????
1)?-?????
???????????????????
??????????,??????,??????
????????????????????
??PP,??????,?????,?????
??PP???PP,???????,?????? ?????,?????????? ??PP?Tm?
175?,???????
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2)??????
????????
???????
?? Tm128? ?? Tm156?
1,2-???
1,4-???
???????? Tg-80?, Tm148?
??-1,4???
??????? Tg-108?, Tm2 ?
??-1,4???
?
??????,?????????!
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3)????????
??????????????????
?????????????????????
?? ?? ?? ???? ????????
??????? ???????
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6.4 Ziegler-Natta????
1. Z-N??????
1)???? ?????????????
????
??? ???? ????? ?????
?????-?????!
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??Co?Ni?Ru?Rh ????????,???????????
2)????
????????????,???
R?111?????
???????TiCl3,???????????? ????,???AlEt2Cl?
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??Z-N??????
(i)???????? ??
(ii)???? ?? g??/gTi
??????????Ziegler-Natta????
?????500?1000 g/gTi
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????????????????????????????(?????),??????N?P?O?S
?????
?????5104 g/gTi
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??????????????,??? ???,?MgCl2?Mg(OH)Cl?
?????6105 g/gTi
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2.???????????

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3.??Z-N????????
????????,??????,????????????,????????????
???????,??????,???,???? ??????????????????
??? 1)?????????????????N2????
2)??????,???????????,??? ?????
3)????,????????????????
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? ?
1.?????????????????????? ??????????????????
2.???????? 1)????????????????????? ?????? 2)
Z-N???????????????????? 3)???TiCl3-AlEt3????,?????
???? ????
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3.????????????????????? ?????????????????????? ???
????????
4.????????????????????