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1 PVC[1

]

dehydrochlorination allylic chloride 3ochloride butyl, 1,3-di(2-chloroethyl),

PVC 2,4-dichloro-n-

Carbonylallyl

center

quasi-ionic

route

Six-center

four-

allylic chloride

PVC

1. tertiary halogen CO(CH=CH)nCHCl PVC (n 1) allylic .2.1. 2. -unsaturated ketone dehydrochlorination 2.1.2 2.1. Allylic chloride 2 .

2-Cl shift 2 3 radical 4 monomer 3.2 shift 1. A2) 1.4 chaintransfer chloroallylic end groups (A1.3 1 polymerization (VC) P k2 1 head to head radical 2 monomer 3 1.4 methyl branch ethyl branch radical 3.2-dichloroethyl radicals .

3O 3 .4 2 polymerization (VC) P ks 2.3.1.

4- propagation active site LB dichloro-n-butyl branch (BB) 4 2.4-dichloro-n-butyl branch (BB) .5 proton (LB) 2.

allylic tertiary chloride a a b b) 6 7 .4.1.6 5 ( 2.

allylic (conformation ) tertiary chloride .7 8 2.1.5.5.1. carbonylallyl four center PVC 16 n=1 cis-16 furan (17 ) dehydrochlorination trans-16 2.

1.1. 2.2.2. mr triad(heterotactic) r diad.2. . ( Unzipping) 2.2.2. 2.2.8 isotactic>heterotactic>syndiotactic nucleophile m diad mm triad triad(syndiotactic). rr 2.2. 2.2.2.

3.9 9 PVC 10 2. .2.

4.10 11 PVC 2. Six-center concerted .2.

11 Six-center concerted BF 12 dehydrochlorination PVC 13 Six-center concerted dehydrochlorination PVC BF .

Six-center dehydrochlorination 37 36 3.12 34 dehydrochlorination cyclic chloride 140-170 OC 140OC 35 36 70 30 % 35 34 sixcenter concerted process 35 3 1. allylic 37 2.5.2. HCl36 35 35 36 140OC 5-chloro-534 methlnonane HCl 2. .

(C) (a) HCl HCl (d) (e) allylic methylene hydrogen C-Sn organotin .13 14 PVC dehydrochlorination (polaron) PVC CHClCH2C H- CHClCH2C H(b) CHClCH2C H.

.14 autoacceleration HCl Cyclization â 1. è è Jr. W..H. Structural and mechanistic aspects of the thermal degradation of .S.

27: p. Sci. 2133-2170. Polym. 2002.15 poly(vinyl chloride).. Prog. .