KINETICS OF POLYMERIZATION BY ACTIVATED MONOMER MECHANISM

被引：47

作者：

BIEDRON, T ^{[1
]}

SZYMANSKI, R ^{[1
]}

KUBISA, P ^{[1
]}

PENCZEK, S ^{[1
]}

机构：

[1] CTR MOLEC & MACROMOLEC STUDIES,DEPT POLYMER CHEM,SIENKIEWICZA 112,PL-90363 LODZ,POLAND

来源：

MAKROMOLEKULARE CHEMIE-MACROMOLECULAR SYMPOSIA | 1990年 / 32卷

关键词：

D O I：

10.1002/masy.19900320114

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Polymerization of cyclic ethers by activated monomer mechanism involves consecutive additions of protonated monomer molecules to the growing macromolecules fitted with hydroxyl groups at their ends. For oxirane itself and symmetrically substituted oxiranes there is only one kind of hydroxyl groups and one, unique way of ring‐opening. Unsymmetrically substituted oxiranes provide however two sites of attack and two different hydroxyls, resulting from these ring‐openings. Kinetics of polymerization of epichlorohydrin (chloromethyloxirane) has been studied and all four rate constants determined, namely rate constants of the primary and secondary alcoholate chain ends with a protonated monomer, opening in result of the attack on substituted or unsubstituted carbon atom. These rate constants are (in mol−1·1·s−1 at 25°C, in CH2Cl2 solvent): k11 = 0.055, k12 = = 0.41, k22 = 0.135, and k21 = 0.0011 (e.g. k12 is the rate of reaction of the primary alcohol producing the secondary alcohol). Thus, polymerization proceeds almost exclusively on the secondary alcoholate groups, reproducing themselves (k22). Copyright © 1990 Hüthig & Wepf Verlag

引用

页码：155 / 168

页数：14

共 7 条

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[3]

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[5]

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[6]

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[7]

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