羧化聚丙烯载体的链结构对丙烯腈聚合的影响

研究了羧化聚丙烯载体(不饱和羧酸接枝聚丙烯)接枝链的结构对丙烯腈聚合速度的影响。在引发活性方面对聚羧酸氧钒(聚合物负载催化剂)、异丁酸氧钒(小分子同系物)和硫酸氧钒(小分子非同系物)作了对比。实验结果表明:(1)(P-COO)_2VO两羧基之间存在着协同作用;(2)大分子链效应加强了羧基的协同作用;(3)聚羧酸链的d-、1-构型、羧基间距和载体的传质效应对聚合速度均有影响;(4)在本实验条件下,引发机理与高分子载体的链结构无关。

THE EFFECT OF THE CHAIN STRUCTURE OF CARBOXY- LATED POLYPROPYLENE CARRIER ON THE POLYMERIZATION OF ACRYLONITRILE

The effect of the chain structure of carboxylated polypropylene carrier (polypropylene grafted with unsaturated carboxylic acid) on the polymerization rate of acrylonitrile was investigated. The comparison on the initiation activity of vanadyl polycarboxylate (polymer supported catalyst) with vanadyl iso-butyrate (low molecular homologue) and vanadyl sulfa-te (low molecular non-homologue) was made. The experimental results indicated that (1) the cooperation effect exists between the carboxyl groups of (P-COO)2 VO; (2) the chain effect of carrier enhances the cooperation effect of carboxyl groups; (3) the polymerization rate was affected by the d-1-configuration of the chains of polycarboxylic acid, the distance of carboxyl groups and the mass transfer effect of carrier and (4) under our experimental conditions, the mechanism of initiation does not depend upon the chain structure of polymer supporters.