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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 structure of graft chains of carboxylated polypropylene carrier (unsaturated graft polypropylene) on the polymerization rate of acrylonitrile was studied. Comparison of vanadyl polycarboxylate (polymer supported catalyst), vanadyl isobutyrate (small molecule homologue) and vanadyl sulfate (small molecule non-homologue) was made in terms of initiating activity. The experimental results show that: (1) synergistic effect exists between (P-COO) _2VO two carboxyl groups; (2) macromolecular chain effect strengthens the synergistic effect of carboxyl groups; (3) d-, Type, the distance between carboxyl groups and the mass transfer effect of the carrier have an impact on the polymerization rate; (4) Under this experimental conditions, the initiation mechanism has nothing to do with the chain structure of the polymer carrier.