催化剂浓度对超支化聚4-氯甲基苯乙烯支化度的影响

Effect of feed ratio of catalysts to self-initiator monomer on branching degree of hyperbranched poly (4-chlormethylstyrene)

以4-氯甲基苯乙烯（4-CMS）为自引发单体，CuCl和2，2’-联吡啶（Bipy）为催化剂，氯苯作为溶剂，通过改变催化剂与自引发单体的摩尔比，制备了一系列具有不同支化度的超支化聚4-氯甲基苯乙烯[P（4-CMS）]，分析了催化剂浓度对聚合产物支化度的影响，利用凝胶渗透色谱和核磁共振对聚合产物进行了表征．摩尔比很低或较高时，生成的P（4-CMS）支化度较低；当摩尔比为0．1—0．2时，生成的P（4-CMS）支化度较高．反应产物的结构可以通过改变摩尔比来调整．动力学分析表明：假定一个催化剂单体激活基团活化2．6次，试验数据与理论分析结果很吻合．

A series of hyperbranehed poly （4 - chlormethylstyrene） [ P（4 - CMS） ] with various degree of branching were prepared with self-initiator monomer of 4- CMS and CUC1/2,2＇-Bipyridine as cata- lysts in solvent of chlorobenzene. The effect of the molar ratio of catalyst to monomer on the degree of branching of products was investigated. The products were characterized by GPC and NMR. The results show that the degree of branching is small at very low or high molar ratio. The highest degree of branching is achieved at the molar ratio range from 0.1 to 0.2. The architecture of the products can be designed by adjusting the molar ratio. Based on the kinetic analysis, if one catalyst molecule can activate 2.6 average times, the theoretical kinetic calculations are in good agreement with the experimental results.