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本工作研究了氯代正丁烷、氯代异丙烷、氯代叔丁烷、氯仿、四氯化碳、二氯甲烷、氯化苄、氯代苯、四氯化碳等对丁二烯用三异丁基铝及四碘化钦催化聚合的影响。结果指出,氯代正丁烷或氯代异丙烷能引起凝胶的生成。氯代叔丁烷或氯化苄能抑制聚合。氯仿或四氯化碳能降低产物分子量,但后者同时使聚合转化率降低。四氯化钛既降低产物分子量又改变产物结构。氯代苯或二氯甲烷则对聚合几无影响。为阐明上述现象,本工作还研究了上述合氯化合物与三异丁基铝的反应。结果指出,氯化苄或氯代叔丁烷均能与三异丁基铝瞬时反应生成氯离子。氯代苯或二氯甲烷等则反应很少,氯代正丁烷或氯代异丙烷须经一诱导期后与三异丁基铝爆发反应生成大量氯离子。经实验证明,氯代正丁烷或氯代异丙烷引起凝胶生成的原因即在于当时所生成的三氯化铝引起交联的结果。
In this work, the effects of n-butane, chloroisopropane, tert-butyl chloride, chloroform, carbon tetrachloride, dichloromethane, benzyl chloride, chlorobenzene and carbon tetrachloride Effect of triisobutylaluminum and tetrakis iodination on catalytic polymerization of. The results indicate that n-butyl chloride or chloropropane can cause gel formation. Chlorinated tert-butane or benzyl chloride can inhibit the polymerization. Chloroform or carbon tetrachloride can reduce the molecular weight of the product, but at the same time the latter reduces the conversion of the polymerization. Titanium tetrachloride not only reduces the product molecular weight but also changes the product structure. Chlorobenzene or methylene chloride has little effect on the polymerization. In order to elucidate the above phenomenon, this work also studied the above reaction of chloro compounds with triisobutylaluminum. The results indicate that both benzyl chloride and tert-butyl chloride react with triisobutylaluminum to form chloride ions. Chlorobenzene or methylene chloride reaction is very small, n-butyl chloride or chlorinated isopropylate after an induction period and the reaction of triisobutyl aluminum generated a large number of chloride ions. It has been experimentally proved that the generation of gel due to n-butane or chloroisopropane is the result of the aluminum chloride produced at that time causing the crosslinking.