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纸质出版日期:1963-8-20,
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谢洪泉, 李平生. 含氯化合物对丁二烯定向聚合的作用[J]. 高分子学报, 1963,5(1):11-18.
SHIEH HONG-CHUAN, LI PING-SUNG. THE EFFECTS OF CHLORINE-CONTAINING COMPOUNDS ON THE STEREOSPECIFIC POLYMERIZATION OF BUTADIENE[J]. Acta Polymerica Sinica, 1963,5(1):11-18.
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。
The effects of n-butyl chloride,i-propyl chloride,t—butyl chloride,chloroform,carbon tetrachloride,methylene chloride,benzyl chloride, chlorobenzene and titanium tetra-chloride on the stereospecific polymerization of butadiene catalyzed by triisobutyl alu-minum and titanium tetraiodide have been studied.n-Butyl chloride or i-propyl chloride induces gel-formation during the polymerization.t-Butyl chloride or benzyl chloride in- hibits the polymerization,when,its quantity added is larger than the excess moles of triisobutyl aluminum. Both chloroform and carbon tetrachloride can lower the molecular weight of the polymer formed,but the latter does so more seriously and at the same time lowers the conversion of the polymer.Titanium tetrachloride also reduces the mole-cular weight of the polymer,but meanwhile changes the structure of the polymer.Neither methylene chloride nor chlorobenzene exerts any effect on the stereospecific polymeriza-tion of butadiene. In order tO explain the above phenomena,the reaction between tri-isobutyl aluminum and the chlorine-containing compounds has been studied.It has been observed that benzyl chloride or t-butyl chloride reacts with triisobutyl aluminum in-stantaniously,forming chloride ion equivalent tO the chlorine atom present in the com-pound,while chlorobenzene or methylene chloride reacts only very slightly. n-Butyl chloride or i-propyl chloride reacts with triisobutyl aluminum violently after an induction period,forming a large quantity of chloride ion.It has been shown that the gel-formation induced by n-butyl chloride during the polymerization is due to the concurrent cationic polymerization catalyzed by the aluminum chloride formed between the excess triisobutyl aluminum and the n-butyl chloridc after ao induction period.
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