HTPB/TDI、HDI聚合反应动力学研究

Study on Reaction Kinetics of Hydroxylated Polybutadiene with Tolulene Diisocyanates and Hexamethylene Diisocyanate

对端羟基聚丁二烯／甲苯二异氰酸酯，端羟基聚丁二烯／己二异氰酸酯甲苯溶液体系进行了反应动力学研究，用基团分析方法计算了相应体系的活化能，并对无催化剂和有催化剂的体系作了比较。结果表明，二丁基二月桂酸锡对上述体系有强的催化作用，使体系的活化能降低，反应速度加快。对于对端羟基聚丁二烯／甲苯二异氰酸酯体系，无催化剂时前后期反应活化能分别为２９．１ｋＪ／ｍｏｌ、３７．４ｋＪ／ｍｏｌ，有催化剂时前后期反应活化能分别为２５．０ｋＪ／ｍｏｌ、２９．９ｋＪ／ｍｏｌ。而对于端羟基聚丁二烯／己二异氰酸酯催化剂体系，前后期反应活化能基本一致，为３２．１ｋＪ／ｍｏｌ。

The polymerization kinetics of hydroxyl terminated polybutadiene(HTPB) with toluene diisocyanate(TDI) or hexamethylene diisocyanate(HDI) in tolulene has been studied in this paper. With the method of chemical titration, the activation energy(E a) was found out . By the comparison of the uncatalyzed and catalyzed system, it can be concluded that dibutyltin dilaurate can strongly catalyzed the reaction . The E a is decreased and the reaction rate is increased in the present of catalyst . For the HTPB/TDI system , the uncatalyzed E a values are 29.1 kJ/mol and 37.4 kJ/mol for beginning and late stage ,respectively .And catalyzed E a are 25.0 kJ/mol and 29.9 kJ/mol for beginning and late stage ,respectively. And for the HTPB/HDI system with catalyst , the E a value is 32.1 kJ/mol.