不同二异氰酸酯三聚反应分子模拟与反应动力学研究

Study on the Different Diisocyanate Trimerization Reaction Kinetics and Molecular Simulation

利用DMol3分子模拟软件对二苯基甲烷二异氰酸酯(MDI)、氢化二苯基甲烷二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)3种异氰酸酯自聚反应进行了模拟计算;利用傅里叶变换红外光谱(FT-IR)对不同异氰酸酯在催化剂2,4,6-三(二甲胺基甲基)苯酚(DMP-30)作用下的三聚反应进行了跟踪,研究了不同催化剂用量、反应温度、反应时间下3种异氰酸酯的自聚反应动力学。结果表明,异氰酸酯自聚反应倾向生成稳定的六元环结构;3种异氰酸酯三聚反应均为二级反应,MDI在加入催化剂质量分数0.05%时,反应的活化能为26.1 kJ/mol,IPDI和HMDI在加入催化剂质量分数2%时,反应的活化能分别为13.5 kJ/mol和49.9 kJ/mol。

The self-polymerizations of three kinds of isocyanate, incuding phenyl methane diisocyanate （ MDI）, isophorone diisocyanate （IPDI） and hydrogenation of phenyl methane diisocyanate （HMDI） were simulated calcula- tion by using molecular simulation software DMol3. The trimerization reaction of diisocyanate were tracked by Fou- rier Transform Infrared Spectroscopy （FT-IR） at selected 2,4,6-three （ dimethylamino methyl） phenol （ DMP-30 ） as catalyst. The influences of different catalyst dosage, reaction temperature, reaction time under three kinds of di- isocyanate on trimerization reaction kinetics were researched. The results showed that three kinds of diisocyanate trimerization were second-order reaction. The reaction activation energy of MDI trimerization with 0.05% catalyst was 26. 1 kJ/mol, while the reaction activation energy of IPDI and HMDI with 2% catalyst were 13.5 kJ/mol and 49.9 kJ/mol respectively.