PS-co-TMI与己内酰胺反应研究

Study on Reaction between PS-co-TMI and ε-Caprolactam

苯乙烯-3-异丙烯基-α,α′-二甲基苄基-异氰酸酯共聚物(PS-co-TMI)与9-(甲胺基-甲基)蒽(MAMA)和己内酰胺(ε-CL)之间的竞争反应可用于表征大分子反应体系中的微观混合特性,PS-co-TMI与ε-CL的反应速率慢于微观混合速率,动力学数据是该方法定量表征微观混合特性的基础。在500mL的夹套式搅拌反应器中以二甲苯为溶剂研究了PS-co-TMI与ε-CL反应,采用核磁13C和傅立叶红外对反应产物进行表征,应用红外定量方法研究了反应动力学。结果表明:在76.0℃～129.0℃、ε-CL和PS-TMI的摩尔比2.95～27.5的范围内,PS-TMI与ε-CL反应为可逆的二级加成反应,正反应活化能Ea+=82.1kJ·mol-1,频率因数A+=6.83×108;逆反应活化能Ea-=117.8kJ·mol-1,频率因数A-=2.43×1012。

The parallel competitive reaction system composed by the reaction between PS-CO-TMI （the copolymer of styrene and α,α＇-dimethyl meta-isopropenyl benzyl isocyanate） and MAMA （9-（methylamino-methyl） anthracene） and the reaction between PS-co-TMI and ε-caprolaetam （ε-CL） can be used to assess micromixing in viscous media, and the detailed kinetics of the reaction between PS-co-TMI and ε-CL is necessary for quantitative analysis of the micromixing. The study of the kinetics of reaction between PS-co-TMI and ε-CL was carried out in a 500 mL jacketed vessel and the product was characterized by ^13C NMR and FT-IR. Reaction kinetics was examined by FT-IR quantificational method. The results indicate that the reaction between PS-co-TMI and ε-CL is a reversible addition reaction resulted in PS-co-TMI-CL. It was found that, at 76.0-129.0℃ and molar ratio ε-CL/PS-co-TMI=2.95 -27.5, the activation energy of positive reaction is equal to 82.1 kJ·mol^-1 with frequency factor equal to 6.83 × 10^8; the activation energy of negative reaction is equal to 117.8 kJ·mol^-1 with frequency factor equal to 2.43 × 10^12.