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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。
(PS-co-TMI) with 9- (methylamino-methyl) anthracene (MAMA) and caprolactam (ε- CL) can be used to characterize the micromixing properties in the macromolecule reaction system. The reaction rate between PS-co-TMI and ε-CL is slower than the micromixing rate. The kinetic data is the quantitative characterization of micromixing properties by this method basis. The reaction between PS-co-TMI and ε-CL was studied in a 500mL jacketed stirred reactor using xylene as solvent. The reaction products were characterized by 13 C NMR and Fourier transform infrared spectroscopy. The reaction kinetics was studied by infrared quantitative method. The results showed that PS-TMI reacted with ε-CL to a reversible second-order reaction at the molar ratio of ε-CL to PS-TMI of 76.0 ℃ -129.0 ℃. The activation energies of Ea + 82.1kJ · mol-1, the frequency factor A + = 6.83 × 108; the activation energy Ea = 117.8kJ · mol-1 and the frequency factor A- = 2.43 × 1012.