【摘要】 采用红外光谱、核磁共振、高分辨质谱对甲苯二异氰酸酯（TDI）与三羟甲基丙烷（TMP）反应预聚物进行表征,并通过高效液相色谱-质谱联用追踪反应中各低聚物中间体的含量,研究TDI和TMP的反应动力学.研究表明:TDI-TMP加成反应为二级反应;温度对TDI中2位和4位—NCO的反应选择性有显著影响,反应温度从50℃升高到80℃,2位—NCO选择性从0.41增加到0.64;在80℃下,三步反应的反应速率常数分别为0.185 40、0.037 89和0.011 40 mol^-1·L^-1·min^-1,活化能分别为12.76、16.58和25.63 k J/mol,反应第三步较前两步对温度更加敏感,故反应后期适当提高温度有利于反应的充分进行.更多还原

【Abstract】 FT-IR,NMR and high-resolution MS were used to characterize the chemical structure of toluene diisocyanate（ TDI）-trimethylolpropane（ TMP） prepolymer,and HPLC-MS was adopted to detect the concentration of each oligomer in the reaction intermediates and to further reveal the reaction kinetics of TDI and TMP. The results indicate that（ 1） the TDI-TMP addition reaction is a second-order reaction;（ 2） temperature significantly affects the reaction selectivity of 2’-and 4’-NCO in TDI;（ 3） the 2’-NCO selectivity increases from 0. 41 to 0. 64 when the temperature increases from 50 ℃ to 80 ℃;（ 4） the reaction rate constants of the three steps of the reaction at 80 ℃are 0. 185 40,0. 037 89 and 0. 011 40 mol^-1·L^-1·min^-1,respectively,with the corresponding activation energy being 12. 76,16. 58 and 25. 63 k J/mol,respectively; and（ 5） the third step of the reaction is more sensitive to temperature than the first two steps,so that appropriately raising temperature in the later reaction may result in a more sufficient reaction.更多还原