【摘要】 采用原位红外光谱法研究了PTPEG/GAP反应动力学.利用PTPEG/GAP反应体系在2100 cm-1和1086 cm-1吸光度比值与反应时间的关系得到了PTPEG/GAP本体末端点击化学交联反应的动力学曲线.曲线拟合表明,PTPEG/GAP本体末端交联反应过程分为明显的两个阶段;30℃时第一阶段反应动力学结束于535 min,40℃时为305 min,50℃时为295 min,60℃时为115 min.黏度测试表明,PTPEG/GAP反应体系黏度(η)随时间(t)变化曲线呈"L"型;30℃时η-t曲线拐点出现于540 min,40℃时为320 min,50℃时为305min,60℃时为118 min,拐点前后分别对应PTPEG/GAP凝胶前、凝胶后状态;且η-t曲线拐点时间与PTPEG/GAP第一阶段反应动力学结束时间相吻合.Arrhenius公式拟合表明,凝胶前,PTPEG/GAP末端点击化学交联反应表观活化能Ea1为(45.57±2.77)k J/mol;凝胶后,表观活化能Ea2为(59.50±4.01)k J/mol.更多还原

【Abstract】 In order to study the kinetic characters of bulk end-cross-linking Cu AAC "click"reaction,in situ FTIR method was employed to investigate the kinetics of PTPEG / GAP bulk end-cross-linking Cu AAC "click"reaction based on the spectral character of PTPEG and GAP. The kinetics curves of PTPEG / GAP bulk endcross-linking Cu AAC "click"reaction were obtained on the basis of the relationship of the absorbance ratio at2100 cm- 1and 1086 cm- 1changing with time. The results of fitting curves indicated that during the whole reaction,two obvious stages were observed. At 30 ℃,40 ℃,50 ℃ and 60 ℃,the first stage ended at 535 min,305 min,295 min and 115 min,respectively. Shear viscosity( η) results showed that the curves of η changed along with reaction time showed an "L-like"shape. At 30 ℃,40 ℃,50 ℃ and 60 ℃,the inflection point ofη-t curves appeared at 540 min,320 min,305 min and 118 min,respectively. The inflection point time of η-t curves was consistent with the end time of first stage of the PTPEG / GAP. Arrhenius equation fitting results indicated that the activation energy of the first stage corresponding to the reaction before gelation of PTPEG /GAP was( 45. 57 ± 2. 77) k J / mol while that of the second stage corresponding to the reaction after gelation was( 59. 50 ± 4. 01) k J/mol.更多还原