采用原位乳液聚合法制备水性聚氨酯-丙烯酸酯乳液(PUA),以甲基丙烯酸乙酰氧基(AAEM)为酮单体,己二酰肼、碳酸二酰肼、草酸二酰肼、丁二酸二酰肼为肼单体对其进行交联改性,得到不同酮肼交联型的 PUA 乳液.通过非等温差示扫描量热法(DSC)和热重分析法(TGA)研究了不同肼单体对聚氨酯-丙烯酸酯胶膜的固化动力学及降解动力学的影响,采用T ~β外推法确定了固化工艺温度,根据 Kissinger-Ozawa 和 Crane 方程计算出不同 PUA 乳胶膜的固化反应表观活化能,反应级数和频率因子,并采用 Kis-singer 法对乳胶膜的热降解动力学进行了分析.结果表明4种肼单体所制的 PUA 乳胶膜中,选取草酸二酰肼所制的乳胶膜的固化反应表观活化能最高,为3．153 kJ/mol,反应级数为1．148,碰撞因子为57．943,而选取碳酸二酰肼制备的乳胶膜的固化反应表观活化能最低,为1．639 kJ/mol,反应级数为1．317,碰撞因子为1．917；选取碳酸二酰肼制备的乳胶膜的热稳定性最佳,而选取己二酰肼制备的乳胶膜的热稳定性最差.
The waterborne polyurethane-acrylate emulsions were prepared by in-situ polymerization and modified by ketone hydrazine crosslinking reaction,using methyl methacrylate acetoxy (AAEM)as ketone monomer,a-dipic dihydrazide,carbodihydrazide,oxalylhydrazide and succinohydrazide as hydrazine monomers.Effects of hydrazine monomers on the curing kinetics and degradation kinetics of polyurethane-polyacrylate latex films were studied by non-isothermal differential scanning calorimetry (DSC ) and thermal gravimetric analysis (TGA).The temperatures of the curing process were obtained by T-βextrapolation method,the curing reaction activation energy,reaction order and frequency factor were calculated by Kissinger-Ozawa and Crane equation, and the thermal degradation kinetics of latex films were analyzed by Kissinger method.The results showed that the apparent activation energy of latex film with oxalylhydrazide was the highest,which was 3.153 kJ / mol, the reaction order was 1.148 and the frequency factor is 57.943.While the apparent activation energy of latex film with carbodihydrazide is the lowest,which was 1.639 kJ/mol,the reaction order was 1.317 and the fre-quency factor was 1.917.In addition,the polyurethane-acrylate latex film with carbodihydrazide exhibited the highest thermal stability,while with adipic dihydrazide showed the poor thermal stability.
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