CAJ | 학술논문

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.
채용원위유액취합법제비수성취안지-병희산지유액(PUA),이갑기병희산을선양기(AAEM)위동단체,기이선정、탄산이선정、초산이선정、정이산이선정위정단체대기진행교련개성,득도불동동정교련형적 PUA 유액.통과비등온차시소묘량열법(DSC)화열중분석법(TGA)연구료불동정단체대취안지-병희산지효막적고화동역학급강해동역학적영향,채용T ~β외추법학정료고화공예온도,근거 Kissinger-Ozawa 화 Crane 방정계산출불동 PUA 유효막적고화반응표관활화능,반응급수화빈솔인자,병채용 Kis-singer 법대유효막적열강해동역학진행료분석.결과표명4충정단체소제적 PUA 유효막중,선취초산이선정소제적유효막적고화반응표관활화능최고,위3．153 kJ/mol,반응급수위1．148,팽당인자위57．943,이선취탄산이선정제비적유효막적고화반응표관활화능최저,위1．639 kJ/mol,반응급수위1．317,팽당인자위1．917；선취탄산이선정제비적유효막적열은정성최가,이선취기이선정제비적유효막적열은정성최차.
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.