无胺型水性聚氨酯-丙烯酸酯的制备及其热稳定性  

Synthesis and Thermal Stability of Amine-free Waterborne Polyurethane-polyacrylate

作　　者：赖小娟[1,2] 刘贵茹 王磊 赵倩云[3] 郭钢[3] 范华波[3] LAI Xiao-juan;LIU Gui-ru;WANG Lei;ZHAO Qian-yun;GUO Gang;FAN Hua-bo(Key Laboratory of Auxiliary Chemistry ＆ Technology for Chemical Industry, Ministry of Education, Shaanxi University of Science ＆ Technology, Xi＇an 710021, Shaanxi, China;Shaanxi Research Institute of Agricultural Products Processing Technology, Xi＇an 710021, Shaanxi, China;Research Institute of Oil~Gas Technology, Changqing Oilfield Branch Company, PetroChina, Xi ＇an 710021, Shaanxi, China)

机构地区：[1]陕西科技大学教育部轻化工助剂化学与技术重点实验室,陕西西安710021 [2]陕西农产品加工技术研究院,陕西西安710021 [3]中国石油长庆油田分公司油气工艺研究院,陕西西安710021

出　　处：《精细化工》2018年第6期1060-1067,共8页Fine Chemicals

基　　金：国家自然科学基金(51103081);陕西省科技计划项目(2016GY-241)~~

摘　　要：以不同种类聚二元醇（NCL2000、PCL1000）、不同种类异氰酸酯[4,4？-二环己基甲烷二异氰酸酯（HMDI）、异佛尔酮二异氰酸酯（IPDI）]、甲基丙烯酸甲酯（MMA）为主要原料,采用不同种类扩链剂（羧酸型亲水扩链剂和磺酸型亲水扩链剂）,通过无有机溶剂法制备了满足烟盒包装行业要求的零挥发性有机物（VOC）、无三乙胺的耐高温型水性聚氨酯-丙烯酸酯（WPUA1-6）乳液。通过FTIR、TEM、粒径分析仪、TGA等考察了WPUA乳液及其胶膜的结构和性能。探讨了聚二元醇种类、异氰酸酯种类和扩链剂种类对胶膜热稳定性的影响。结果表明：加入乙二胺基乙磺酸钠（AAS）后乳液的平均粒径均减小。当热失重分别为20%、30%、50%时,以耐高温NCL2000、HMDI和对苯二酚双（β-羟乙基）醚（HQEE）为原料合成的WPUA5胶膜热稳定性比以聚己内酯二元醇（PCL1000）、IPDI和1,4-丁二醇（BDO）为原料合成的WPUA2胶膜热分解温度分别提高了60.96、69.37和139.70℃。WPUA5分子的对称性增强使其结晶性增强,玻璃化转变温度（Tg）也增大。Zero VOC and triethylamine-free aqueous waterborne polyurethane-polyacrylate（WPUA1-6） emulsion was synthesized from different kinds of poly diols（NCL2000,PCL1000）,different kinds of isocyanates[4,4？-dicyclohexyl methane diisocyanate（HMDI） and isophorone diisocyanate（IPDI）] and methyl methacrylate（MMA） using different kinds of hydrophilic chain extender agents（carboxylic acid and sulfonate） by solvent-free method,and WPUA1-6 emulsion met the requirements of cigarette packaging industry. The WPUA emulsions and films were characterized by FTIR,transmission electron microscope（TEM）,particle size analyzer and thermogravimetric analysis（TGA）. The effects of isocyanate type,polyalcohol type and chain extender type on the thermal stability of WPUA films were investigated. The results showed that the addition of aliphatic diamine sulphonate（AAS） could reduce the average particle size of emulsion. TGA results revealed that the decomposition temperature of WPUA5 film synthesized by NCL2000,HMDI and hydroquinone bis（β-hydroxyethy） ether（HQEE） was higher than that of WPUA2 film synthesized by polycaprolactone diol（PCL1000）,IPDI and 1,4-butanediol（BDO）. The 20%,30% and 50% weight loss temperatures of WPUA5 film were increased by 60.96,69.37,139.70 ℃ compared with those of WPUA2 film. And the enhancement of both crystallization and glass transition temperature（Tg） of WPUA5 was attributed to the enhancement of the symmetry of molecules.

关 键 词：水性聚氨酯-丙烯酸酯 乳液聚合 热稳定性 耐热性 造纸化学品 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]