超支化聚硫醚改性环氧丙烯酸酯光固化涂料的制备及性能研究  

Synthesis and Properties of Hyperbranched Polythioether Modified Epoxy Acrylate UV Curable Coatings

作　　者：钱佳怡 李平 魏玮 刘晓亚 李小杰 QIAN Jia-yi;LI Ping;WEI Wei;LIU Xiao-ya;LI Xiao-jie(School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,China)

机构地区：[1]江南大学化学与材料工程学院,江苏无锡214122

出　　处：《表面技术》2021年第7期337-344,共8页Surface Technology

基　　金：江苏省研究生科研与实践创新计划项目(SJCX20_0749)。

摘　　要：目的研究超支化聚硫醚的结构对环氧丙烯酸酯复合光固化涂层性能的影响。方法利用存在明显反应速率差异的巯基-点击化学反应,首先以三羟甲基丙烷三(3-巯基丙酸)酯(TMPMP)和甲基丙烯酸缩水甘油酯(GMA)为原料,一锅法合成端巯基超支化聚硫醚(HBP-SH);然后以四氢呋喃丙烯酸酯(THFA)为改性单体,按HBP-SH与THFA物质的量比分别为1∶1、1∶0.9和1∶0.8,一锅法合成端基改性比例分别为100%、90%、80%的超支化聚硫醚(HBP-x THFA, x=100%, 90%, 80%);最后将HBP-x THFA加入商业化环氧丙烯酸酯(EA)中,制备超支化聚硫醚改性环氧丙烯酸酯光固化涂层。结果添加HBP-x THFA的复合光固化涂层的综合性能均高于纯EA涂层。通过附着力和固化收缩率测试表明,随着超支化聚硫醚末端基团改性比例的增加,涂层的附着力增加,固化收缩率减小。当端基改性比例为100%、添加量为2%时,复合涂层的附着力最好,固化收缩率最小。通过抗冲击和拉伸测试结果表明,添加HBP-x THFA的复合光固化膜的脆性得到改善。实时红外测试表明,加入HBP-x THFA的固化膜仍维持较高的双键转化率。结论一锅法制备的超支化聚硫醚合成步骤简单,加入EA体系能降低固化收缩率,提高附着力并改善涂层的脆性,具有工业化应用前景。The work aims to study the effects of the structure of hyperbranched polythioether on properties of epoxy acrylate composite UV-curable coatings.At first,trimethylolpropane tris(3-mercaptopropionate)(TMPMP)and glycidyl methacrylate(GMA)were used as raw materials to synthesize thiol-terminated hyperbranched polythioether(HBP-SH)by one-pot method,using the thiol-click chemistry reaction with significant difference in reaction rate.Further then,tetrahydrofurfuryl acrylate(THFA)was used as the modified monomer,and the molar ratio of thiol-terminated hyperbranched polythioether(HBP-SH)to tetrahydrofurfuryl acrylate(THFA)was 1∶1,1∶0.9 and 1∶0.8,respectively.The hyperbranched polythioethers(HBP-xTHFA,x=100%,90%,80%)with end group modification ratios of 100%,90%,and 80%were also synthesized by one-pot method.Finally,the prepared HBP-xTHFA were added to commercial epoxy acrylate(EA)to prepare hyperbranched polythioether modified epoxy acrylate composite UV curable coatings.The comprehensive performance of the composite UV curable coatings with HBP-xTHFA was higher than that of pure epoxy acrylate(EA)coatings.The adhesion and curing shrinkage rate test results indicated that as the modification ratio of hyperbranched polythioether end groups increases,the adhesion of coatings increased and the curing shrinkage rate decreased.When the end group modification ratio was 100%and the addition amount was 2wt%,the composite UV curable coating exhibited the best adhesion and the smallest curing shrinkage.The impact resistance and tensile test results showed that the brittleness of composite UV curable films added with HBP-xTHFA was improved.The composite UV curable films with HBP-xTHFA still maintained high double bond conversion by real-time infrared.The prepared hyperbranched polythioethers by one-pot method have simple synthesis steps.Adding it to commercial epoxy acrylate(EA)system can reduce the curing shrinkage rate of UV curable system,improve the adhesion of coatings and improve the brittleness of UV curable epoxy acr

关 键 词：超支化聚硫醚 改性 光固化 环氧丙烯酸酯 复合涂层 收缩率 

分 类 号：TG174.46[金属学及工艺—金属表面处理] TQ630.7[金属学及工艺—金属学]