环氧树脂/不饱和聚酯自由基-阳离子混杂光固化及自分层特性的研究  

Study on free radical-cationic hybrid photocuring and self-stratification characteristics of epoxy resin/unsaturated polyester

作　　者：赵晨晶 韩宝煜 张天宇 余云 侯桂香 Zhao Chenjing;Han Baoyu;Zhang Tianyu;Yu Yun;Hou Guixiang(Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials,College of Materials Science and Engineering,North China University of Science and Technology,Tangshan 063210,Hebei,China)

机构地区：[1]华北理工大学材料科学与工程学院,河北省无机非金属材料重点实验室,河北唐山063210

出　　处：《中国胶粘剂》2022年第5期32-37,共6页China Adhesives

基　　金：河北省大学生创新项目(X2021107);河北省教育厅项目(QN2021114);唐山市功能高分子材料基础创新团队项目(21130201D)。

摘　　要：以酸酐和二元醇为单体制备了不饱和聚酯,后加入活性稀释剂甲基丙烯酸六氟丁酯,制备了含氟不饱和聚酯(F-UPR)。将F-UPR与双酚A型环氧树脂(ER)按照不同的质量比进行复合,以二苯基碘六氟磷酸盐为光引发剂,以异丙基硫杂酮为光敏剂,进行固化成膜,得到ER/F-UPR复合体系。对其光固化过程及机理进行分析,对不同质量配比的ER/F-UPR涂膜的凝胶率、力学性能、动态力学性能及固化膜的微观结构进行测试与表征。研究结果表明:ER/F-UPR复合体系进行了自由基和阳离子协同反应的固化过程;随着环氧树脂含量的增加,ER/F-UPR复合涂膜的附着力和硬度增加,冲击强度先增后降;当m(ER/F)∶m(UPR)=3∶1时,固化膜具有较佳的力学性能,凝胶率最大为93.2%,玻璃化转变温度为79.8℃,涂膜上表面对水接触角为98.8°;微观结构分析表明,氟元素在固化膜的上表面富集,环氧树脂则在固化膜的底面富集,形成自分层涂层。Fluorine-containing unsaturated polyester(F-UPR)was prepared by using anhydride and diol as monomers and adding hexafluorobutyl methacrylate as active diluent. F-UPR was compounded with bisphenol A epoxy resin(ER)according to different mass ratios,diphenyl iodine hexafluorophosphate was used as photoinitiator,isopropyl thioxanthone was used as photosensitizer,and then the ER/F-UPR composite system was obtained by forming a film. The photocuring process and mechanism were analyzed,and the gelation rate,mechanical properties,dynamic mechanical properties of ER/F-UPR coating film and microstructure of cured film with different mass ratios were tested and characterized. The research results showed that ER/F-UPR composite system underwent the curing process of synergistic reaction of free radical and cation. With the increase of epoxy resin content,the adhesion and hardness of ER/F-UPR composite coating film increased,and the impact strength increased first and then decreased. When m(ER/F)∶m(UPR)=3∶1,the cured film had relatively good mechanical properties,the maximum gelation rate was 93.2%,the glass transition temperature was 79.8 ℃,and the water contact angle of the upper surface of coating film was 98.8°. Microstructure analysis showed that fluorine was enriched on the upper surface of the cured film,while epoxy resin was enriched on the bottom surface of the cured film,which formed the self-stratification coating.

关 键 词：环氧树脂 不饱和聚酯 甲基丙烯酸六氟丁酯 光固化 自由基-阳离子固化 自分层 

分 类 号：TQ327.1[化学工程—合成树脂塑料工业]