甲基丙烯酸十三氟辛酯改性胺固化剂增韧环氧清漆涂层的性能和机理研究  

Properties and toughening mechanism of epoxy varnish coating prepared with amine curing agent modified by tridecafluorooctyl methacrylate

作　　者：张博伦 张海宝[1,3] 王振军 张松林[1] 李兆睿 陈玉生 ZHANG Bolun;ZHANG Haibao;WANG Zhenjun;ZHANG Songlin;LI Zhaorui;CHEN Yusheng(School of Materials Science and Engineering,Chang’an University,Xi’an 710061,China;Shaanxi Jiaokong New Materials Co.,Ltd.,Xi’an 710077,China;Xi’an Sipai New Material Technology Co.,Ltd.,Xi’an 710600,China;Shaanxi Hongdazhongwei Petroleum Technology Co.,Ltd.,Xi’an 710000,China)

机构地区：[1]长安大学材料科学与工程学院,陕西西安710061 [2]陕西交控新材料有限公司,陕西西安710077 [3]西安斯派新材料科技有限公司,陕西西安710600 [4]陕西弘大众为石油科技有限公司,陕西西安710000

出　　处：《电镀与涂饰》2024年第7期134-143,共10页Electroplating & Finishing

基　　金：陕西省科技计划项目(2024GX-YBXM-378);西安市科技计划项目(23KGDW0035-2023)。

摘　　要：[目的]氢化双酚A二缩水甘油醚环氧树脂(HBPA-EP)基涂层应用时脆性大、韧性不足、疏水性较差等问题亟待解决。[方法]使用甲基丙烯酸十三氟辛酯(C6F)对异佛尔酮二胺(IPDA)固化剂进行改性后,与HBPA-EP反应固化为涂层,研究了改性剂掺量对涂层疏水性能、力学性能、耐化学品性能和耐沾污性能的影响。采用傅里叶变换红外光谱仪(FT-IR)和核磁共振氢谱仪(1H-NMR)分析了C6F对IPDA的改性机理。采用扫描电子显微镜(SEM)和能量色散谱仪(EDS)对涂层拉伸断面形貌及表面氟元素的分布进行表征。[结果]C6F的氟碳链结构被成功引入到IPDA分子中。采用C6F改性IPDA制备的涂层在疏水性能和力学性能上都得到明显提高。C6F与IPDA的物质的量比为0.5∶1.0时所得涂层的性能最佳,其水接触角为118.2°,铅笔硬度达到2H,柔韧性为1 mm,粘结强度为16.2 MPa,在浸水、浸碱和浸酸8 d后未出现吸水溶胀现象,表面也具有良好的抗涂鸦沾污性能。[结论]改性后的IPDA与HBPA-EP反应形成了交联网状结构,氟碳键的存在使网状结构交联更加致密,实现了对HBPA-EP交联体系的有效调节,令改性涂层的疏水性能和力学性能均得到改善。[Introduction]The hydrogenated bisphenol A diglycidyl ether epoxy resin(HBPA-EP)based coatings exhibit issues such as high brittleness,insufficient toughness,and poor hydrophobicity during their applications,which urgently need to be addressed.[Method]The isophorone diamine(IPDA)curing agent was modified by tridecafluorooctyl methacrylate(C6F)and then reacted with HBPA-EP to form a coating.The effect of the dosage of modifier on hydrophobicity,mechanical properties,chemical resistance,and stain resistance of the coating was studied.The modification mechanism of C6F on IPDA was analyzed by Fourier-transform infrared spectroscopy(FT-IR)and proton nuclear magnetic resonance(1H-NMR)spectroscopy.The fracture morphology and surface fluorine distribution of the coating were characterized by scanning electron microscopy(SEM)and energy-dispersive spectroscopy(EDS).[Result]The fluorocarbon chain structure of C6F was successfully introduced into the IPDA molecule.The coatings cured with C6F-modified IPDA showed significant improvements in both hydrophobicity and mechanical properties.The optimal performance of the coating was achieved at a molar ratio of C6F to IPDA of 0.5:1.0,featuring a water contact angle of 118.2°,pencil hardness of 2H,flexibility of 1 mm,and adhesion strength of 16.2 MPa.No water absorption or swelling was observed for the coating after immersion in water,alkali,and acid for 8 days,and its surface also exhibited good resistance to graffiti and staining.[Conclusion]A crosslinked network structure is formed by the reaction of HBPA-EP with the modified IPDA.The presence of fluorocarbon bonds makes the crosslinked network structure more compact,effectively regulating the crosslinking system of HBPA-EP and improving the hydrophobicity and mechanical properties of the modified coating.

关 键 词：甲基丙烯酸十三氟辛酯 异佛尔酮二胺 固化剂 改性 环氧涂层 力学性能 疏水性 耐久性 

分 类 号：TQ632.4[化学工程—精细化工] TU561.1[建筑科学—建筑技术科学]