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氟改性丙烯酸酯共聚物的制备及其涂层表面疏水性能
韩东晓1, 侯劲松1, 苗夫传1, 张志远1, 李雪冰1, 马敬芳1, 郑勇1, 朱立群2
1.北京航天新立科技有限公司, 北京 100039;2.北京航空航天大学 材料科学与工程学院, 北京 100191
摘要:
使用含有不同长度全氟碳链的全氟烷基乙基醇分别与甲基丙烯酸氯和甲苯二异氰酸酯反应,制备了两种不同的含氟单体 TEMAc-n 和 FnTDI,然后分别通过自由基共聚合反应和对合成好的常规含羟基丙烯酸酯共聚物进行后改性两种路线,制备了两类含有相同全氟碳链结构的氟改性丙烯酸酯共聚物 xTEMAc-n 和 xFnTDI 及其涂层。 利用傅里叶变换红外光谱(FT-IR)和核磁共振(19F NMR)技术对单体和相应共聚物的化学结构进行了表征,用示差扫描量热法(DSC) 测试了共聚物的玻璃化转变温度,通过静态水接触角、X 射线光电子能谱(XPS)和原子力显微镜(AFM)对共聚物膜层的表面性能进行了表征。 结果表明,制备合成了预期的含氟单体和含氟共聚物。 随着含氟单体的引入,共聚物的玻璃化转变温度升高,涂层的疏水性能提高。 含氟链段的长度对涂层疏水性的贡献大于氟含量的影响,与自由基共聚合方法制备氟改性共聚物 xTEMAc-n 相比,使用异氰酸酯基含氟单体对常规含羟基丙烯酸酯共聚物进行后改性制备的氟改性共聚物 xFnTDI,成膜时含氟链段更容易向涂层表面迁移,引入较少的含氟单体就可以获得优异的疏水性能。
关键词:  含氟单体  含氟共聚物  丙烯酸酯共聚物  疏水性  涂层  全氟链段
DOI:10.11933/j.issn.1007-9289.20201102001
分类号:TG174.46;TB324
文章编号:1007-9289(2020)05-0018-12
文献标识码:A
基金项目:
Preparation of Fluoro-modified Acrylate Copolymer and Hydrophobicity of Coatings Therefrom
Han Dongxiao1, Hou Jingsong1, Miao Fuchuan1, Zhang Zhiyuan1, Li Xuebing1, Ma Jingfang1, Zheng Yong1, Zhu Liqun2
1.Beijing Aerospace Xinli Technology Co., Ltd., Beijing 100039 ,China;2.School of Material Science & Engineering, Beihang University,Beijing 100191 , China
Abstract:
Perfluoroalkyl ethyl alcohol containing different length of perfluoroalkyl chains were employed to prepared two series of flourine-containing monomers TEMAc-n and FnTDI by reaciton with chlorine methacrylate and toluene diisocyanate. Two se- ries of fluoro-modified acrylate copolymers xTEMAc-n and xFnTDI, and coatings therefrom were prepared with the TEMAc-n monomers through free radical polymerization with vinyl monomers and FnTDI via reaction of the isocyanate groups in their own molecules with the hydroxyl groups in the side chains of the acrylic copolymers, respectively. The chemical structure of the mon- omers and the corresponding copolymers were investigated by Fourier transform infrared spectroscopy (FT-IR) and nuclear mag- netic resonance (19F NMR). Glass-transition temperature (Tg) of the copolymers were confirmed with differential scanning calo- rimetry (DSC). Surface properties of the copolymer coatings were characterized by static water contact angle, X-ray photoelec- tron spectrometer (XPS) and atomic force microscope (AFM), respectively. Results showed that the fluorine-containing mono- mers and the fluoro-modified copolymers were prepared as expected. Both Tg of the copolymers and hydrophobicity of the corre- sponding coatings increased as the fluorine-containing monomers were copolymerized. The length of the perfluoroalkyl chains played a more important role in improvement of the copolymer coatings hydrophobicity than fluorine content. More fluorine-con- taining segments migrated to the coatings surface during the film formation of the copolymers xFnTDI, resulting in more excellent hydrophobicity of the coatings, compared with the copolymers xTEMAc-n.
Key words:  flourine-containing monomers  fluoro-modified copolymers  acrylate copolymers  hydrophobicity  coatings  perflu- oroalkyl chains