高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (4): 1007.doi: 10.7503/cjcu20120829

• 高分子化学 • 上一篇    下一篇

SiO2 @P(MMA/BA/3FMA)复合纳米粒子的制备及膜性能

潘爱钊, 和玲, 张文伟   

  1. 西安交通大学理学院应用化学系, 西安 710049
  • 收稿日期:2012-09-10 出版日期:2013-04-10 发布日期:2013-01-31
  • 通讯作者: 和玲,女,博士,教授,博士生导师,主要从事功能材料研究.E-mail:heling@mail.xjtu.edu.cn E-mail:heling@mail.xjtu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:51073126);国家"九七三"计划项目(批准号:2012CB720904)和国家文物局项目(批准号:20110128)资助.

Preparation and Film Properties of SiO2@P(MMA/BA/3FMA) Composite Nanoparticles

PAN Ai-Zhao, HE Ling, ZHANG Wen-Wei   

  1. Department of Applied Chemistry, School of Science, Xi'an Jiaotong University, Xi'an 710049, China
  • Received:2012-09-10 Online:2013-04-10 Published:2013-01-31

摘要:

通过溶胶-凝胶法与半连续种子乳液聚合法相结合, 以正硅酸乙酯(TEOS)制备的纳米SiO2为核, 以甲基丙烯酸甲酯(MMA)、 丙烯酸丁酯(BA)和甲基丙烯酸三氟乙酯(3FMA)的共聚物P(MMA/BA/3FMA)为壳, 合成了SiO2@P(MMA/BA/3FMA)核-壳结构纳米复合粒子. 为防止纳米SiO2的团聚, 提高其与共聚物的结合力, 用乙烯基三甲氧基硅烷(VTMS)对纳米SiO2进行改性. 通过红外光谱、 透射电子显微镜、 动态激光散射粒度仪、 静态接触角测试仪、 X射线光电子能谱分析和热重分析等表征了乳液结构及膜性能. 结果表明, 获得的复合纳米粒子呈现粒径分布为40~50 nm的核-壳结构球型颗粒. 由于含氟官能团的迁移使得氟元素在膜-空气界面富集, 有效降低了膜的表面自由能. 当3FMA质量分数达到25%时, 膜表面自由能达到最低值(23.13 mN/m). 随着3FMA含量的增加, 共聚物初始热分解温度由350 ℃提高到390 ℃.

关键词: SiO2, 核壳乳液, 含氟丙烯酸酯共聚物, 复合纳米粒子, 膜性能

Abstract:

Nano-SiO2@P(MMA/BA/3FMA) core-shell composite nanoparticles were synthesized by emulsion polymerization with the modified nano-SiO2 from tetraethyl orthosilicate(TEOS) hydrolysis as the core and the fluorinated copolymer of methyl methacrylate(MMA), n-butyl acrylate(BA) and 2,2,2-trifluoroethyl methacrylate(3FMA) as the shell. In order to overcome the agglomeration of nano-SiO2 particles and to improve the chemical integration to the shell copolymer, vinyltrimethoxysilane(VTMS) was used as the surface modifier for nano-SiO2 particles. Fourier transforms infrared spectroscopy(FTIR), transmission electron microscope(TEM), dynamic light scattering(DLS), static contact angles(SCA), X-ray photoelectron spectroscopy(XPS) and thermogravimetric analysis(TGA) were employed to characterize the structures of the composite nano-particles and the film properties. The results indicated that SiO2@P(MMA/BA/3FMA) composite presented the uniform spherical core-shell partials with 40—50 nm in diameter. 25%(Mass fraction) 3FMA gave the lowest surface energy due to the migration of fluorine to the surface during the film formation. The thermal behavior of SiO2@P(MMA/BA/3FMA) was improved with the increase of 3FMA content.

Key words: SiO2, Core-shell, Fluorinated acrylate copolymer, Composite nanoparticles, Film property

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