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机构地区:[1]西安交通大学理学院应用化学系,西安710049
出 处:《高等学校化学学报》2013年第4期1007-1013,共7页Chemical Journal of Chinese Universities
基 金: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);国家文物局项目(批准号:20110128)资助
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℃.Nano-SiO2@ P(MMA/BA/3FMA) core-shell composite nanoparticles were synthesized by emul- sion 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 im- prove the chemical integration to the shell copolymer, vinyhrimethoxysilane (VTMS) was used as the surface modifier for nano-SiO2 particles. Fourier transforms infrared spectroscopy ( FYIR), transmission electron micro- scope ( 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.
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