Xi'an Jiaotong University, School of Science, Xi'an 710049, China.
J Colloid Interface Sci. 2013 Apr 15;396:129-37. doi: 10.1016/j.jcis.2013.01.020. Epub 2013 Jan 24.
The novel inorganic/organic core-shell SiO2/P(MMA/BA/3FMA) nanocomposite for coating application is synthesized in this paper by seed emulsion polymerization, in which the inorganic phase is composed of nano-SiO2 modified by vinyl-trimethoxysilane (VMS) or γ-methacryloxy propyl trimethoxylsilane (MPMS), and the organic phase is made of terpolymer by 2,2,2-trifluoroethyl methacrylate (3FMA), methyl methacrylate (MMA), and n-butyl acrylate (BA). The chemical structure of SiO2/P(MMA/BA/3FMA) is characterized by FTIR. The effect of surfactant polyvinylpyrrolidone (PVP), sodium dodecyl sulfate (SDS)/octyl phenyl polyoxyethylene ether (TX-10), sodium dodecyl benzene sulfonate (SDBS)/TX-10 and sodium hexametaphosphate (SHMP) on the grafting ratio (GR) of VMS and MPMS, the dispersion of nano-SiO2 particles and the film properties of SiO2/P(MMA/BA/3FMA) are investigated by TGA, DLS, TEM, SEM, and XPS. The morphology variation and the particle size distributions of SiO2/P(MMA/BA/3FMA) with the content of surfactant and P(MMA/BA/3FMA) are characterized. It is found that MPMS is more effective than VMS in improving GR and the dispersion of nano-SiO2 particles. The surfactants are favor of gaining the higher GR in the multilayer grafted nano-SiO2, especially SDS/TX-10 for 17.6% GR. The morphology of SiO2/P(MMA/BA/3FMA) is controlled by the amount of SDS/TX-10 and P(MMA/BA/3FMA) as the core-shell particles, the stacked pomegranate seed with multicore and the multicore-single shell structure when w(MMA)/w(BA)/w(3FMA)=1.3/1/1. Among the different surfactants, SDBS/TX-10 and PVP could give the monodispersing nano-SiO2 in the terpolymer matrix of the films, but SDS/TX-10 and SDBS/TX-10 could perform the fluorine-rich surface.
本文通过种子乳液聚合合成了新型无机/有机核壳 SiO2/P(MMA/BA/3FMA)纳米复合材料,用于涂层应用。其中无机相由乙烯基三甲氧基硅烷(VMS)或γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPMS)改性的纳米 SiO2 组成,有机相由 2,2,2-三氟乙基甲基丙烯酸酯(3FMA)、甲基丙烯酸甲酯(MMA)和 n-丁基丙烯酸酯(BA)组成的三元共聚物组成。通过傅里叶变换红外光谱(FTIR)对 SiO2/P(MMA/BA/3FMA)的化学结构进行了表征。考察了表面活性剂聚乙烯吡咯烷酮(PVP)、十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)、十二烷基苯磺酸钠(SDBS)/TX-10 和六偏磷酸钠(SHMP)对 VMS 和 MPMS 接枝率(GR)、纳米 SiO2 粒子分散性以及 SiO2/P(MMA/BA/3FMA)薄膜性能的影响。采用热重分析(TGA)、动态光散射(DLS)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)和 X 射线光电子能谱(XPS)研究了纳米 SiO2 粒子的形貌变化和粒径分布。考察了表面活性剂和 P(MMA/BA/3FMA)含量对 SiO2/P(MMA/BA/3FMA)形貌和粒径分布的影响。结果表明,MPMS 比 VMS 更有效地提高 GR 和纳米 SiO2 粒子的分散性。表面活性剂有利于在多层接枝纳米 SiO2 中获得较高的 GR,特别是 SDS/TX-10,GR 为 17.6%。SiO2/P(MMA/BA/3FMA)的形态由 SDS/TX-10 和 P(MMA/BA/3FMA)的量控制,形成具有核壳结构的石榴籽状堆积体、多核和多核-单壳结构,当 w(MMA)/w(BA)/w(3FMA)=1.3/1/1 时。在不同的表面活性剂中,SDS/TX-10 和 PVP 可以在薄膜的三元共聚物基质中得到单分散的纳米 SiO2,但 SDS/TX-10 和 SDBS/TX-10 可以得到富氟表面。