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通过表面引发的氮氧自由基介导的自由基聚合制备的聚苯乙烯接枝二氧化钛纳米颗粒及其在聚合物杂化薄膜中的应用。

Polystyrene-grafted titanium oxide nanoparticles prepared through surface-initiated nitroxide-mediated radical polymerization and their application to polymer hybrid thin films.

作者信息

Matsuno Ryosuke, Otsuka Hideyuki, Takahara Atsushi

机构信息

Institute for Materials Chemistry and Engineering, Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan.

出版信息

Soft Matter. 2006 Apr 18;2(5):415-421. doi: 10.1039/b601197g.

DOI:10.1039/b601197g
PMID:32680256
Abstract

Polystyrene (PS)-grafted-titanium oxide (TiO) nanoparticles with a diameter of 15 nm were prepared by the 'grafting-from' method using the surface initiator for nitroxide-mediated radical polymerization (NMRP). The graft densities were estimated to be 0.04-0.28 chains nm. Under this graft dense region it is assumed that surface polymer chains form a polymer brush structure in good solvents. Wide-angle X-ray diffraction suggested that the tacticity of the PS chains on the nanoparticle surface is mainly atactic. PS-grafted-TiO nanoparticles were stably dispersed in good solvents for PS chains due to the steric repulsion between the grafted chains derived from the osmotic pressure effect and their affinity for the solvents. When the PS-grafted-TiO particles were finely dispersed, the ultraviolet absorption due to TiO was strong and the difference in absorbance between the visible and ultraviolet regions was ten or more times greater than that for non-grafted TiO. By adding PS-grafted-TiO particles with PS matrix powder in CHCl, hybrid films were prepared by solvent casting. The PS-grafted-TiO-PS hybrid films showed high transmittance in the visible light region accompanied by ultraviolet absorption characteristic of TiO due to the fine dispersion of nanoparticles in the PS matrix. Furthermore, friction tests revealed that the wear resistance of PS thin films with PS-grafted-TiO was improved compared with PS film.

摘要

采用用于氮氧自由基介导的自由基聚合(NMRP)的表面引发剂,通过“接枝生长”法制备了直径为15纳米的聚苯乙烯(PS)接枝二氧化钛(TiO₂)纳米粒子。接枝密度估计为0.04 - 0.28条链/纳米²。在该接枝密度区域内,假定表面聚合物链在良溶剂中形成聚合物刷结构。广角X射线衍射表明,纳米粒子表面PS链的立构规整度主要为无规立构。由于渗透压效应产生的接枝链之间的空间排斥作用以及它们对溶剂的亲和力,PS接枝TiO₂纳米粒子在PS链的良溶剂中稳定分散。当PS接枝TiO₂颗粒精细分散时,由于TiO₂产生的紫外吸收很强,可见光区和紫外区的吸光度差异比未接枝的TiO₂大十倍或更多倍。通过在CHCl₃中加入PS接枝TiO₂颗粒和PS基体粉末,采用溶液浇铸法制备了混合薄膜。由于纳米粒子在PS基体中的精细分散,PS接枝TiO₂ - PS混合薄膜在可见光区具有高透射率,并伴有TiO₂的紫外吸收特性。此外,摩擦测试表明,与PS薄膜相比,含有PS接枝TiO₂的PS薄膜的耐磨性有所提高。

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