Unique Hydrophobization and Hybridization via Direct Phase Transfer of ZrO2 Nanoparticles from Water to Toluene Producing Highly Transparent Polystyrene and Poly(methyl methacrylate) Hybrid Bulk Materials
Unique Hydrophobization and Hybridization via Direct Phase Transfer of ZrO2 Nanoparticles from Water to Toluene Producing Highly Transparent Polystyrene and Poly(methyl methacrylate) Hybrid Bulk Materials
复制标题
通过 ZrO2 纳米颗粒从水到甲苯的直接相转移进行独特的疏水化和杂化，生产高透明的聚苯乙烯和聚甲基丙烯酸甲酯混合散装材料
DOI：
10.1021/acs.macromol.7b02155
复制
发表时间：
2017
期刊：
影响因子：
5.5
通讯作者：
Kawaguchi Seigou
中科院分区：
文献类型：
--
作者：
Enomoto Kazushi;Ichijo Yusuke;Nakano Masahiko;Kikuchi Moriya;Narumi Atsushi;Horiuchi Shin;Kawaguchi Seigou
提出了一种具有广泛应用前景的有机-无机杂化法制备高透明聚苯乙烯(PST)/聚甲基丙烯酸甲酯(PMMA)杂化块体材料的方法。已开发的两项关键技术是将原来分散在水中的纳米氧化锆进行表面处理、疏水和功能化，以及将其纳米分散到聚合物连续相中，而不会发生任何凝聚和/或团聚。展示了一种独特的、引人入胜的表面处理方法，该方法同时实现了纳米氧化锆从水到甲苯的疏水和相转移。由水、甲苯和甲醇组成的三元混合溶剂通过温和的溶剂交换，在甲苯中获得了透明的表面修饰的二氧化锆纳米分散体。添加具有四个以上碳原子的羧酸作为表面处理剂使这种疏水成为可能。通过小角X射线散射(SAXS)、动态光散射(DLS)、扫描电子显微镜、热重分析、核磁共振和红外光谱等手段对制备的羧酸修饰的纳米氧化锆进行了表征。干燥后的表面处理过的ZrO_2NP粉末在多种有机溶剂和乙烯基单体中具有再溶解或纳米分散的能力。在此基础上，以甲基丙烯酸酯功能化的纳米氧化锆为交联剂，以苯乙烯(St)或甲基丙烯酸甲酯(MMA)为代表单体，通过共聚反应制备了厚度为10 mm的PSt/PMMA杂化块体材料。测量了高折射率杂化材料的光学性质，并与基于菲涅耳折射、Lorentz-Lorenz有效介质展开、Lambert-Beer和Rayleigh散射方程的理论进行了比较。本方法为无机和有机材料组成的不同透明杂化材料提供了有前景的候选材料。
A versatile and promising organic–inorganic hybridization method is proposed for the fabrication of highly transparent polystyrene (PSt) and poly(methyl methacrylate) (PMMA) hybrid bulk materials containing highly crystalline ZrO2nanoparticles (NPs) having a number-average diameter of 3.11 nm. The two key technologies that have been developed are the surface treatment, hydrophobization, and functionalization of ZrO2NPs originally dispersed in water and their nanodispersion into a polymer continuous phase without any coagulation and/or agglomeration. A unique and fascinating surface treatment method is demonstrated in which the hydrophobization and phase transfer of ZrO2NPs from water to toluene is simultaneously achieved. Transparent surface-modified ZrO2nanodispersions in toluene are obtained by a gentle solvent exchange from a ternary solvent mixture composed of water, toluene, and methanol. The addition of carboxylic acids having more than four carbon atoms as the surface treatment agent enables this hydrophobization. The carboxylic acid-modified ZrO2NPs prepared by the method are thoroughly characterized by small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), scanning TEM, TGA, and NMR, and IR spectroscopies. The surface-treated ZrO2NP powders after drying possess the ability of redissolution or nanodispersion in several organic solvents and vinyl monomers. Further, optically transparent PSt and PMMA hybrid bulk materials with thicknesses of 10 mm are fabricated by the copolymerization of styrene (St) or methyl methacrylate (MMA) as a representative vinylic monomer with methacrylate-functionalized ZrO2NPs as the multivinyl cross-linking agent. The optical properties of hybrid materials having a higher refractive index than that of the original homopolymers are measured and compared with the theories based on Fresnel refraction, Lorentz–Lorenz effective medium expansion, and Lambert–Beer and Rayleigh scattering equations. The present method provides promising candidates for different transparent hybrid materials consisting of inorganic and organic materials.