Yin Quanyi, Tu Shuhua, Chen Min, Wu Limin
Department of Materials Science and State Key Laboratory of Molecular Engineering of Polymers, Advanced Coatings Research Center of Ministry of Education of China , Fudan University , Shanghai 200433 , China.
Langmuir. 2019 Sep 3;35(35):11524-11532. doi: 10.1021/acs.langmuir.9b02062. Epub 2019 Aug 22.
The fabrication of hollow organosilica nanoparticles with high elasticity is greatly desirable but still challenging. Herein, we present a new and simple strategy to prepare such nanoparticles by using hyperbranched polyvinylpolytrimethoxysilane (PVPMS) via a soap-free oil in water (O/W) emulsion system. PVPMS was synthesized through the radical polymerization of vinyltrimethoxysilane (VMS) followed by the acid-catalyzed hydrolytic polycondensation of trimethoxysilyl groups, which works not only as an organosilica precursor but also as a sole emulsion stabilizer due to its hydrolysis-induced amphiphilicity at the oil/water interface. When styrene was used as the oil phase and initiated to polymerize, hybrid polystyrene (PS) core-organosilica shell (PS@organosilica) nanoparticles were obtained by controlling the reaction conditions. Furthermore, highly elastic hollow organosilica nanospheres with low Young's modulus (∼220 MPa) were yielded through solvent etching of the core. This study expands the scope of organosilica precursor from small molecule organosilane to polymeric macromolecule and provides useful guidance for application in other polyorganosilsesquioxane related hybrid organosilica particles and functional hollow nanoparticles.
制备具有高弹性的中空有机硅纳米粒子极具吸引力，但仍具有挑战性。在此，我们提出了一种新的简单策略，通过在无皂水包油（O/W）乳液体系中使用超支化聚乙烯基聚三甲氧基硅烷（PVPMS）来制备此类纳米粒子。PVPMS是通过乙烯基三甲氧基硅烷（VMS）的自由基聚合，随后进行三甲氧基硅烷基团的酸催化水解缩聚反应合成的，它不仅作为有机硅前驱体，还因其在油/水界面水解诱导的两亲性而作为唯一的乳液稳定剂。当使用苯乙烯作为油相并引发聚合反应时，通过控制反应条件获得了杂化聚苯乙烯（PS）核-有机硅壳（PS@有机硅）纳米粒子。此外，通过对核进行溶剂蚀刻，得到了具有低杨氏模量（约220MPa）的高弹性中空有机硅纳米球。本研究将有机硅前驱体的范围从小分子有机硅烷扩展到聚合物大分子，并为其在其他聚有机倍半硅氧烷相关的杂化有机硅粒子和功能性中空纳米粒子中的应用提供了有益的指导。
