Reparation of silica/poly(methacrylic acid)/poly(divinylbenzene-co-methacrylic acid) tri-layer microspheres and the corresponding hollow polymer microspheres with movable silica core

Abstract

Hollow poly(divinylbenzene-co-methacrylic acid) (P(DVB-co-MAA)) microspheres were prepared by the selective dissolution of the non-crosslinked poly(methacrylic acid) (PMAA) mid-layer in ethanol from the corresponding silica/PMAA/P(DVB-co-MAA) tri-layer hybrid microspheres, which were afforded by a three-stage reaction. Silica/PMAA core-shell hybrid microspheres were prepared by the second-stage distillation polymerization of methacrylic acid (MAA) via the capture of the oligomers and monomers with the aid of the vinyl groups on the surface of 3-(methacryloxy)propyl trimethoxysilane (MPS)-modified silica core, which was prepared by the Stöber hydrolysis as the first stage reaction. The tri-layer hybrid microspheres were synthesized by the third-stage distillation precipitation copolymerization of functional MAA monomer and divinylbenzene (DVB) crosslinker in presence of silica/PMAA particles as seeds, in which the efficient hydrogen-bonding interaction between the carboxylic acid groups played as a driving force for the construction of monodisperse hybrid microspheres with tri-layer structure. The morphology and the structure of silica core, silica/PMAA core-shell particles, the tri-layer hybrid microspheres and the corresponding hollow polymer microspheres with movable silica cores were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy (XPS).