Synthesis and characterization of well-defined poly(methyl methacrylate)/CaCO3/SiO2 three-component composite particles via reverse atom transfer radical polymerization

The attempt to prepare structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO3/SiO2 three-component composite particles, via reverse atom transfer radical polymerization (ATRP), using 2-2'-azo-bis-isobutyronitrile as initiator and Cu(II) bromide as catalyst was reported. CaCO3/SiO2 two-component composite particles were first obtained through sol-gel method, and their morphology and surface element information were determined by transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. The results indicate that the CaCO3 was encapsulated by the obtained SiO2. After being modified by silane coupling agent, the CaCO3/SiO2 composite particles copolymerized with methyl methacrylate (MMA) under standard reverse ATRP conditions to produce PMMA/CaCO3/SiO2 three-component composite particles. In the case concerned, first-order kinetic plots and linear increase of molecular weight (Mn) vs conversion and narrow molecular weight distribution for the graft polymer samples were observed. Furthermore, the gel permeation chromatography results illustrated that both the free PMMA chains from the solvent and the graft PMMA chains from the surface of CaCO3/SiO2 two-component composite particles were growing at the same rate. Characterizations of the PMMA-grafted CaCO3/SiO2 composite particles were done by Fourier transform infrared and thermogravimetric analysis. The results showed that the surface of the modified inorganic particles was grafted by the MMA and that the grafting percentage was about 8.7%.