Synthesis and Characterization of Poly (phenylene oxide)-Based Block Copolymers via Cobalt Mediated Radical Polymerization (CMRP)

Abstract

Novel well-defined poly(phenylene oxide) (PPO) based block copolymers were polymerized from 4-bromo-2,6-dimethylphenol (BDMP) in the presence of a cobalt acetylacetonate (Co(acac)2) catalyst with dimethyl formamide (DMF) as a ligand and initiated with benzoyl peroxide (BPO) at 60 °C. The monomer copolymerized with vinyl acetate (VAc), polymethyl(meth)acrylate-b-poly(dimethyl siloxane)-b-polymethyl(meth)acrylate (PMMA-b-PDMS-b-PMMA) and polystyrene-b-poly(dimethyl siloxane)-b-polystyrene (PSt-b-PDMS-b-PSt) triblock copolymers in good yield. Characterization indicated a very narrow molecular weight distribution. The solid polymer obtained is a stable polymer with high thermal stability at 220 °C. The block copolymer indicated a new microstructure of phenylene oxide which was analyzed by proton-nuclear magnetic resonance (1H-NMR), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetriy (DSC) and gel permeation chromatography (GPC). Meanwhile, the number average molecular weights calculated from the 1H-NMR spectra were in very good agreement with the theoretically calculated values. The DSC results also indicated the successful formation of these new block copolymers.