TEMPO-controlled radical suspension polymerization of poly(styrene)-block-poly(styrene-co-acrylonitrile) and poly(styrene)-block-poly(styrene-co-butyl methacrylate)

Abstract

Suspension polymerization expands the study of controlled radical polymerization to high conversions and is known as a method to synthesize polymers with high molecular weights. The radical block copolymerizations of styrene (S) and acrylonitrile (AN) or butyl methacrylate (BUMA) controlled by 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) was performed in an oil/water pressure reactor system at a temperature of 125°C. TEMPO-terminated styrene homopolymer was employed as macroinitiator. The systems were examined by varying the composition of the monomer mixture at a constant reaction time, as well as by varying the reaction time for a characteristic monomer composition to get all of the possible conversion range. The solubility effects of acrylonitrile in the suspension medium were considered. Furthermore, the yield of the reaction was improved through initiator addition by taking control of the reaction. The polymerizations could proceed under control up to a conversion of 80–90%. By using the copolymerization equations, the solubility of pure acrylonitrile in the suspension medium could be calculated and was found to be 8 wt.-%.