The redox system of ceric salt and alpha,omega-dihydroxy poly(dimethylsiloxane) is used to polymerize vinyl monomers such as acrylonitrile and styrene to produce block copolymers. The concentration and type of alpha,omega-dihydroxy poly(dimethylsiloxane) affects the yield and the molecular weight of the copolymers. The copolymers have about 20 degrees C lower glass-transition temperatures and much higher contact angle values than of the corresponding homopolymer of vinyl monomers, although the weight percent of alpha,omega-dibydroxy poly(dimethylsiloxane) of the copolymers is in the range of 1-2%. (c) 2006 Wiley Periodicals, Inc.