Synthesis of networked polystyrene endowed with nucleophilic reaction sites by the living anionic polymerization technique

The living anionic copolymerization of styrene with 1,2-bis(4'-ethenylpheny l)ethane (1) or p-divinylbenzene (PDVB) with sec-butyllithium in benzene wa s carried out. The copolymerizations of styrene with more than 20 mol % of 1 gave insoluble polymers in quantitative yields, whereas the yield showed the maximum (97%) for PDVB at 15 mol %. The content of unreacted double bon ds of the network polymer formed by the copolymerization with PDVB was four times as large as that formed with 1. Gas chromatographic analyses of the copolymerization suggested close reactivities of the double bonds between s tyrene and 1, whereas a rapid consumption of PDVB compared with styrene was observed in their copolymerization. The r(1), r(2), and r(1)r(2) values fo r the copolymerization of styrene with 1 were determined to be 1.00, 1.09, and 1.09, respectively, which suggests that a more homogeneous network stru cture can be attained with 1. The living chain end of the produced living g el initiated the polymerization of tert-butyl methacrylate to give an insol uble block copolymer in a good yield. The hydrolysis of the ester group of the block copolymer led to an amphiphilic copolymer that exhibited a charac teristic property of a hydrogel. (C) 2000 John Wiley & Sons, Inc.