A two-step synthetic route to novel copolymer networks, consisting of polymethacrylate and polyacetal components, was developed by combining the polyaddition and anionic polymerization techniques. The functional polymethacrylates containing hydroxyl or vinyloxyl side groups were used as crosslinkers. They were anionically synthesized as follows: the copolymer of 2-hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) was prepared by the anionic copolymerization of 2-(trimethylsiloxy)ethyl methacrylate and MMA, followed by hydrolysis. The copolymer poly(HEMA-co-MMA) thus obtained possessed a hydroxyl group in each of its HEMA units. Another kind of vinyloxyl-containing (co)polymer was prepared by the anionic homopolymerization of 2-(vinyloxy)ethyl methacrylate (VEMA) or its copolymerization with MMA. The resulting (co)polymer possessed reactive vinyloxyl side groups. The copolymer networks were obtained by reacting each of the above-mentioned (co)polymers with a polyacetal prepared via the polyaddition between a divinyl ether and a diol. Three divinyl ethers (ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,6-hexanediol divinyl ether) and three diols (ethylene glycol, 1,4-butanediol, and 1,6-hexanediol) were employed as monomers in the polyaddition step, and their combinations generated nine kinds of polyacetals. When a polyaddition reaction was terminated with a divinyl ether monomer, a polyacetal with two vinyloxyl end groups was obtained, which could further react with the hydroxyl groups of poly(HEMA-co-MMA) to generate a copolymer network. On the other hand, when a diol was used as terminator in the polyaddition, the resulting polyacetal possessed two hydroxyl end groups, which could react with the vinyloxyl groups of poly(VEMA) or poly(VEMA-co-MMA), to generate a copolymer network. All the copolymer networks exhibited degradation in the presence of acids. (C) 2000 John Wiley & Sons, Inc.