Living anionic polymerization of hydroxystyrene derivatives

Living anionic polymerization and block copolymerization of 4-methoxymethoxystyrene (MMS) and 4-methoxystyrene (MS) were studied in order to prepare poly(4-hydroxystyrene) having controlled molecular weight and narrow molecular weight distribution. The objective precursors,poly(MMS) and poly(MS), could be obtained by the polymerization using sec-butyllithium as an initiator in tetrahydrofuran (THF) at 195 K. Both the monomers were found to copolymerize anionically with styrene under the same conditions. Quantitative elimination of methoxymethyl group with hydrochloric acid in THF and that of methyl group with trimethylsilyl iodide in chloroform gave poly(4-hydroxystyrene)s, showing that methoxymethyl and methyl groups can be efficiently used for protection of hydroxyl group in the anionic polymerization process as well as tert-butyldimethylsilyl and tert-butyl groups.