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The polymers poly[(2,2-dimethyl-1,3-dioxolane-4yl) methyl acrylate] (PDMDMA) and four-armed PDMDMA with well-defined structures were prepared by the polymerization of (2,2-dimethyl-1,3-dioxolane-4yl) methyl acrylate (DMDMA) in the presence of an atom transfer radical polymerization (ATRP) initiator system. The successive hydrolyses of the polymers obtained produced the corresponding water-soluble polymers poly(2,3-dihydroxypropyl acrylate) (PDHPA) and four-armed PDHPA. The controllable features for the ATRP of DMDMA were studied with kinetic measurements, gel permeation chromatography (GPC), and NMR data. With the macroinitiators PDMDMA–Br and four-armed PDMDMA–Br in combination with CuBr and 2,2'-bipyridine, the block polymerizations of methyl acrylate (MA) with PDMDMA were carried out to afford the AB diblock copolymer PDMDMA-b-MA and the four-armed block copolymer S{poly[(2,2-dimethyl-1,3-dioxolane-4yl) methyl acrylate]-block-poly(methyl acrylate)}4, respectively. The block copolymers were hydrolyzed in an acidic aqueous solution, and the amphiphilic diblock and four-armed block copolymers poly(2,3-dihydroxypropyl acrylate)-block-poly(methyl acrylate) were prepared successfully. The structures of these block copolymers were verified with NMR and GPC measurements. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3062–3072, 2001

The graft copolymer with polytetrahydrofuran (PTHF) as branch chain was prepared by atom transfer radical copolymerization of styrene (St) and PTHF with an end-standing methacrylate (MA-THF). GPC and 1H NMR were used to characterize PTHF macromers and copolymers. The straight line on the profile of the molecular weight versus yield of copolymer was obtained, and the molecular weight distribution is relative narrow, supporting that the copolymerization is controllable. The relative reactivity ratio (1/rSt) of MA-PTHF to St was measured, and is independent of polymerization degree of the macromer. Atom transfer radical polymerizations (ATRP) of PTHF macromer were also investigated.