Synthesis of water-soluble statistical copolymers and terpolymers containing pendent oligo(ethylene glycol derivatives)

A series of water-soluble pendent oligo(ethylene glycol)-based statistical copolymers and terpolymers were synthesised using group transfer polymerisation (GTP). More specifically, oligo(ethylene glycol) monomethyl ether monomethacrylate (OEGMA) macromonomers containing 6, 21 or 44 ethylene glycol units were copolymerised with either benzyl methacrylate (BzMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA) or tetrahydropyranyl methacrylate (THPMA) to give statistical copolymers. The analogous terpolymers were obtained by copolymerising the oligo(ethylene glycol) monomethyl ether monomethacrylates with n-butyl methacrylate (nBuMA) and either BzMA or DMAEMA. Gel permeation chromatography was used to determine copolymer molecular weights and polydispersities, while proton NMR spectroscopy was used to assess their compositions. In all cases, the final copolymers were near-monodisperse (M-w/M-n's < 1.2) and good molecular weight control was achieved. The BzMA-containing copolymers were deprotected via catalytic hydrogenolysis to selectively remove the benzyl groups, giving polymers containing carboxylic acid groups. Similarly, the THPMA-containing polymers were deprotected by acidic hydrolysis to remove the tetrahydropyranyl groups, also resulting in acidic statistical polymers. Comparison of the degrees of deprotection achieved using the BzMA and THPMA protected monomers suggests that THP is the preferred protecting group since it is removed quantitatively regardless of the copolymer composition. In contrast, incomplete deprotection was obtained for the copolymers containing more than 67 mol% BzMA. (C) 1999 Elsevier Science Ltd. All rights reserved.