Synthesis and aqueous solution properties of novel sugar methacrylate-based homopolymers and block copolymers

We report the facile preparation of a range of novel, well-defined cyclic sugar methacrylate-based polymers without recourse to protecting group chemistry. 2-Gluconamidoethyl methacrylate (GAMA) and 2-lactobionamidoethyl methacrylate (LAMA) were prepared directly by reacting 2-aminoethyl methacrylate with D-gluconolactone and lactobionolactone, respectively. Homopolymerization of GAMA and LAMA by atom transfer radical polymerization (ATRP) gave reasonably low polydispersities as judged by aqueous gel permeation chromatography. A wide range of sugar-based block copolymers were prepared using near-monodisperse macroinitiators based on poly(ethylene oxide) PEO], poly(propylene oxide) PPO], or poly(e-caprolactone) PCL] and/or by sequential monomer addition of other methacrylic monomers such as 2-(diethylamino)ethyl methacrylate DEA], 2-(diisopropylaminoethyl methacrylate DPA], or glycerol monomethacrylate GMA]. The reversible micellar self-assembly of selected sugar-based block copolymers PEO23-GAMA50-DEA100, PEO23-LAMA30-DEA50, PPO33-GAMA50, and PPO33-LAMA50] was studied in aqueous solution as a function of pH and temperature using dynamic light scattering, transmission electron microscopy, surface tensiometry, and 1H NMR spectroscopy.