Amphiphilic Block and Statistical Copolymers with Pendant Glucose Residues: Controlled Synthesis by Living Cationic Polymerization and the Effect of Copolymer Architecture on Their Properties

摘要

Amphiphilic block and statistical copolymers of vinyl ethers (VEs) with pendant glucose residues were synthesized by the living cationic polymerization of isobutyl VE (IBVE) and aVE carrying 1,2:5,6-di-O-isopropylidene-D-glucose (IpGlcVE), followed by deprotection. The block copolymer was prepared by a two-stage sequential block copolymerization, whereas the statistical copolymer was obtained by the copoly- merization of a mixture of the two monomers. The monomer reactivity ratios estimated with the statistical copolymerization were r1 (IBVE) = 1.65 and r2 (IpGlcVE) = 1.15. The obtained statistical copolymers were nearly uniform with the comonomer compo- sition along the main chain. Both the block and statistical copolymers had n~rrow molecular weight distributions (weight-average molecular weightlnumber-average mo- lecular weight approx 1.1). Gel permeation chromatography, static light scattering, and spin-lattice relaxation time measurements in a selective solvent revealed thatthe block copolymer formed multimolecular micelles, possibly with a hydrophobic poly(IBVE) core and a glucose-carrying poly(VE) shell, whereas the statistical copolymer with nearly the same molecular weight and segment composition was molecularly dispersed in solution. The surface properties of the solvent.cast films of the block and statistical copolymer were also investigated with the contact-angle measurement.