|Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2002: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2001: ¥1,800,000 (Direct Cost: ¥1,800,000)
Carbohydrate-carrying synthetic polymers, which are referred to as "glycopolymers", provide very promising functional materials in a variety of scientific fields. In this study were synthesized AB block copolymer-type glycopolymers, fullerene (C_<60>)-glycopolymer conjugates, and multi-branched glycopolymers with well-defined molecular architectures through the living radical polymerization technique.
1. Two types of styrene derivatives having a pendant D-glucosamine or lactose residue, where hydroxyl groups are protected by acetyl functions, were polymerized at 90??-125?? In N,N-dimethylformamide with the initiators (BS-TEMPO or BS-DBN) to give nitroxyl-end-capped glycopolymers with controlled molecular weights and narrow molecular weight distributions (MWDs) (M_w/M_s < 1.2). The alkoxyamine initiators were prepared from styrene, benzoyl peroxide, and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or di-f-butyl nitroxide (DBN). Saccharide-substituted AB-block copolymers were successfully
synthesized by the post-polymerization of styrene utilizing the isolated TEMPO- or DBN-end-capped glycopolymers. All the copolymers possessed relatively narrow MWDs and controlled compositions. The block copolymers were converted into the amphiphilic counterparts quantitatively by treating them with hydrazine monohydrate. The solubility of the lactose-carrying amphiphilic block copolymers in various solvents strongly depended on their segment composition.
2. Fullerene (C_<60>)-glycopolymer conjugates were successfully synthesized through the radical addition reaction of the TEMPO- or DBN-end-capped block copolymer-type glycopolymers to C_<60> at 145℃ In 0-dichlorobenzene (ODCB) or ODCB/DMF (3/2, v/v) mixture. GPC and UV-vis spectroscopic analyses indicated that the conjugates possess 1,4-bisadduct structure, where a couple of glycopolymers are covalently connected to Coo at 1,4-positions.
3. Multi-branched glycopolymers with controlled chain lengths for both the backbone and the side chain were synthesized through atom transfer radical polymerization (ATRP) of glucose-carrying poly(vinyl ether) macromonomers which have been synthesized living cationic polymerization. Less