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제118회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Synthesis of well-defined amphiphilic topological block copolymers via super base-catalyzed ring-opening polymerization of epoxide

2016년 8월 29일 14시 20분 52초
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금 09시 : 00분
고분자화학 - Architecture Controlled Polymers: Dendrimer, Hyperbranched, Star, Cycle and beyond
저자 및
Toshifumi SATOH
Faculty of Engineering, Hokkaido University, Japan, Japan
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승인 1건
The synthesis of well-defined amphiphilic topological block copolyethers (star, cyclic, figure-eight-shaped, tadpole-shaped, and trefoil-shaped BCPs) together with the linear BCP counterpart were achieved by the t-Bu-P4-catalyzed block copolymerization of decyle glycidyl ether (DGE) and triethylene glycol glycidyl methyl ether (TEGGE). The four-armed star-block copolyether was synthesized by the sequential t-BuP4-catalyzed block copolymerization of DGE and TEGGE using the tetra-alcohol initiator according to the core-first method. The synthesis of the miktoarm star copolyethers was achieved by the combination of the t-BuP4-catalyzed ring-opening polymerizwtion and intermolecular click reaction of the precursor polyethers. The synthesis of cyclic, figure-eight-shaped, and trefoil-shaped BCPs were carried out through three reaction steps; (i) t-Bu-P4-catalyzed block copolymerization of DGE and TEGGE using the alcohol which have azido groups as an initiator, (ii) ω-end functionalization using propargyl bromide, and (iii) intramolecular cyclization using click reaction. The tadpole-shaped BCP was synthesized by five steps; (i) t-Bu-P4-catalyzed polymerization of DGE using 3-phenyl-1-propanol as an initiator (PDGE), (ii) synthesis of PDGE with an azido and a hydroxyl group at ω-chain end (PDGE-(N3)-OH), (iii) t-Bu-P4-catalyzed post-polymerization of TEGGE using PDGE-(N3)-OH as a macroinitiator, (iv) ω-end propargylation, and (v) intramolecular click cyclization. The products were identified to be targeted star, cyclic, figure-eight-shaped, tadpole-shaped, and trefoil-shaped BCPs by SEC, IR and 1H NMR measurements. In addition, the number-average molecular weights (Mns,NMR) of BCPs were agreed with the calculated values based on initial monomers to initiator ratio, and the dispersitys of BCPs were narrow (1.04-1.08). In order to investigate the aggregation behavior of topological BCPs, the hydrodynamic diameter, the critical aggregation concentration, and the cloud point were determined by dynamic light scattering, fluorescence technique using pyrene, and variable-temperature UV-Vis absorption measuremant, respectively.