| Project/Area Number |
04403021
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
高分子合成
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| Research Institution | Nagoya University |
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Principal Investigator |
OKAMOTO Yoshio Nagoya University, School of Engineering, Professor, 工学部, 教授 (60029501)
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| Co-Investigator(Kenkyū-buntansha) |
HABAUE Shigeki Nagoya University, Research Associate, 工学部, 助手 (30252266)
NAKANO Tamaki Nagoya University, Research Associate, 工学部, 助手 (40227856)
YASHIMA Eiji Nagoya University, Lecturer, 工学部, 講師 (50191101)
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| Project Period (FY) |
1992 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥36,200,000 (Direct Cost: ¥36,200,000)
Fiscal Year 1994: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1993: ¥7,900,000 (Direct Cost: ¥7,900,000)
Fiscal Year 1992: ¥26,300,000 (Direct Cost: ¥26,300,000)
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| Keywords | Helix / Optically active polymer / Polymethacrylate / Polyacrylate / Polyacetylene / Polyisocyanate / HPLC / Chiral recognition / ポリイソシアナート / 不斉識別能 / 高速液体クロマトグラフィー用充填剤 / 光学活性ポリマー / 不斉アニオン重合 / ラジカル重合 / メタクリル酸エステル / イソシアナート / オリゴマー |
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| Research Abstract |
1. Optically active, helical polymers were successfully synthesized from novel methacrylates, acrylates, and acrylamides. Diphenyl-3-pyridylmethyl methacrylate, phenyl-bis (2-pyridyl) methyl methacrylate, 1-phenyldibenzosuberyl methacrylate, and 1- (2-pyridyl) dibenzosuberyl methacrylate gave almost perfectly isotactic, one-handed helical polymers through anionic polymerization using the complex of N,N'-diphenylethylenediamine monolithium amide with (+) -1- (2-pyrrolidinylmethyl) pyrrolidine. Helix-sense-selective polymerization of the latter two monomers was realized also through radical mechanism using optically active transfer agents and solvents.
2. Optically active polymers were obtained from aromatic isocyanates. Polymerization of m-methylphenyl and m-methoxyphenyl isocyanates with (+) -1- (2-methoxymethyl) pyrrolidine monolithium amide gave optically active polymers having single-handed helical structure in excess. It was clarified that these polymers have one-handed helical part extending from the alpha-end to the chain length corresponding to 12-13 monomeric units and thereafter, helix reversal takes place.
3. Novel phenylacetylene derivatives bearing chiral carbamate groups in the side chain gave optically active, helical polymers by homopolymerization and copolymerization with archiral monomers using Rh catalysts. The polymers resolved many racemic compounds when used as a chiral packing material for HPLC.
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