| Project/Area Number |
09450345
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
高分子合成
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| Research Institution | HOKKAIDO UNIVERSITY |
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Principal Investigator |
YOKOTA Kazuaki Hokkaido Univ., Grad. School of Eng., Professor, 大学院・工学研究科, 教授 (30001217)
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| Co-Investigator(Kenkyū-buntansha) |
HASHIMOTO Hisaho Tomakomai National College of Technology, Professor, 教授 (70180833)
SATOH Toshifumi Hokkaido Univ., Grad. School. Of Eng., Instructor, 大学院・工学研究科, 助手 (80291235)
KAKUCHI Toyoji Hokkaido Univ., Grad. School of Env. Earth. Assoc. Professor, 大学院・地球環境科学研究科, 助教授 (80113538)
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| Project Period (FY) |
1997 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥9,300,000 (Direct Cost: ¥9,300,000)
Fiscal Year 1999: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1998: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1997: ¥6,200,000 (Direct Cost: ¥6,200,000)
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| Keywords | Asymmetric polymerization / Cyclopolymerization / Chiral template / Optically active polymer / Divinyl monomer / Main-chain chirality / Chirality induction / 光学活性ポリマー / 不斉重合 / キラルテンフレート / キラル四連子 / キラルビニルポリマー |
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| Research Abstract |
(1) When the diad sequence A-A is a racemo configuration, the triad sequence A-A-B becomes chiral in a copolymer. This phenomenon was synthetically realized by cyclocopolymerization, because cleave of the cyclic unit affords the diad sequence A-A. Bis(p-vinylbenzoate) derivatives of chiral diol templates were copolymerized with styrene. The resulting poly[methyl methacrylate-co-styrene]s were optically active.
(2) The cyclocopolymerization of the dimethacrylate (MィイD21ィエD2), which was derived from 1,2: 5,6-di-O-isopropylidene-D-mannitol, with styrene (MィイD22ィエD2) induced new chirality in the polymer chain. The resulting poly [(methyl methacrylate)-co-styrene] had more active chirality with increasing the MィイD21ィエD2 unit, thus indicating that the new chirality was induced by the chiral A-A-A-A tetrad unit rather than the isolated A-A unit.
(3) The diad unit A-B without mirror planes affords chiral poly [A-alt-B]. The new aspect is realized by the enantioselective cyclopolymerization of unsymmetrical diene monomers. Methacryloyl and methyl fumaroyl derivative of chiral diol is a suitable monomer for this purpose. The resulting poly [(methy methacrylate)-alt-(methyl fumarate)]s were optically active.
(4) The bis(4-vinylbenzoate) monomers were useful for determining the absolute configuration of the cyclic units using the exciton chirality method. The chirality of dibenzoate showed the configurational change in the polymerization, and thus the template transmitted its chirality to the main chain during the intramolecular cyclization to form an enantiomeric cyclic unit.
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