| Project/Area Number |
15550108
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Polymer chemistry
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| Research Institution | Yamaguchi University |
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Principal Investigator |
OISHI Tsutomu Yamaguchi University, Faculty of Engineering, Professor, 工学部, 教授 (30091169)
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| Co-Investigator(Kenkyū-buntansha) |
ONIMURA Kenjiro Yamaguchi University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (90284265)
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| Project Period (FY) |
2003 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2003: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Keywords | Optically Active Polymer / Asymmetric Polymerization / Maleimide Derivatives / Optical Resolution / Atom Transfer Radical Polymerization / Chiral Polymer / Chiral Stationary Phase / HPLC / キラルリガンド / イタコンイミド / 分子認識 / N-置換マレイミド / 有機金属 / 理論計算 |
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| Research Abstract |
Asymmetric polymerization of N-substituted maleimide (RMI) and N-substituted itaconimide (RII) were performed with chiral ligand/organometal complexes as an initiator. The polymerizabilities of the monomers, chiroptical properties of polymers and optical resolution of the polymers were investigated. Precision asymmetric radical polymerizations of RMI were carried out to find living radical and stereo-specific polymerization abilities. The results are shown as follows :
1.Asymmetric Radical Polymerization and Atom Transfer Radical Polymerization (ATRP) of RMI : The ATRP of N-1-phenylethylmaleimide, N-naphthyl maleimide (NMI) and N-phenyl maleimide were performed to obtain chiral polymers. However, the living radical polymerization character was not observed. The radical polymerization of NMI using chiral cobalt complex gave chiral NMI polymers with relatively high specific rotations.
2.Asymmetric Polymerization of Chiral RMI and Optical Resolution of Their Polymers : RMI including amino a
… More
cid derivatives, i.e., L-alanine, L-leucine, L-valine, (R) or (S)-phenylalanine and (R) or (S) phenylglycine, were synthesized and polymerized anionically using chiral ligand and organometal complex to obtain polymers with high specific rotations. Asymmetric induction onto the polymer main chain took place judging from the circular dichroism (CD) and NMR spectra. Chiral stationary phases (CSP) for HPLC were prepared from silica gel and the polymers. The coated type CSP can resolve some racemic compounds.
3.Preparation of Chemically Bonded CSP : Chemically bonded CSPs for HPLC were prepared from silica gel and the polymers to find the possibility of optical resolution. Some of the CSPs can resolve racemic compounds completely and can be used in all solvents.
4.Synthesis and Asymmetric Polymerization of Novel RMI : Some novel types of RMI having an azacrown-ether or an acetylene derivative as N-substituent were synthesized and polymerized. The polymerization properties of the monomers and chiroptical properties of the polymers were investigated by NMR and CD spectra.
5.Synthesis and Asymmetric Polymerization of Novel RII : Some new types of RII containing amino acid derivatives were synthesized and polymerized with chiral ligand and organometals complex to give chiral polymers. Chiroptical and optical resolution properties of the polymers were investigated. Less
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