| Project/Area Number |
02650663
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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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 | Tokohama National University |
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Principal Investigator |
TOMOI Masao Yokohama National University, Faculty of Engineering, Professor, 工学部, 教授 (20017940)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 1991: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1990: ¥2,300,000 (Direct Cost: ¥2,300,000)
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| Keywords | Crown ethers / Polymer-supported crown ethers / Spacer / Cooperative coordination / Polymer-supported polyetheramines / Pseudo cryptands / Phase transfer catalysts / モノアザテトラエチレングリコ-ル / アルコキシド / 固定化クラウン / 錯体 / アルカリイオン捕捉 |
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| Research Abstract |
(1) Polystyrene resins with crown ether structures and hydroxyl groups adjacent to the macro rings were prepared by the reaction of crosslinked polystyrene resins containing epoxide groups with monoaza-15-crown-5 or monoaza-18-crown-6. The polymeric catalysts with 30-40% ring substitution exhibited high activity for the dehydrobromonation of 2-bromoethylbenzene with aqueous KOH under tn-phase conditions. The active site of the catalysts was suggested to have a structure in which the K^+ ion was bound by the cooperative coordination of the ring donors and the alkoxide anions in the sidearms.
(2) Crown ethers bound to microporous polystyrene resins by oxyethylene spacers were prepared by the reaction of monoazacrown ethers with 2-tosyloxyethoxymethylated or 2-(2-tosyloxyethoxy)-ethoxymethylated polystyrene resins crosslinked with 2 mol% of divinylbenzene. The lariat catalysts with extra oxygen donors in the spacer chain exhibited higher phase transfer catalytic activity than the correspon
… More
ding immobilized catalysts without the donors in the spacer. The increased activity of the catalyst containing 15-crown-5 unit and two extra donors for the reaction of 1-bromooctane with Kl was concluded to result from the enhanced complexation with the K^+ ion, induced by the cooperative coordination of the crown unit donors and the donors in the spacer chain.
(3) Soluble or insoluble polystyrenes with hydroxyl-containing polyetheramine structures were prepared by the reaction of linear or crosslinked polystyrenes containing haloalkyl, tosyloxyalkyl, or epoxy groups with bis(2-(2-hydroxyethoxy)ethyl)amine (ATEG). The introduction of oxygen-containing spacer chains between ATEG residue and the polymer backbone resulted in the formation of cryptand-like alkoxides, in which the counter cations were bound by the cooperative coordination of the oxygen donors in the ATEG residue and in the spacers. The soluble and insoluble polymers with ATEG residue exhibited high catalytic activity for the dehydrobromonation of 2-bromoethylbenzene with aqueous NaOH or KOH under two-and three-phase conditions, respectively. Less
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