1996 Fiscal Year Final Research Report Summary
Synt6hesis and Ring Opening-Closure Behavior of Polymers Containing a Five-Membered Lactone Unit
| Project/Area Number |
07651071
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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 |
高分子合成
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| Research Institution | Utsunomiya University |
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Principal Investigator |
KIMURA Takao Utsunomiya Univ.Faculty of Engineering, Associate Professor, 工学部, 助教授 (10114159)
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| Project Period (FY) |
1995 – 1996
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| Keywords | 4-Butanolides / Diamines / Polyamides / Ring-Opening of Lactone / Reversible Reaction / Hydrolysis / NMR / GPC |
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| Research Abstract |
Bifunctional five-membered lactone monomers were prepared by the chemical transformation of t-butyl methacylate and dimethyl itaconate dimers telomerized using bromotrichloromethane. Polymerizations of these lactone monomers with some aliphatic and aromatic diamines and diols afforded polyamides, polyesters, polyamic acids, and polyimides. The polyamides prepared using aliphatic primary diamines had a high hydrophilicity owing to partial hydrolytic cleavage of the lactone moiety.
The ring-opening and -closure reactions of condensation compounds of (2R^<**>,4S^<**>) -4-chloroformyl-2-chloroformylmethyl-2,4-dimenthyl-4-butanolide with monoamines and monools served to elucidate the ring-opening behavior of the resulting condensation polymers. The variation of ring-opening ratio with the passage of time was traced by the ^1H-NMR method. The behavior of model compounds was affected considerably by such factors as pH,solvent, structure of substrate, and so on. As these ring-opening and -closure reactions finally attain equilibrium, the ring-opening of the lactone moiety is presumed to be a reversible reaction. On the other hand, the ring-opening of lactone unit in the model compound derived from aliphatic primary amine proceeded completely in a phosphate buffer solution and it was independent of enzyme.
Hydrolysis of titled polyamides is affected by the ring-opening ratio and aromatic site, and the results suggest the scission of end-type.
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