1997 Fiscal Year Final Research Report Summary
Synthesis of oligomer reducing similarly to enzyme
| Project/Area Number |
07651090
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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 | Niihama National College of Technology |
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Principal Investigator |
TABUCHI Kenzo Niihama National College of Technology, Department of Industrial Chemistry, Professor, 工業化学科, 教授 (00044090)
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| Co-Investigator(Kenkyū-buntansha) |
NAKAGAWA Katsuhiko Niihama National College of Technology, Department of Industrial Chemistry, Asso, 工業化学科, 助教授 (40149977)
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| Project Period (FY) |
1995 – 1997
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| Keywords | N-Cetylpyridinium Chloride / Potassium Thiocyanate / Methyl Methacrylate / Oligomer / N-Cetylpyridinium Thiocyanate / Dihydropyridine / Photopolymerization |
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| Research Abstract |
When photopolymerization of methyl methactylate (MMA) with N-cetylpyridinium chloride (CPC) -KSCN was carried out in aqueous-organic two-phase system, MMA oligomer was obtained. The oligomer was expected to have reducing power similar to coenzyme NADH,because it must have 1,4-dihydrapyridine end. In this investigation, the photo-oligo-merizations were examined in aqueous-n-hexane two-phase and in aqueous-ethyl acetate two-phase.
Photo-oligomerizations were performed by the use of photochemical reaction apparatus with a Fuji Glass High Pressure Mercury Lamp HL-100 (100W), at 303 K,under vigorous stirring by flow in N_2. After irradiation, the reaction contents were poured into a large amount of methanol. If polymer compornent was precipitated, it was filtered. The filtrate was concentrated and extracted with chloroform. Crude oligomer was obtained by concentration of extract and purified on a silica gel column.
Following oligomerization mechanism was suggested from experimental results. N-Cetylpyridinium thiocyanate (CPT) is rapidly formed from CPC and KSCN in aqueous phase and transfers to organic phase. Using ethyl acetate as a solvent in organic phase, CPT transfers easily to organic phase and there formes effectively CT complex. CT complex of CPT photochemically decomposes to thiocyano and pyridinyl radicals due to CT absorption. The former radical initiates the radical polymerization of MMA,and the latter stable radical terminates it. Consequently, oligomer having dehydropyridine end is formed. Using n-hexane as a solvent in organic phase, transfer of CPT to oraganic phase is difficult. Therefore, the oligomerization ends in a short period, followed by the polymerization photoinitiated with the oligomer to form high polymer.
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