2000 Fiscal Year Final Research Report Summary
Design of unconjugated dienes with high polymerizability and high cyclization tendency using functional groups with no homopolymerizability
| Project/Area Number |
10650864
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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 | Fukui University |
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Principal Investigator |
KODAIRA Toshiyuki Fukui University. Faculty of Engineering Professor, 工学部, 教授 (40020226)
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| Co-Investigator(Kenkyū-buntansha) |
HAHIMOTO Tamotsu Fukui University. Faculty of Engineering Associate Professor, 工学部, 助教授 (00198681)
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| Project Period (FY) |
1998 – 2000
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| Keywords | 1, 6-diene / cyclopolymerization / radical polymerization / anionic polymerization / highly cyclized polymer / stereospecific polymerization / α-substituted acryloyl group / five-membered ring |
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| Research Abstract |
This research project has three aims. The first is to get evidence which supports the concept that 1, 6-dienes with high cyclization tendency and high polymerizability can be obtained by using functional groups with high conjugative nature along with no homopolymerization tendency. For this purpose, N-phenyl-N-methacryloyl-2-(methoxycarbonyl) allylamine was designed, since its allyl group has high conjugative nature despite its no homopolymerizability. Its cyclopolymerizability was investigated to confirm it has the characteristic desired.
The second aim is to see the effect of bulky substituent on cyclopolymerizability of 1, 6-dienes from the standpoint to get those with high cyclopolymerizability. N-Substituted N-(meth) acryloy1-2-(alkoxycarbonyl) allylamines were synthesized to attain the goal. These monomers have two positions to which bulky substituents can be introduced, i.e., N-substituent and alkoxy group. It was found that the bulky N-substituents enhances the cyclization tende
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ncy but retards overall polymerization rate. On the contrary, the bulky alkoxy group has almost no effect on cyclization tendency but increases the polymerization tendency. Therefore, one can obtain 1, 6-dienes with desired properties by introducing bulky substituents to N-position and alkoxy group.
The third aim is to see the possibility for controlling the structure of polymers derived from 1, 6-dienes by employing anionic polymerization. Structure of polymers is strongly dependent on polymerization conditions in ionic polymerization. This is because the aspect of propagating active species changes extensively depending on polymerization conditions. Monomers investigated are N-methyl-N-allyl-2 (ethoxycarbonyl) allylamine (MAEA) and N-phenyl-N-methacryloyl-2-(methoxycarbonyl) allylamine (PMEA). Polymerization of MAEA by lithium compound yielded highly isotactic polymers with no cyclic unit, while Grignard reagent yielded polymers with almost the same structure as that obtained by radical polymerization. PMEA afforded polymers with similar structure to those formed through radical mechanism irrespective of the initiator used. Less
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