2019 Fiscal Year Final Research Report
New Syhtnetic Stratedy of Cyclic Vinyl Polymers via Ring-Closing of Telechelic Polymers without Need of Highly Diluted Conditions
| Project/Area Number |
18K19112
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| Research Category |
Grant-in-Aid for Challenging Research (Exploratory)
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| Allocation Type | Multi-year Fund |
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| Review Section |
Medium-sized Section 35:Polymers, organic materials, and related fields
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| Research Institution | Nagoya Institute of Technology |
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Principal Investigator |
TAKASU Akinori 名古屋工業大学, 工学(系)研究科(研究院), 教授 (30303697)
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| Project Period (FY) |
2018-06-29 – 2020-03-31
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| Keywords | 環状高分子 / 無希釈条件 / ビニルポリマー / N-ヘテロ環状カルベン / ソルビン酸エステル / メタクリル酸メチル / メタクリル酸アリル / １：１付加体 |
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| Outline of Final Research Achievements |
We proposed the new synthetic procedure of cyclic vinyl polymers via anionic chain-growth polymerization of vinyl monomers including methyl sorbate (MS) initiated by a typical N-heterocyclic carbene (NHC), 1,3-di-tert-butylimidazol-2-ylidene (NHCtBu), as initiator. In the presence of an aluminum Lewis acid, the propagation was predominant compared with ring-closing; i.e. after monomer consumption, a ring-closure occurred to give cyclic 1,4-trans poly(MS) via threo selective addition. This is the first synthetic trial of a cyclic vinyl polymer via chain-growth polymerization which escaped entropic drawback (extremely high dilution). Such study triggered us to extentend a range of suitable vinyl monomers. Using an adduct of NHCtBu and MS as the initiator, umpolung (dipole inversion) of Michael acceptors via alpha-terminal proton abstraction by the propagating anion, were suppressed, which enabled us to synthesize cyclic poly(methyl methacrylate) and poly(allyl methacrylate).
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| Free Research Field |
高分子化学
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| Academic Significance and Societal Importance of the Research Achievements |
我々の暮らしを支えるソフトマテリアル（高分子）材料の高性能化はますます要求が高くなり、その構造の多様化のみならず分子鎖の絡み合いなどトポロジー制御が不可欠となってきた。環状ビニルポリマーを合成するには、分子間の反応を抑制するために高希釈条件が必要であったが、申請者の独創的な発想に基づいて、開始剤として働いたN-ヘテロ環状カルベンが対カチオンとして成長アニオンに隣接することで、高希釈条件を必要としない新規合成法を提案し、いくつかの環状ビニルポリマーが合成できた。この研究により、新たな性質を有するソフトマテリアル（高分子）材料の開発がよりアクセスしやすくなったという学術意義は非常に大きい。
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