Development of controlled polymerization of vinylpyridines by multinuclear electrophilic organometallic initiators for the synthesis of functional polymers

Research Project

Project/Area Number	18K05214
Research Category	Grant-in-Aid for Scientific Research (C)
Allocation Type	Multi-year Fund
Section	一般
Review Section	Basic Section 35010:Polymer chemistry-related
Research Institution	Tokyo Institute of Technology
Principal Investigator	Oishi Masataka 東京工業大学, 物質理工学院, 助教 (20376940)
Co-Investigator(Kenkyū-buntansha)	野村信嘉名古屋大学, 生命農学研究科, 准教授 (70291408)
Project Period (FY)	2018-04-01 – 2021-03-31
Project Status	Completed (Fiscal Year 2020)
Budget Amount *help	¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000) Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000) Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000) Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Keywords	有機金属錯体 / 精密重合 / ビニルピリジン / 親電子性金属 / 立体規則性 / 立体規則性重合 / 共重合 / 超高分子量重合体 / 機能性高分子
Outline of Final Research Achievements	Synthesis and structure characterization of electrophilic organometallic complexes supported by well-available substituted phenolate ligands were studied, and these complexes were evaluated in the polymerization of 2-vinylpyridine (2VP). As a result, organoyttrium complexes appeared to be one of the most active initiators with exceedingly high-isotactic control. Moreover, both molecular weight control in a high molecular weight region and the high stereoregularity were attained by co-use of excess organoaluminums. Polymerization of 2VP by an on organoyttrium initiator derived from a sterically demanding salicylaldimine enabled molecular weight control in a low molecular weight region with moderate to high isotacticities. Interestingly, the latter yttrium system displayed polymerization activity toward some acrylates and lactide monomers, and block copolymerization of 2VP was examined.
Academic Significance and Societal Importance of the Research Achievements	ポリ（２－ビニルピリジン）は、ピリジル極性基の存在のためより強い分子間力や水素結合が働く。立体規則性の制御された(ブロック)重合体において興味深い機能が発現できると期待される。本研究では、イットリウムを中心に親電子性の金属錯体を設計し、高活性で立体規則性の制御された２－ビニルピリジンの重合、さらに他のモノマーに対する重合活性を見出した。立体規則性と同時に、分子量制御や他モノマーの重合を可能とする錯体はほとんど知られず、本研究の成果は学術的に有意である。