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

2020 Fiscal Year Final Research Report

• 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
• 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

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.

Free Research Field

有機金属化学

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。