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Cooperative catalysis and function integration created by random coil structure of polymer chain as nano-sized reactor

Research Project

Project/Area Number 19K05149
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 27030:Catalyst and resource chemical process-related
Research InstitutionJapan Advanced Institute of Science and Technology

Principal Investigator

Taniike Toshiaki  北陸先端科学技術大学院大学, 先端科学技術研究科, 教授 (50447687)

Co-Investigator(Kenkyū-buntansha) THAKUR Ashutosh  北陸先端科学技術大学院大学, 先端科学技術研究科, 特任助教 (80836833)
Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2021: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2020: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2019: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords協奏的触媒作用 / 機能集積 / 高分子鎖担持型触媒 / 精密設計 / オレフィン重合 / エチレン重合
Outline of Research at the Start

本研究の狙いは、固体触媒の多機能性と分子触媒の精密設計を併せ持つ新しい触媒系の提案にある。精密合成された高分子鎖に同種ないしは異種の活性金属中心を集積させる。この高分子鎖担持型触媒は、溶液中でナノサイズのランダムコイル状態を取るため、その中に束縛された活性金属中心間に協奏作用が働くものと期待される。活性金属中心の集積度や高分子鎖の分子設計を通して機能集積と協奏的触媒作用の制御を実現する。

Outline of Final Research Achievements

In this study, we developed a polymer chain-supported catalyst, in which a defined number of molecular catalysts are supported on monodisperse polymer chains obtained by precise polymerization, aiming to establish a novel catalyst concept that combines the precision of molecular catalysts design with the multifunctionality of solid catalysts. The polymer chain, with a random coil state in the solvent, can be regarded as a nano-sized reactor in which the grafted molecular catalysts act in concert. The polymer chain-supported catalysts showed higher activity in ethylene polymerization than the unsupported molecular catalyst, and the activity increased along with the number of active centers per polymer chain. In addition, the integration of different molecular catalysts in the same polymer chain and the control of catalytic performance by using properties of the polymer chain were also realized.

Academic Significance and Societal Importance of the Research Achievements

現行の化学プロセスの約2/3を支える触媒材料には、「分子触媒」と「固体触媒」という2つの概念が存在する。分子触媒は、分子構造と機能の対応を精密設計できるため活性や選択性に優れるが、単機能的である。一方、固体触媒は、安価かつリサイクル性に優れ、役割の異なる活性成分を表面上に集積する多機能化に利点があるが、構造の不均一性などにより精密設計が難しく選択性に劣る。本研究では、制限のない機能集積と設計の均一性を兼ね備えた、分子触媒と固体触媒の概念を融合する新規な高分子鎖担持型触媒を提唱し、触媒の協奏的作用や多機能性の系統的な設計につながる重要な科学的知見を得た。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (5 results)

All 2021 2019

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Open Access: 1 results) Presentation (2 results) (of which Int'l Joint Research: 1 results)

  • [Journal Article] Solution-state NMR study of organic components of industrial Ziegler-Natta catalysts: Effect of by-products on catalyst performance2021

    • Author(s)
      Thakur Ashutosh、Chammingkwan Patchanee、Wada Toru、Onishi Rikuo、Kamimura Wataru、Seenivasan Kalaivani、Terano Minoru、Taniike Toshiaki
    • Journal Title

      Applied Catalysis A: General

      Volume: 611 Pages: 117971-117971

    • DOI

      10.1016/j.apcata.2020.117971

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Bottom-Up Synthesis of Multi-Grained Ziegler?Natta Catalyst Based on MgO/MgCl2/TiCl4 Core?Shell Catalyst2021

    • Author(s)
      Ikeda Tomohiro、Wada Toru、Bando Yusuke、Chammingkwan Patchanee、Taniike Toshiaki
    • Journal Title

      Catalysts

      Volume: 11 Issue: 9 Pages: 1092-1092

    • DOI

      10.3390/catal11091092

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Cooperative Catalysis by Multiple Active Centers of Half-Titanocene Catalyst Integrated in Polymer Random Coil2019

    • Author(s)
      Ashutosh Thakur, Ryuki Baba, Toru Wada, Patchanee Chammingkwan, Toshiaki Taniike
    • Journal Title

      ACS Catalysis

      Volume: 9 Issue: 4 Pages: 3648-3656

    • DOI

      10.1021/acscatal.9b00214

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] Origin of Cooperative Ethylene Polymerization Among Multiple Active Centers Integrated in Polymer Random Coils2019

    • Author(s)
      Ashutosh Thakur, Minoru Terano, Toshiaki Taniike
    • Organizer
      Asian Polyolefin Workshop 2019
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Origin of Multicenter Mediated Synergistic Ethylene Polymerization with Polynorbornene-Supported Half-Titanaocene Catalysts2019

    • Author(s)
      Ashutosh Thakur, Toshiaki Taniike
    • Organizer
      第49回石油・石油化学討論会
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2023-01-30  

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