Preparation of aluminum-boron cluster compounds and their application as cocatalysts of olefin polymerization

• Project/Area Number: 26810070
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Polymer chemistry
• Research Institution: Hiroshima University
• Principal Investigator: Tanaka Ryo 広島大学, 工学研究院, 助教 (60640795)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2016: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2015: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2014: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: オレフィン重合 / 助触媒 / アルミノキサン / クラスター化合物 / 有機ホウ素化合物 / Lewis酸性

Outline of Final Research Achievements

Boron-moiety-containing aluminoxanes were prepared from Me3Al and various arylboronic acids and compared its cocatalyst ability of olefin polymerization with methylaluminoxane (MAO), which is versatile activator of transition-metal catalysts. Incorporation of electron-withdrawing group and boron atoms to MAO greatly improved the cocatalyst ability of propylene polymerization using various group 4 metal complexes. Several spectroscopic analyses such as DOSY, 27Al, 11B NMR and IR spectroscopy revealed that the increase of cocatalyst ability is owing to the increase of Lewis acidity and bulkiness of aluminum by the incorporation of boron moieties.

Research Products

• [Journal Article] The preparation of boron-containing aluminoxanes and their application as cocatalysts in the polymerization of olefins (2016)
  • Author(s): Tanaka, R.; Hirose, T.; Nakayama, Y.; Shiono, T.
  • Journal Title: Polymer Journal Volume: 48 Issue: 1 Pages: 67-71
  • DOI: 10.1038/pj.2015.81
  • NAID: 40020685239
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 新規含ホウ素アルミニウム錯体の合成とオレフィン重合触媒としての応用 (2014)
  • Author(s): 田中亮, 廣瀬貴彰，中山祐正, 塩野毅
  • Journal Title: 次世代ポリオレフィン総合研究 Volume: 8 Pages: 59-62
  • Acknowledgement Compliant
• [Presentation] 13族元素の特徴を生かした立体特異的重合反応の開発 (2016)
  • Author(s): 田中 亮
  • Organizer: 2016年日本化学会中国四国支部大会
  • Place of Presentation: 香川大学
  • Year and Date: 2016-11-05
• [Presentation] 含ホウ素アルミノキサンを助触媒として用いたオレフィン重合 (2016)
  • Author(s): 田中 亮, 廣瀬 貴彰, 中山 祐正，塩野 毅
  • Organizer: 高分子学会第65年次大会
  • Place of Presentation: 神戸国際会議場
  • Year and Date: 2016-05-25
• [Presentation] Effect of the protic source on the preparation of aluminoxane and its activation behavior of olefin polymerization catalysts (2015)
  • Author(s): Tanaka, R.
  • Organizer: World Polyolefin Congress (WPOC 2015)
  • Place of Presentation: 首都大学東京
  • Year and Date: 2015-11-24
  • Int'l Joint Research / Invited
• [Presentation] Preparation of boron-containing aluminoxane as a cocatalyst of olefin polymerization (2015)
  • Author(s): Tanaka, R.
  • Organizer: IUPAC 11th International Conference on Advanced Polymers via Macromolecular Engineering (APME2015)
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2015-10-21
  • Int'l Joint Research
• [Presentation] 廣瀬 貴彰, 田中 亮, 中山 祐正, 塩野 毅 (2014)
  • Author(s): 新規オレフィン重合助触媒を志向したアルミニウム錯体の合成
  • Organizer: 第29回中国四国地区高分子若手研究会
  • Place of Presentation: サンポートホール高松
  • Year and Date: 2014-10-30
• [Presentation] 嵩高いボロン酸を用いた新規オレフィン重合助触媒の合成・構造および性質 (2014)
  • Author(s): 廣瀬 貴彰, 田中 亮, 中山 祐正, 塩野 毅
  • Organizer: 第63回高分子討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2014-09-24
• [Presentation] 新規含ホウ素アルミニウム錯体の合成とオレフィン重合触媒としての応用 (2014)
  • Author(s): 田中 亮, 廣瀬 貴彰, 中山 祐正, 塩野 毅
  • Organizer: 第9回ポリオレフィン総合研究会
  • Place of Presentation: 首都大学東京秋葉原サテライトキャンパス
  • Year and Date: 2014-08-07
• [Presentation] 嵩高いホウ素化合物を用いたアルミニウム錯体の合成と新規重合助触媒としての応用 (2014)
  • Author(s): 廣瀬 貴彰, 田中 亮, 中山 祐正, 塩野 毅
  • Organizer: 第63回高分子学会年次大会
  • Place of Presentation: 名古屋国際会議場
  • Year and Date: 2014-05-29