非常に活発なオレフィンポリメリゼーションとコポリメリゼーションのためのステリックに拡張された"制約された幾何学触媒":不屈のコモノマー効果
Levi J Irwin1, Joseph H Reibenspies, Stephen A Miller
1Department of Chemistry, Texas A&M University, College Station, TX 77843-3255, USA.
Journal of the American Chemical Society
|December 23, 2004
まとめ
オクタメチロタヒドロディベンゾフローレンの部分を持つ新しい制約型幾何学触媒は,アルファ-オレフィンに対して高い反応性を示す. この触媒は,メチルアルミノキサン (MAO) で活性化されると,エチレン共ポリマー化におけるコモノマー濃度に比例する活性を示します.
科学分野:
- 有機金属化学 有機金属化学
- ポリマーサイエンスの科学
- カタリシス カタリシス カタリシス
背景:
- 制限された幾何学触媒 (CGC) は,オレフィンポリメリゼーションにおいて極めて重要です.
- 金属中心の周りのステリック塊は,触媒の活性とポリマーの特性に影響します.
- 大容量のリガンドを組み込むことは,触媒の性能を向上させることができます.
研究 の 目的:
- 14Aオクタメチロタヒドロディベンゾフローレン基を組み込んだステリック膨張CGCを合成し,特徴づけること.
- オレフィンポリメリゼーションにおける新しい触媒 (1) の触媒活性,特にアルファ-オレフィンに対する触媒活性を評価する.
- エチレンとより高いアルファ-オレフィンとの触媒の共ポリメリ化行動を調査する.
主な方法:
- 制約された幾何学の触媒Me2Si (((eta1-C29H36) (((eta1-N-tBu) ZrCl2.OEt2 (1) の合成について
- カタリストの固体構造分析.
- メチルアルミノキサン (MAO) で活性化された触媒を用いたオレフィンポリメリゼーションおよびコポリメリゼーション実験.
- ポリメリゼーション活動の運動分析.
主要な成果:
- 触媒 (1) の固体構造は,空間的なアクセシビリティが顕著であることを示しています.
- カタリスト (1) /MAOは,アルファオレフィンに対する異常な反応性を示し,エチレンに対する反応性を上回る.
- エチレンとの共ポリメリゼーションにおける活性性は,4メチル-1-ペンテンまたは1オクトン濃度に線形かつ連続的に比例する.
結論:
- ステリカルに拡張されたリガンドの設計は,触媒のアクセシビリティと反応性を高めます.
- 触媒は,エチレンよりも高いアルファ-オレフィンに対する選択的反応性を示す.
- アクティビティとコモノマー濃度の間の観察された線形関係は,コポリメリゼーション運動学への洞察を提供します.
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