• Preparation of Tetraphenyl Substituted Disiloxane Bridged Ansa-Metallocene and Investigation of Its Polymerization Properties
  • Jung J, Noh SK, Lee H, Park SK, Lee DH, Kang KS
  • Tetraphenyl 치환제를 가진 Disiloxane 다리 Ansa-Metallocene의 합성과 중합연구
  • 정재훈, 노석균, 이헌봉, 박성근, 이동호, 강경석
Abstract
The tetraphenyl substituted disioxane bridged ansa-zirconocene has been generated to probe the effect of bridging ligand on metallocene polymerization. The indicated zirconocene has been synthesized by the reaction of ZrClsub>4 with the distannylated precursor compound. The new disiloxane bridged ansa-metallocene was characterized by 1H and 13 C NMR, mass analysis, and elemental analysis. Ethylene polymerization was carried out to investigate the polymerization properties of the prepared complex. Polymerization experiments exhibited that the catalytic activity increases with the increase in polymerization temperature as well as the amount of cocatalyst. On the other hand, the molecular weights of the polymers decreased with the increase in polymerization temperature. It turned out that tetraphenyl replacement caused about 50 to 70% activity reduction. The most important feature associated in tetramethyl to tetraphenyl substitution was that molecular weights of the polymers from the tetraphenyl substituted complex were enormously improved comparing to those of th polymers from the tetramethyl one.

본 연구에서는 ansa-metallocene 화합물의 구조 중 다리리간드가 촉매의 특성에 미치는 영항을 조사하기 위하여 tetraphenyl이 치환된disiloxane 기간드를 가진 ansa-metallocene을 합성하여 중합특성을 조사하였다. 새로운 메탈로센으로서 tetraphenyl치환제를 가진 disiloxane bridged ansa-metallocene은 해당되는 리간드의 trimethyltin 전구체를 ZrCl4>2와 반응시켜 성공적으로 합성되었다. 전구체를 사용하지 않고 리간드의 금속염과 ZrCl4>2 반응시켜서도 ansa-metallocene을 제조할 수 있으나 수율이 10%정도롤 매우 낮았다. 생성된 화합물은 수소 및 탄소 NMR과 질량분석을 통해 구조와 조성이 확인되었다. 합성된 메탈로센의 에틸렌 중합결과 중합온도가 상승할수록 촉매의 활성은 증가하는 반면 생성되는 고분자의 분자량은 감소하는 메탈로센 중합특성의 일반적인 경향을 나타내었다. 촉매의 활성은 tetramethyl 다리리간드가 합성된 tetraphenyl 다리리간드보다 2배정도 높았으나 생성된 폴리에틸렌의 분자량은 tetraphenyl 리간드로 제조된 고분자가 40-100배나 컸다.

Keywords: ansa-zirconcene; tetraphenyl disiloxane bridge; polymerization; bridge effect

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This Article

  • 1999; 23(2): 189-196

    Published online Mar 25, 1999