Article
  • Copolymerization of Ethylene and 1-Hexene via Polymethylene Bridged Cationic Dinuclear Constrained Geometry Catalysts
  • Bian FL, Que DHD, Lyoo WS, Lee DH, Noh SK, Kim YM
  • 폴리메틸렌 다리로 연결된 양이온 이핵 CGC를 이용한 에틸렌과 1-헥센의 공중합
  • 비안팽링, 당황단웨이, 류원석, 이동호, 노석균, 김용만
Abstract
We have prepared the dinuclear half-sandwich CGC(constrained geometry catalyst) with polymethylene bridge [Zr((η5：η1-C9H5SiMe2NCMe3)Me2)2 [(CH2)n] [n=6(4), 9(5), 12(6)] by treating 2 equivalents of MeLi with the corresponding dichlorides compounds. To study the catalytic behavior of the dinuclear catalysts we conducted copolymerization of ethylene and 1-hexene in the presence of three kinds of boron cocatalysts, Ph3C+[B(C6F5)4]-(B1), B(C6F5)3 (B3), and Ph3C+[(C6F5)3B-C6F4-B(C6F5)3]2-(B2). It turned out that all active species formed by the combination of three dinuclear CGCs with three cocatalyst were very efficient catalysts for the polymerization of olefins. The activities increase as the bridge length of the dinuclear CGCs increases. At the same time the dinuclear cocatalyst exhibited the lowest activity among three cocatalysts. The prime observation is that the dinuclear cocatalyst gave rise to the formation of the copolymers with the least branches on the polyethylene backbone.

길이가 다른 폴리메틸렌 다리로 연결된 이핵 CGC(constrained geometry catalyst)[Zr(η5：η1-C9H5 -SiMe2NCMe3)Me2]2 [(CH2)n] [n=6(4), 9(5), 12(6)]를 2 당량의 MeLi과 대응되는 염소화합물을 반응시켜 합성하고 이들의 구조를 확인하였다. 합성된 이핵메탈로센의 중합 특성을 에틸렌과 1-hexene의 공중합을 통해 조사하였다. 이때에 사용된 조촉매로는 일반 조촉매 Ph3C+[B(C6F5)4]- (B1)과 (B(C6F5)3 (B3)그리고 이핵조촉매 Ph3C+[(C6F5)3B-C6F4-B(C6F5)3]2- (B2)을 이용하였다. 중합 결과 촉매의 활성은 이핵메탈로센에서는 다리길이가 길수록 크게 나타났으며, 조촉매에서는 이핵조촉매가 가장 낮은 활성을 보였다. 조촉매의 특성은 공중합체에 존재하는 가지의 함량에서 잘 나타났다. 이핵조촉매(B2)를 사용하면 가장 가지수가 작은 고분자가 생성되었고, 조촉매 B3에서 가장 많은 가지를 가진 공중합체가 생성되었다.

Keywords: constrained geometry catalyst; ethylene copolymerization; cationic dinuclear metallocene

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  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2007; 31(6): 497-504

    Published online Nov 25, 2007

  • Received on Jul 4, 2007
  • Accepted on Sep 6, 2007