Article
  • Copolymerization of Ethylene and Cycloolefin with Metallocene Catalyst: Ⅰ. Effect of Catalyst
  • Lee DH, Jung HK, Kim WS, Min KE, Park LS, Seo KH, Kang IK, Noh SK
  • 메탈로센 촉매를 이용한 에틸렌과 시클로올레핀의 공중합: Ⅰ. 촉매의 영향
  • 이동호, 정희경, 김우식, 민경은, 박이순, 서관호, 강인규, 노석균
Abstract
The copolymerization to ethylene (E) and norbornene (N) was examined by using various metallocene catalysts and modified-MAO(MMAO) cocatalyst. For C2-symmetry catalysts such as rac-Et(Ind)2ZrCl2, Me2Si(Ind)2ZrCl2, Me2Si(Cp)2ZrCl2 and Cs-symmetrical iPr(FluCp)ZrCl2 as well as CGC and di-briged zirconocene, the effects of catalyst structure and [N]/[E] feed ratio on catalyst activity, thermal property and [N] content of copolymer (COC) was investigated. For rac-Et(Ind)2ZrCl2 catalyst of a constant [N]/[E] feed ratio, the appropriate conditions of [Al]/[Zr] mole ratio, polymerization temperature and cocatalyst structure were found to be 3000, 40℃, MMAO cocatalyst, respectively. As [N]/[E] feed ratio increased, the incorporation of norbornene to copolymer increased while the activity of catalyst decreased except fro iPr(FluCp)ZrCl2. With consideration of catalyst activity as well as N content, it was found that rac-Et(Ind)2ZrCl2/MMAO system exhibited relatively high activity and controllable Tg. Monomer reactivity ratio was determined by Kelen-00 method.

다양한 종류의 메탈로센 촉매와 공촉매인 개질-MAO(MMAO)을 이용한 에틸렌(E)과 노르보르넨(N)의 공중합에서 중합조건이 촉매 활성 및 공중합체의 구조와 성질 등에 미치는 영향을 조사하였다. 즉 C2-대칭구조를 가지는 rac-Et(Ind)2ZrCI2, M2Si(Ind)2ZrCl2, Me2Si-(Cp)2ZrCl2 및 CS-대칭구조를 가지는 iPr(FluCp)ZrCl2, 그리고 constrained geometry catalyst(CGC)와 이중다리(di-bridged) 지그코노센 등의 다양한 메탈로센 촉매를 사용하여 [N]/[E]공급비에 따른 촉매 활성, 공중합체(COC)의열적 성질 및 N 함량을 조사하였다. rac-Et(Ind)2ZrCI2를 촉매로 사용한 경우에 공촉매의 몰비, 중합 온도 및 공촉매 종류 등의 중합조건을 조사한 결과 [Al]/[Zr]=3000, 40℃, MMAO 공촉매 등이 적합하였다. [N]/[E]공급비가 증가됨에 따라 COC내의 N 함량이 증가하는 일반적인 경향을 보였으나, 촉매 활성은 감소하였으나 Cs-대칭구조의 경우에는 증가하였다 촉매활성과 N함량 등을 고려해 보면 rac-Et(Ind)2ZrCI2/MMAO계에서 비교적 높은 촉매 활성과 COC의 Tg제어가 용이한 결과를 얻을 수 있었다. 촉매종류에 따른 단랑체의 반응성비를 Kelen-Tudos방법으로 구하였다.

Keywords: metallocene; ethylene; morbornene; copolymer; cycloolefin

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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

  • 2000; 24(4): 445-452

    Published online Jul 25, 2000