Polymer(Korea) (폴리머)

The Polymer Society of Korea (한국고분자학회)
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Polymerization of $\alpha$-Olefin Catalyzed by rac-(EBI) M($NMe_2$)$_2$(M=Zr, Hf)/$AlR_3$/[$Ph_3C$][$B(C_{6}F_{5})$)$_4$]

rac-(EBI) M($NMe_2$)$_2$(M=Zr, Hf)/$AlR_3$/[$Ph_3C$[$B(C_{6}F_{5})$)$_4$ 촉매를 이용한 $\alpha$-올레핀의 중합

  • Kim, Il (Department of Chemical Engineering, University of Ulsan) ;
  • Choi, Chang-Soo (Department of Chemical Engineering, University of Ulsan) ;
  • Kim, Ki-Tae (Department of Chemical Engineering, University of Ulsan)
  • 김일 (울산대학교 공과대학 화학공학부) ;
  • 최창수 (울산대학교 공과대학 화학공학부) ;
  • 김기태 (울산대학교 공과대학 화학공학부)
  • Published : 2000.09.01
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Abstract

Polymerizations of higher $\alpha$-olefins were carried out in toluene by using highly isospecific catalyst, rac-(EBI)M(NMe$_2$)$_2$ (EBI=1,2-ethylenebis-(1-indenyl); M=Zr(rac-1); M=Hf(rac-2)) In the presence of Al(i-Bu)$_3$/[Ph$_3$C][B($C_{6}F_{5}$)$_4$]. The polymerization of high $\alpha$-olefin showed high activity and similar polymerization behavior. The polymerization activity was affected by both monomer size and lateral size of polymer chain. The conversion of monomer to polymer decreases with the increased lateral size in the order of 1-pentene>1-hexene>1-octene>1-decene. The same dependences of melting behavior and intrinsic viscosity of polyolefin on lateral size were observed according to the results obtained by differential scanning calorimetry and intrinsic viscosity. All poly($\alpha$-olefin)s showed very high isotacticity (triad) and the isotacticity increases in the order of poly(1-pentene)$^1H$ NMR and Raman spectra analysis showed that chain transfer to cocatalyst, which generates saturated methyl groups, Is a main chain termination. The $\beta$-hydride eliminations, which generate unsaturated vinylidene, tri-substituted, and vinylene end group. are found to be minor chain terminations.

이소특이성 촉매인 rac-(EBI)M($NMe_2$)$_2$ [EBI=1,2-ethylenebis-(1-indenyl); M=Zr (rac-1), M=Hf(rac-2)와 공촉매계로서 Al(iBu)$_3$/[Ph$_3$C][B($C_{6}F_{5}$)$_4$]를 이용하여 고차 $\alpha$-올레핀의 중합특성을 조사하였다. 고차 $\alpha$-올레핀의 중합은 높은 활성을 나타냈으며, rac-1과 rac-2의 두 촉매계는 유사한 중합거동을 나타냈다. 중합 활성은 단량체의 크기와 중합된 고분자 가지의 길이에 의해 영향을 받았다. 단량체의 전환율은 1-pentene>1-hexene>1-octene>1-decene의 순서로 감소하였다. 또한 합성된 폴리($\alpha$-올레핀)의 고유점도값과 시차주사열분석기에 의한 용융거동도 유사한 경향을 나타냈다. 폴리 ($\alpha$-올레핀)은 매우 높은 이소탁틱도 트리에드를 나타냈으며 poly(1-pentene)$^1H$ NMR과 Raman 스펙트럼을 이용한 고분자 사슬의 말단기 분석 결과로부터, 주로 일어나는 사슬정지반응은 말단에 포화된 메틸기를 생성하는 공촉매로의 전이이며, 소수 반응으로 비닐리덴, 삼차치환 및 비닐렌 이중결합을 생성하는 $\beta$-수소제거 반응이 일어남을 알 수 있었다.

Keywords

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