Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Preparation of (n-BuCp)2ZrCl2 Catalyst Supported on SiO2/MgCl2 Binary Support and its Ethylene-1-hexene Copolymerization

SiO2/MgCl2 이원 담체에 담지된 (n-BuCp)2ZrCl2 합성과 에틸렌-1-헥센 공중합

  • Carino, Ann Charise (Department of Chemical Engineering, Kongju National University) ;
  • Park, Sang Jun (Department of Chemical Engineering, Kongju National University) ;
  • Ko, Young Soo (Department of Chemical Engineering, Kongju National University)
  • Received : 2018.05.09
  • Accepted : 2018.05.16
  • Published : 2018.08.10
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Abstract

In this study, $(n-BuCp)_2ZrCl_2$, was supported on $SiO_2/MgCl_2$ binary support. Before supporting the catalyst, the $SiO_2/MgCl_2$ binary support was surface treated with three different alkyl aluminum compound, namely trimethylaluminum, triethylaluminum, and ethylaluminum sesquichloride. The synthesized surface-treated $SiO_2/MgCl_2$ supported metallocene catalysts were used for the copolymerization of ethylene and 1-hexene. Their catalytic properties and performances were analyzed through BET, XPS analysis, ICP-AES analysis, and FE-SEM. While the resulting copolymers were analyzed through DSC analysis, GPC analysis, 13C-NMR analysis, and FE-SEM. The analysis of synthesized surface-treated $SiO_2/MgCl_2$ supported metallocene catalysts showed that the Zr content of these catalysts is relatively lower compared to that of the catalyst supported on $SiO_2$. This could be attributed to the reduction in the surface area of $SiO_2$ due to the presence of recrystallized $MgCl_2$ and alkyl aluminum. Furthermore, they exhibited a better copolymerization activity compared to that of $SiO_2$ supported catalyst, particularly the EASC-surface treated binary support, which has the highest activity of 1.9 kg PE/($mmol-Zr^*hr$) because EASC acts as a strong Lewis acid. It could also be observed that the larger the ligand of alkyl aluminum used, the rougher the particle surface of the resulting polymer.

본 연구에서는 $(n-BuCp)_2ZrCl_2$를 $SiO_2/MgCl_2$ 이원 지지체에 담지시켰다. 촉매를 담지하기 전, $SiO_2/MgCl_2$ 이원 지지체를 3종의 알킬알루미늄 화합물, 트리메틸알루미늄, 트리에틸알루미늄 또는 에틸알루미늄 세스퀴클로라이드로 표면처리 하였다. 합성된 표면 처리된 $SiO_2/MgCl_2$에 담지된 메탈로센 촉매로 에틸렌 및 1-헥센의 공중합을 하였다. 촉매 특성 및 성능을 BET, XPS 분석, ICP-AES 분석 및 FE-SEM을 통해 비교 분석하였다. 생성된 공중합체를 DSC 분석, GPC 분석, 13C-NMR 분석 및 FE-SEM을 통해 비교 분석하였다. 합성된 $SiO_2/MgCl_2$ 담지된 메탈로센 촉매의 분석은 이들 촉매의 Zr 함량이 $SiO_2$에 담지된 촉매에 비해 상대적으로 낮다는 것을 보여 주었다. 이것은 재결정된 $MgCl_2$ 및 알킬알루미늄의 존재로 인한 $SiO_2$의 표면적 감소에 기인할 수 있다. 또한, $SiO_2/MgCl_2$ 담지된 메탈로센 촉매는 $SiO_2$에 담지된 메탈로센 촉매보다 활성이 높았으며 이 중 EASC-표면 처리 이원 지지체에 담지된 메탈로센촉매가 1.9 kg PE/($mmol-Zr^*hr$)의 가장 높은 활성을 보였다. 이것은 EASC가 강한 루이스 산으로 작용하기 때문이다. 또한, 사용된 알킬알루미늄의 리간드가 클수록 생성된 중합체의 입자 표면이 더 거칠었다.

Keywords

References

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