• Proceedings of the KAIS Fall Conference
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• 2003.06a
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• pp.337-339
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• 2003

본 연구에서는 여러 종류의 담체 중에서 Davison 952 실리카를 선택하여 실리카 표면의 하이드록시기의 양을 진공 열처리 방법을 사용하여 조절하였다. 표면 처리된 실리카를 사용하여 담지촉매를 제조한 후 폴리에틸렌(PE) 중합을 수행, 소성온도에 따른 실리카 표면의 하이드록시기 양의 변화와 담지되는 조촉매(MAO) 및 메탈로센 촉매의 양과의 상관관계를 조사하였고 실리카 표면처리와 중합 활성도 간의 상관관계를 고찰하였다. 폴리에틸렌(PE) 중합 결과 메탈로센 촉매가 가장 많이 담지된 200℃ 보다 400℃ 또는 600℃에서 메탈로센 당(g PE/mol Zr)활성도가 높았으며, 담체에 흡착된 MAO와 메탈로센의 비율이 400℃와 600℃에서 가장 크게 나타났다.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.4 no.3
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• pp.204-208
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• 2003

본 연구에서는 여러 종류의 담체 중에서 Davison 952 실리카를 선택하여 실리카 표면의 하이드록시기의 양을 진공열처리 방법을 사용하여 조절하였다. 표면 처리된 실리카를 사용하여 담지촉매를 제조한 후 폴리에틸렌 (PE) 중합을 수행, 소성온도에 따른 실리카 표면의 하이드록시기 양의 변화와 담지되는 조촉매(MAO) 및 메탈로센 촉매의 양과의 상관관계를 조사하였고 실리카 표면처리와 중합 활성도 간의 상관관계를 고찰하였다. 폴리에틸렌(PE) 중합 결과 메탈로센 촉매가 가장 많이 담지된 200℃ 보다 400℃ 또는 600℃ 에서 메탈로센 당(g PE/mol Zr) 활성도가 높았으며, 담체에 흡착된 MAO와 메탈로센의 비율이 400℃와 600℃에서 가장 크게 나타났다.

• Polymer Science and Technology
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• v.9 no.1
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• pp.17-23
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• 1998

지금까지 다양한 종류의 촉매 시스템에 의한 폴리올레핀 제조법에 관하여 알아보았다. 특히, 기존의 불균일계 착체 전이 금속 촉매 시스템 및 균일계 촉매 시스템에 의한 폴리올레핀 합성법과 비교하여 활성도 및 입체 규칙성 측면에서 최근 세계적인 '핫 잇슈'가 되고 있는 메탈로센 촉매 시스템을 이용한 폴리올레핀 제조법에 대하여 검토하였다. 이들에 대한 상세한 반응기구 및 반응 속도론(kinetics)에 대한 사항은 생략하였다. 이들에 대한 상세한 설명들은 여러 문헌에 잘 소개되어 있으며, 메탈로센 촉매 제조를 위한 다양한 리간드 합성법도 문헌에 잘 소개되어 있다. 이미 설명한 폴리올레핀 신합성법에 사용되는 메탈로센 촉매 및 비메탈로센계 촉매 이외에도 최근 크롬계 촉매 역시 올레핀 중합에 긴요하게 사용될 수 있을 것으로 판단된다. 이러한 관점에서, 현재 국내에서 폴리올레핀 공급과잉 현상은 새로운 기술에 의한 각종 그레이드(grade)의 특화만이 문제점 해결의 지름길이 될 것이라 판단된다.

• Journal of the Korean Applied Science and Technology
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• v.33 no.4
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• pp.698-705
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• 2016

In this study, we have studied the polymerization of polyethylene wax using metallocene catalysts and its physical properties. Various polymerization conditions were tried for polymerization of polyethylene wax. We have evaluated hydrogen reactivity and studied on characteristics of polymerization effected by ligand structure of metallocene catalysts against Ziegler-Natta catalysts which are widely used for polymerization of polyethylene. We have also checked hydrogen used for chain transfer agent, molecular weight change and distribution by different ratios of ethylene gas. Finally, we suggest proper structure of metallocene catalysts for polymerization of polyethylene wax.

• Journal of the Korean Applied Science and Technology
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• v.34 no.4
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• pp.857-865
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• 2017

This study was conducted to analyze and characterize the properties of polyethylene wax polymerized and polymerized using various metallocene catalysts based on Indene and Cyclopentadien, which are different from Ziegler-Natta catalysts used in polyethylene polymerizatio n. The polymerization of polyethylene wax was carried out under various conditions by adjusting the polymerization temperature and the ratio of hydrogen gas used as a chain transfer agent and ethylene gas to metallocene catalysts containing ligands of different structures. The molecular weight and molecular weight distribution, The catalyst yields were compared and analyzed. As a result, the structure of a metallocene catalyst suitable for having a low molecular weight and a narrow molecular weight distribution was proposed and the ideal polyethylene wax could be polymerized.

• Polymer(Korea)
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• v.25 no.6
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• pp.833-839
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• 2001

The crystallization characteristics of metallocene linear low density polyethylene was investigated by small angle light scattering and comparison was made with Ziegler-Natta linear low density polyethylene. The special efforts were made to find out the effects of branching number, length of branching and co-monomer content of m-LLDPE on the crystallization behavior of m-LLDPE. It was found that m-LLDPE has longer induction time to start crystallization from the amorphous state than that of conventional LLDPE with similar branching number, but the rate of crystallization seems not change much in both LLDPEs. Lowering of branching number in m-LLDPE resulted in both increasing of rate of crystallization and reducing induction time to crystallize. In general, the maximum size of spherulites of m-LLDPE is bigger than that of conventional LLDPE.

• Polymer(Korea)
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• v.32 no.6
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• pp.566-572
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• 2008

Polyethylene has been prepared via metallocene catalysts [(TMDS)$Cp_2$]$ZrCl_2$, 1, and [$(n-Bu)_2Cp_2$]$ZrCl_2$, 2, in the presence of hydrogen as a chain transfer reagent. Increase of hydrogen flow to the polymerization reactor resulted in the drop of catalytic activity, reduction of molecular weight of polyethylene, getting narrow of molecular weight distribution of polyethylene, and melting point of the polyethylene wax. It should be noticed that it was possible to control molecular weight down to 1500 and melting temperature to 60 $^\circ$C of polyethylene wax using the catalyst 1 that has been developed by authors as well as the catalyst 2 from Exxon.

• Journal of the Korean Chemical Society
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• v.41 no.9
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• pp.502-517
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• 1997

This review deals with (1) the catalytic systems and mechanisms for the dehydropolymerization of silanes to polysilanes, (2) the dehydropolymerization of versatile silanes, (3) the preparation of polysilane derivatives, and (4) the applications of catalytic dehydropolymerizing systems to ceramics. The efforts to maximize the catalytic efficiency of group 4 metallocenes were introduced. Finally, the future of this dehydropolymerizing techniques of silanes was foreseen.

• Korean Chemical Engineering Research
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• v.54 no.4
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• pp.574-581
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• 2016

In this study, CNT functionalized with pyrrolidine ring via 1,3-dipolar cycloaddition reaction with various amino acid and aldehyde was synthesized. Metallocene was subsequently immobilized on the functionalized CNT and CNT/polyethylene composite was prepared via in-situ ethylene polymerization. The polymerization activities of metallocene supported on CNT functionalized with glycine and benzaldehyde (Gly+BA-CNT) were similar to those of metallocene supported on CNT functionalized with N-benzyloxycarbonylglycine and paraformaldehyde (Z-Gly+PFA-CNT) although its Zr content was lower than that of Z-Gly+PFA-CNT. In the case of metallocene supported on Z-Gly+PFA-CNT, the even distribution of active sites hindered the diffusion of ethylene monomer and cocatalyst MAO due to steric hindrance during ethylene polymerization. Compared to polyethylene produced from homogeneous metallocene catalysts, CNT/PE composites had a higher initial degradation temperature ($T_{onset}$) and maximum mass loss temperature ($T_{max}$). It suggests that pyrrolidine functionalized CNT is uniformly dispersed and strongly interacted with the PE matrix, enhancing the thermal stability of PE.

• Polymer(Korea)
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• v.24 no.4
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• pp.445-452
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• 2000

The copolymerization of ethylene (E) and norbornene (N) was examined by using various metallocene catalysts and modified-MAO(MMAO) cocatalyst. For $C_2$-symmetry catalysts such as rac-Et(Ind)$_2$ZrC $l_2$, M $e_2$Si(Ind)$_2$ZrC $l_2$, M $e_2$Si(Cp)$_2$ZrC $l_2$ and Cs-symmetrical iPr(FluCp)ZrC $l_2$ as well as CGC and di-bridged 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)$_2$ZrC $l_2$ 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, 4$0^{\circ}C$, MMAO cocatalyst, respectively. As [N]/[E] feed ratio increased, the incorporation of norbornene to copolymer increased while, the activity of catalyst decreased except for iPr(FluCp)ZrC $l_2$ With consideration of catalyst activity as well as N content, it was found that rac-Et(Ind)$_2$ZrC $l_2$/MMAO system exhibited relatively high activity and controllable $T_{g}$. Monomer reactivity ratio was determined by Kelen-Tudos method..