• 한국응용과학기술학회지
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• 제33권4호
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• pp.698-705
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• 2016

본 연구는 메탈로센 촉매를 이용한 폴리에틸렌 왁스의 중합과 그 특성에 관한 연구를 진행하였다. 폴리에틸렌 왁스 중합에 사용되는 다양한 중합 조건을 시도하였다. 낮은 분자량을 갖는 폴리에틸렌 중합에 널리 이용되는 Ziegler-Natta 촉매와는 다른 여러가지 구조의 리간드를 갖는 다양한 메탈로센 촉매가 중합 특성에 미치는 영향에 대한 연구와 촉매의 수소 반응성에 관한 연구를 진행하였다. 또한 연쇄이동제인 수소량에 따른 분자량의 변화와 에틸렌 가스의 비율에 따른 분배를 관찰하였다. 마지막으로 본 연구에서는 폴리에틸렌 왁스의 중합에 적합한 메탈로센 촉매 구조를 제안하였다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.556-556
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• 2012

Transition metal-based organometallic complexes have shown great talents as a catalyst in various reactions. Designing organic molecules and coordinating them to such active centers have been a promising route to control the catalytic natures. Metallocene, which has transition metal atoms sandwiched by aromatic rings, is one of the representative systems for organometallic catalysts. Group 4-based metallocene catalysts have been most commonly used for the production of polyolefins, which have great world-wide markets in the real life. Graphenes and carbon nanotubes (CNTs) were composed of extended $sp^2$ carbon networks, showing high electron mobility as well as have extremely large steric bulkiness relative to metal centers. We were inspired by these characteristics of such carbon-based nano-materials and assumed that they could intimately interact with active centers of metallocene catalysts. We examined this hypothesis and, recently, reported that CNTs dramatically changed catalytic natures of group 4-based catalysts when they formed hybrid systems with such catalysts. In conclusion, we produced hybrid materials composed of group-4 based metallocenes, $Cp_2ZrCl_2$ and $Cp_2TiCl_2$, and carbon-based nano-materials such as RGO and MWCNT. Such hybrids were generated via simple adsorption between Cp rings of metallocenes and graphitic surfaces of graphene/CNT. The hybrids showed interesting catalytic behaviors for ethylene polymerizations. Resulting PEs had significantly increased Mw relative to those produced from free metallocene-based catalytic systems, which are not adsorbed on carbon-based nano-materials. UHMWPEs with extremely high Mw were obtained at low Tp.

• Bulletin of the Korean Chemical Society
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• 제19권12호
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• pp.1310-1314
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• 1998

The oligo(methylsilene) (1) was treated with the group 4 metallocene Cp2MCl2/Red-Al (M = Ti, Zr, Hf) combination catalysts and with the group 6 metal carbonyl M(CO)6 (M = Cr, W) catalysts, producing the modified, cross-linked polymers. The average molecular weights and percent ceramic residue yields of modified polymers increase as the catalyst goes down from Ti to Hf and similarly as the catalyst goes down from Cr to W. An interrelationship between average molecular weights and percent ceramic residue yield is found within the respective group of catalysts, but is not observed as the catalyst goes down from Ti to W. The polymers modified with the group 4 metallocene combination catalysts have higher molecular weights and similar percent ceramic residue yields as compared to the polymers modified with the group 6 metal carbonyl catalysts. The catalytic activities of group 4 metallocene combinations appear to be higher -100 ℃, but to be lower at very high temperature than those of group 6 metal carbonyls.

• Elastomers and Composites
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• 제54권4호
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• pp.286-293
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• 2019

In this study, flexible poly(ethylene-ter-1-hexene-ter-divinylbenzene) was prepared using four types of metallocene catalysts (rac-Et(Ind)₂ZrCl₂, rac-SiMe₂(Ind)₂ZrCl₂, rac-SiMe₂(2-Me-Ind)₂ZrCl₂, (C₅Me₅)TiCl₂[O-2,6-ⁱPr₂(C₆H₃)]) and two types of borate catalysts (trityl tetrakisborate and dimethylanilinium tetrakisborate). The yield, catalytic activity, molecular weight, structure, composition, and thermal properties of the terpolymers prepared using the various catalysts and cocatalyst systems were evaluated. Epoxidation of the terpolymers was successfully performed and this transformation was studied by ¹H NMR and FTIR.

• 한국응용과학기술학회지
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• 제34권4호
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• pp.857-865
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• 2017

본 연구는 폴리에틸렌 중합에 이용되는 Ziegler-Natta 촉매와는 다른 Indene및 Cyclopent adien을 기반으로 하는 다양한 메탈로센 촉매를 사용하여 폴리에틸렌 왁스를 중합하고 중합한 폴리에틸렌 왁스의 특성에 대해 분석하고 평가 하였다. 폴리에틸렌 왁스 중합은 각 다른 구조의 리간드를 포함하는 메탈로센 촉매에 대하여 중합온도, 연쇄이동제로 사용되는 수소와 에틸렌가스의 비율을 조정하여 다양한 조건하에서 중합을 시도 하였으며 그에 따른 분자량과 분자량 분포, 촉매 수율을 비교 분석하였다. 결과적으로 본 연구를 통하여 저분자량을 가지며 좁은 분자량 분포를 가지기에 적합한 메탈로센 촉매의 구조를 제안하였으며 이상적인 폴리에틸렌 왁스를 중합 할 수 있었다.

• 한국고분자학회지:고분자과학과기술
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• 제5권3호
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• pp.200-206
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• 1994

• 한국고분자학회지:고분자과학과기술
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• 제5권3호
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• pp.215-226
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• 1994

• Bulletin of the Korean Chemical Society
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• 제18권12호
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• pp.1264-1268
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• 1997

The poly(methylsilene) (1) was modified with the group 4 metallocene Cp2MCl2/Red-Al (M = Ti, Zr, Hf) combination catalyst and with the group 6 metal carbonyl M(CO)6 (M = Cr, Mo, W) catalyst, producing the highly cross-linked isoluble polymer and the lowly cross-linked soluble polymer, respectively. An interrelationship between molecular weight and percent ceramic residue yield with metal within the respective group was not found. The polymers modified with the group 4 metallocene combination catalysts have higher molecular weight and lower percent ceramic residue yield than the polymers modified with the group 6 metal carbonyl catalysts do. The catalytic activity of group 4 metallocene combinations appears to be higher at ∼100 ℃, but to be lower at very high temperature than those of group 6 metal carbonyls. The pyrolysis of the modified 1 yielded SiC ceramic.

• 한국고분자학회지:고분자과학과기술
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• 제5권3호
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• pp.207-214
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• 1994

• 한국정보디스플레이학회:학술대회논문집
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• 한국정보디스플레이학회 2003년도 International Meeting on Information Display
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• pp.1028-1029
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• 2003

The copolymerization of ethylene and norbornene was carried out with ansa-metallocene and modified methylaluminoxane (MMAO) cocatalyst. The copolymerization behavior was changed with the structure of metallocene catalysts. In addition the catalyst activity was dependent on the structure of MMAO, i.e.. MMAO-4 which contains less i-butyl group compared to MMAO-3A exhibited higher catalyst activity than MMAO-3A. The glass transition temperature and the composition of the produced copolymer were not affected by MMAO type.