• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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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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• v.19 no.12
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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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• v.54 no.4
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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.

• 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 Science and Technology
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• v.5 no.3
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• pp.200-206
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• 1994

• Polymer Science and Technology
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• v.5 no.3
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• pp.215-226
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• 1994

• Bulletin of the Korean Chemical Society
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• v.18 no.12
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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.

• Polymer Science and Technology
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• v.5 no.3
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• pp.207-214
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• 1994

• 한국정보디스플레이학회:학술대회논문집
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• 2003.07a
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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.