• Macromolecular Research
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• v.9 no.2
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• pp.71-83
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• 2001

The metallocene compounds had been applied to the polymerizations of olefins and vinyl monomers with methylaluminoxane (MAO) cocatalyst, and they have usually one transition metal atom per molecule, i.e., mononuclear metallocene. Recently it has been found that the dinuclear metallocene compounds containing two transition metal atoms exhibit the peculiar polymerization behaviors for olefins and vinyl monomers. In this article, the dinuclear metallocenes are classified into four groups of dinuclear bent-metallocene, dinuclear ansa-metallocene, dinuclear constrained geometry catalyst and dinuclear half-metallocene, and then the synthesis of dinuclear metallocene of each group as well as the polymerization behaviors for ethylene, propylene, and styrene are described.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.759-761
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• 2006

The compound B(C6F5)3 and its variations have been widely employed as alkyl carbanion abstracting reagents to produce metallocene cations for olefin polymerization.1-3 Weakly coordinating anions containing boron can greatly improve the activity of metallocene catalysts used in industrial olefin polymerization4 and thus group IV and V metallocene complexes of the organohydroborate anions have been intensively investigated.5 Recently, many organohydroborate metallocene complexes have been reported by Shore and co-workers.6-8 A common structural feature of those complexes is the three-center two electron M-H-B bond, like that observed in transition metal tetrahydroborate complexes but the reactivity and fluxional behavior of organohydroborate complexes are unlike those of the tetrahydroborate analogues.6 Although many of those metallocenes have been synthesized, few complexes could be used in the olefin polymerization and then this laboratory has been involved in the chemistry of the cyclic organohydroborate anions, and their group IV metallocene derivatives for the catalyst.9 Described here is recent work that led to the preparation of a novel cyclic organohydroborate hafnocene complex (h5-C5H5)2Hf ？(μ-H)2BC8H14 ,Cl. The hafnocene complex contains the three-center two electron bond Hf-H-B10 in which the hydride abstraction for olefin polymerization may occur.

• Polymer Science and Technology
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• v.5 no.3
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• pp.189-199
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• 1994

• 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.

• 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.

• Polymer Science and Technology
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• v.7 no.4
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• pp.377-383
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• 1996

• 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

• 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.23 no.9
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• pp.1343-1346
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• 2002