• 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(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..

• Bulletin of the Korean Chemical Society
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• v.27 no.7
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• pp.1031-1037
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• 2006

New nickel complexes containing novel tetradentate ligands, 4,5-substituted-1,2-bis(pyridine-2-carboxamide)-benzene ligands but lacking alkyl or halide ligands in the coordination sphere have been prepared. They were activated with MMAO (modified methylaluminoxane) to be proven as efficient catalysts for the polymerization of norbornene. Both electron-donating and -withdrawing substituents on the benzene ring and polar solvents enhance the catalytic activity for olefin polymerization. Improvement in thermal stability of the complexes was observed. Some of these complexes were crystallographically determined to have square planar geometry. A plausible mechanism involving dissociation of ligands is proposed.

• Bulletin of the Korean Chemical Society
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• v.25 no.11
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• pp.1648-1652
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• 2004

A set of unprecedented syndiospecific dimethyl- and diethylamino-functionalized polystyrenes was prepared by catalytically polymerizing the corresponding monomers using (pentamethylcyclopentadienyl)titanatrane/MMAO catalytic system. Dialkylamino-functionalized styrene monomers were synthesized by Wittig reaction from the corresponding aldehyde in high yield. The resulting polymers are soluble in polar organic solvents such as THF and show good thermal stability. The chemical transformation of the syndiospecific poly(4-diethylaminostyrene) also gave new polar polymers, namely syndiotactic poly(4-diethylaminostyrene hydrochloride), which is unattainable by traditional synthetic methods.

• Polymer(Korea)
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• v.25 no.4
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• pp.468-475
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• 2001

For copolymerization of ethylene and norbornene initiated by various metallocene catalysts such as $rac-Et(Ind)_2ZrCl_2,\;rac-Me_2Si(Ind)_2ZrCl_2,\;rac-Me_2Si(Cp)_2ZrCl_2,\;and\;(n-BuCp)_2ZrCl_2$ with modified methylaluminoxane(MMAO) cocatalyst, the ${\alpha}$-olefins such as 1-hexene(H), 1-octene and 1-decene were added as a 3rd monomer. In this situation, the effects of the polymerization condition, the catalyst structure as well as the structure and the amount of added ${\alpha}$-olefin on the catalyst activity as well as the properties and structure of polymer were examined. As results, it was found that the catalyst activity and thermal property of polymer depended on not only catalyst structure but also ${\alpha}$-olefin structure. For $rac-Et(Ind)_2ZrCl_2/MMAO$ catalyst system, it was possible to get high activity and controllable $T_g$ of polymer. Among ${\alpha}$-olefins, H as a 3rd monomer exhibited the maximum enhancement in catalyst activity.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.475-476
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• 2006

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.636-646
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• 2009

A series of the noble palladium complexes containing $\beta$-ketoiminate ligands with internal bases, [Pd(${\eta}^3$-allyl)($\beta$- ketoiminate)], [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] and [Pd(Me)($\beta$-ketoiminate)], have been successfully prepared. Crystallographically determined structures showed that these complexes are distorted square planar and pendant bases of the $\beta$-ketoiminate ligands fail to coordinate to the metal in the first two classes of complexes while bases do coordinate in the 3rd class complexes. These complexes are active towards norbornene polymerization on activation with $H(OEt_2)_2BAr^'_4$ (Ar' = 3,5-bistrifluoromethylphenyl) and modified methylalumioxane (MMAO). MMAO is more efficient for the activation for polymerization. Generally, the polymerization activity increases with the following order; [Pd(allyl)($\beta$-ketoiminate)] < [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] < [Pd(Me)($\beta$-ketoiminate)].

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2537-2543
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• 2011

A self-assembled Al-bridged diiminopyridine-based ligand (3) was synthesized and characterized by FT-IR, ESI-MS and NMR spectroscopy. Electron spectral titrations were performed to confirm the formation of a novel trinuclear bis(imino)pyridyl iron(II) complex (4) upon addition of $FeCl_2$ into Al-bridged ligand 3 in methanol solution. Simultaneously, a typical bis(imino)pyridine-iron(II) complex (2) was synthesized and fully characterized. The X-ray crystal study of the iron(II) complex 2 disclosed a five-coordinate, distorted square-pyramidal structure with the tridentate N^N^N ligand and chlorides. The optimal molecular structure of 4 was obtained by means of molecular mechanics, which showed that each iron atom in the complex 4 is surrounded by two chlorides, a tridentate N^N^N ligand and one oxygen atom, supporting considerations about the possibility of six-coordinate geometry from MMAO or the ethylene access. A comparison of 4 with the reference 2 revealed a remarkable decrease of the catalytic activity and MMAO consumption (activity up to $0.41{\times}10^3\;kg\;{mol_{Fe}}^{-1}h^{-1}bar^{-1}$, Al/Fe = 650 for 4 and $7.02{\times}10^3\;kg\;{mol_{Fe}}^{-1}h^{-1}bar^{-1}$, Al/Fe = 1600 for 2).

• Polymer(Korea)
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• v.24 no.6
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• pp.751-756
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• 2000

The copolymerization of ethylene (E) and cycloolefin (CO) was carried out with rac-Et(Ind)$_2$ZrC $l_2$ and MMAO cocatalyst system to examine the effect of CO structure on catalytic behaviors and properties of copolymer (COC). Various cycloolefins such as norbornene (N), 5-phenyl-2-norbornene (PN) and 5-vinyl-2-norbornene (VN) were used as comonomers. With increasing [CO]/[E] feed ratio, the catalytic activity decreased while the glass transition temperature of copolymer increased. With analysis of the structure of E/VN copolymer by FT-IR and $^{l3}$C-NMR, it was found that the cyclic C=C bond of VN comonomer is selectively polymerized and the vinyl C=C bond remains unreacted. The resulting vinyl C=C bond attached into copolymer provided the functionalization moiety using glycidyl methacrylate.e.

• Bulletin of the Korean Chemical Society
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• v.35 no.10
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• pp.2929-2934
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• 2014

The reaction between $[CdBr_2{\cdot}4H_2O]$ and anhydrous $[ZnCl_2]$ with N,N'-bidentate N-(pyridin-2-ylmethylene)-cyclopentanamine (impy) in ethanol yields dimeric $[(impy)Cd({\mu}-Br)Br]_2$ and monomeric $[(impy)ZnCl_2]$ complexes, respectively. The X-ray crystal structure of Cd(II) and Zn(II) complexes revealed that the cadmium atom in $[(impy)Cd({\mu}-Br)Br]_2$ and zinc in $[(impy)ZnCl_2]$ formed a distorted trigonal-bipyramidal and tetrahedral geometry, respectively. Both complexes showed moderate catalytic activity for the polymerisation of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO), with polymethylmethacrylate (PMMA) syndiotacticity of about 0.70.