• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.153-154
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• 2006

The development of metal catalysts that can polymerize or copolymerize "polar" $Ch_2=CHX$ monomers by insertion mechanisms would significantly expand the scope of metal-catalyzed polymerization and enable the synthesis of new materials with enhanced properties. We have studied the reactions of single-site olefin polymerization catalysts with vinyl chloride, acrylonitrile, and vinyl ethers, in order to probe monomer coordination trends, insertion rates and regioselectivity, and the structures and reactivity of metal alkyls that contain functional groups on the alpha and beta positions of the alkyl chain. These studies provide insights to the key issues that underlie the "polar monomer" problem. Copolymerization of olefins and selected vinyl ethers has been achieved.

• 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.21 no.1
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• pp.39-43
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• 2000

New coordination polymers of general form, $$[CoL_2X_2]_n$$ (L = 3,3'-oxybis(pyridine) (obp), 1,4-bis(3-pyri-doxy) benzene (bpob); X = Cl, NCS), have been prepared via a slow diffusion method. The reaction of the present linkers with cobalt(II) ion affords infinite 2-dimensional sheet products. For $[Co(obp) $_2Cl_2]_n$$, the local geometry of the cobalt center is an octahedral arrangement with four nitrogen donors and two chlorine ions in trans positions. $$[Co(bpob)_2(NCS)_2]_n$$ has provided a similar structure: the local geometry of the cobalt atom is an octahedral arrangement with four pyridine units and two NCS groups in transpositions. The obp and bpob linkers connect two cobalt(II) ions defining the edges of 40- and 60-membered $[Co(II)]_4$ ring, respectively. Thermal analyses of the coordination polymers show significant thermal behavior associated with the characteristic structures.

• Journal of the Korean Chemical Society
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• v.19 no.6
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• pp.463-467
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• 1975

The polymerization of methyl methacrylate(MMA) initiated by cobalt (II) nitrate in tetrahydrofuran (THF) has been studied. From the results of kinetic studies, the overall polymerization rate (Rp) could be expressed as following; $R_p=k\;[cobalt(Ⅱ)\;nitrate]^{0.5}\;[MMA]^{1.5}$ By considering the effects of chelating agent on the polymerization rate, it could be assumed that the monomer, MMA might form a coordination complex with cobalt(II) nitrate. In the presence of radical inhibitor hydroquinone, the inhibition time was observed. And the apparent overall activation energy was calculated to be 14.0 kcal/mole.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.150-151
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• 2006

Perfluoroaryl boranes are widely employed as co-catalysts in olefin polymerization processes. Perfluoroaryl diboranes, possessing borane centers in close proximity, are a subclass of this family of compounds that are in theory capable of chelating neutral and anionic bases. The resulting anions are exceptionally weakly coordinating. We have prepared examples of such compounds and studied their coordination behavior with neutral Lewis bases that have the capability to bridge Lewis acid sites in an effort to delineate the kinetic and thermodynamic factors that influence bonding mode. When protic Lewis bases such as alcohols or water are reacted with diboranes, strong Bronsted acids capable of initiating cationic polymerizations under unusual conditions result.

• Analytical Science and Technology
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• v.8 no.4
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• pp.529-534
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• 1995

The metal ion selective resins were prepared by surface template polymerization using monooleyl phosphoric acid (1), oleyl methyl phosphoric acid (2) or oleyl ethyl phosphoric acid (3) as an amphiphilic host surfactant. The $Cu^{2+}$-imprinted resins prepared in the presence of $Cu^{2+}$ adsorbed $Cu^{2+}$ much more effectively than did their reference resins. On the other hand, the $Cu^{2+}$-imprinted resins showed much less binding ability to $Zn^{2+}$. The template-dependent selectivity should be ascribed to a favorable placement of the surface-anchored metallophilic groups for multidentate coordination to specific metal ion.

• Polymer(Korea)
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• v.29 no.4
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• pp.321-330
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• 2005

In 1990's the Korean polyolefin industry boomed up through the development of magnificient polymerization catalysts. To understand the general situation of polymerization catalyst R & D, the various experimental results had been summarized for the investigation of not only the supported Ziegler-Natta catalyst used presently in polyolefin industry but also the metallocene catalysts applied for the preparation of special grade of polyolefin. In addition, it had been shown that the new polymeric materials were prepared by new developed catalyst, and the polymer in-situ nanocomposites could be obtained with the application of catalyst heterogenization procedures.

• Elastomers and Composites
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• v.48 no.1
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• pp.2-9
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• 2013

We synthesized polyethylene, poly(ethylene-co-1-decene), poly(ethylene-co-p-methylstyrene), and poly(ethylene-ter-1-decene-ter-p-methystyrene) using a rac-$Et(Ind)_2ZrCl_2$ metallocene catalyst and a methylaluminoxane cocatalyst system. The materials were characterized using nuclear magnetic spectroscopy and fourier transform infrared spectroscopy. To identify suitable reaction conditions for terpolymerization, we studied the effects of catalyst content, cocatalyst/catalyst molar ratio, polymerization time, and polymerization temperature. As the catalyst content increased, the catalytic activity and the molecular weight of the terpolymers increased. The catalytic activity sharply increased but little change was observed after a polymerization time of 30 min. The increase in the cocatalyst/catalyst molar ratio resulted in a decrease in the molecular weight of the terpolymers and an increase in the catalytic activity to some degree. The catalytic activity increased with increasing polymerization temperature, while the molecular weight of the terpolymers decreased.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4131-4136
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• 2012

Several palladium complexes containing ${\beta}$-ketoiminate and ${\beta}$-diketiminate ligands successfully produced poly(DCPD) possibly via vinyl addition. It was found that catalysts with ${\beta}$-diketiminate ligands containing bulkier aryl substituents showed the highest activity in the presence of MAO as a cocatalyst. Purity of DCPD is quite essential for the higher activity and small amount of organic solvent such as $CH_2Cl_2$ and toluene is required to reduce the viscosity of the reactant mixture for the higher activity. $^1H$ NMR spectra of produced polymers with N,N-dimethylanilinium tetra(pentafluorophenyl)borate (N,N-DAPFAr"$_4$) show that 5,6-double bond of DCPD is removed with 2,3-double bond remaining. Produced poly(DCPD) with MAO cocatalyst is quite rigid and insoluble in common organic solvents but rather brittle.

• Elastomers and Composites
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• v.48 no.4
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• pp.263-268
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• 2013

In this study, we prepared poly(ethylene-ter-1-hexene-ter-divinylbenzene) using bridged rac-$Et[Ind]_2ZrCl_2$ metallocene catalysts. The effect of 1-hexene on the terpolymerization rate was evaluated. When cocatalyst/catalyst molar ratio was 3,000, catalytic activity indicated more than 8,000 which was very remarkable value. As polymerization time increased, the weight-average molecular weight of the terpolymer gradually increased to some degree. In case of a polymerization time of 50 minutes, the terpolymer became amorphous state. The molecular weight distribution and densities of the terpolymer were 110,000-200,000 and $0.85-0.89g/cm^3$, respectively. Thermal properties and structure of the terpolymer were also identified.