• Polymer(Korea)
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• v.39 no.1
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• pp.169-173
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• 2015

Metallocene was supported on the silica, which was functionalized with aminosilanes such as aminopropyltrimethoxysilane (1NS) or N-[3-(trimethoxysilyl)propyl]ethylenediamine (2NS), and ionic liquids such as 1-butyl-4-methylpyridinium chloride (Cl), tributylmethylammonium chloride (Amm), benzyldimethyltetradecylammonium chloride (Ben), 1-butyl-1-methylpyrrolidinium chloride (Pyr), and then ethylene polymerizations were performed. The Zr contents of $SiO_2/1NS/IL/(n-BuCp)_2ZrCl_2$ and $SiO_2/2NS/IL/(n-BuCp)_2ZrCl_2$ were lower than those of only aminosilane-treated silicas. However, the polymerization activity of $SiO_2/1NS/IL/(n-BuCp)_2ZrCl_2$ was higher than that of $SiO_2/1NS/(n-BuCp)_2ZrCl_2$. The polymerization activity of $SiO_2/2NS/IL/(n-BuCp)_2ZrCl_2$ was lower than that of $SiO_2/2NS/(n-BuCp)_2ZrCl_2$ due to much lower Zr content.

• 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..

• Applied Chemistry for Engineering
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• v.24 no.1
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• pp.55-61
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• 2013

Heterogeneous metallocene catalysts supported on montmorillonite (MMT), [$Cp_2ZrCl_2$/MMT, $Cp_2ZrCl_2$/MAO/MMT, and $Cp_2ZrCl_2$ + MAO/MMT], were prepared with three different methods of immobilization and tested for ethylene polymerization. The heterogeneous catalysts immobilized on organo clay (30B-MMT) showed the higher metal loading and polymerization activity than those immobilized on natural clay $Na^+-MMT$. These results suggest that the hydroxyl groups of organo clay interlayers react with the MAO and catalyst through the chemical bond. The metallocene catalyst supported directly on MMT showed lower activity for ethylene polymerization compared to the homogeneous systems, while MMT/MAO/$Cp_2ZrCl_2$, catalysts treated with MAO before impregnation, showed a higher activity. The polymers obtained from MMT-supported catalysts have higher melting point, molecular weight and molecular weight distributions than those of homogeneous catalysts. The polymer particles with increasing significant size. Ethylene polymerization over 30B-MMT/MAO/$Cp_2ZrCl_2$ catalyst was also performed varying the process variables to optimize the process conditions.

• Applied Chemistry for Engineering
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• v.25 no.4
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• pp.396-400
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• 2014

The pore surface of mesoporous materials, SBA-15 and MCM-41 were functionalized with organosilanes, 3-aminopropyltrimethoxysilane (1NS) and N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS) via grafting method. $(n-BuCp)_2ZrCl_2$ and methylaluminoxane (MAO) were impregnated on the surface-functionalized mesoporous materials for the application to ethylene polymerization. In the case of SBA-15/2NS/$(n-BuCp)_2ZrCl_2$ supported Zr and Al contents decreased as grafted 2NS content increased. However, in the case of MCM-41/2NS/$(n-BuCp)_2ZrCl_2$ supported Al content decreased, but Zr content increased as grafted 2NS content increased. The polymerization activity of SBA-15/2NS/$(n-BuCp)_2ZrCl_2$ increased as the amount of grafted 2NS increased. Increase in the amount of grafted 2NS should caused decrease in pore volume and diameter. Consequently, it decreased the amount of supported metallocene and MAO in general. However, the smaller pore-sized MCM-41 could have lower supported MAO content due to its large molecular size in case that MCM-41 was surface-functionalized with 2NS. Therefore, the supported metallocene content could increase and its polymerization activity was higher than that of SBA-15.

• 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.

• Proceedings of the KAIS Fall Conference
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• 2003.06a
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• pp.337-339
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• 2003

본 연구에서는 여러 종류의 담체 중에서 Davison 952 실리카를 선택하여 실리카 표면의 하이드록시기의 양을 진공 열처리 방법을 사용하여 조절하였다. 표면 처리된 실리카를 사용하여 담지촉매를 제조한 후 폴리에틸렌(PE) 중합을 수행, 소성온도에 따른 실리카 표면의 하이드록시기 양의 변화와 담지되는 조촉매(MAO) 및 메탈로센 촉매의 양과의 상관관계를 조사하였고 실리카 표면처리와 중합 활성도 간의 상관관계를 고찰하였다. 폴리에틸렌(PE) 중합 결과 메탈로센 촉매가 가장 많이 담지된 200℃ 보다 400℃ 또는 600℃에서 메탈로센 당(g PE/mol Zr)활성도가 높았으며, 담체에 흡착된 MAO와 메탈로센의 비율이 400℃와 600℃에서 가장 크게 나타났다.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.11 no.4
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• pp.1348-1353
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• 2010

At the early stage of a bulk syndiotactic polymerization of styrene, the homogeneous reactant mixture transforms to a slurry state consisting of a precipitated solid syndiotactic PS and a liquid reactant mixture. As the reaction proceeds, the slurry transforms into a wet and then a dried powder if proper methods are used to prevent agglomeration. When a large amount of catalyst and co-catalyst is added to the styrene to achieve a high conversion rate, the reactant mixture becomes a lumpy agglomeration and further control of the reaction is impossible. In this study, we introduce a novel approach to avoid such agglomeration while maintaining a high conversion rate. Instead of adding the catalyst and co-catalyst at once, the total amount of the catalyst and co-catalyst is divided into several parts and added successively. This method is found to be very effective to avoid the formation of agglomerate and to maintain a fairly high conversion rate of slurry into powdery product (up to 70 %). It is also observed that this method produces syndiotactic PS of a higher molecular weigh.

• 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.

• 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.

• Korean Chemical Engineering Research
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• v.53 no.3
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• pp.397-400
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• 2015

The effects of surface treatment method of unreacted N-[3-(trimethoxysilyl)propyl]ethylenediamine (2NS), $N^1$-(3-trimethoxysilylpropyl)diethylenetriamine (3NS), and 3-cyanopropyltriethoxysilane (1NCy) after grafting on the surface of silica and of the surface treatment temperature on ethylene polymerization were investigated. The Zr content of supported catalyst employing filtering method was higher than that of washing method, and the activities of supported catalysts prepared by washing method were higher than those of filtering methods significantly. Regardless of surface treatment methods the activities were in order by $SiO_2/2NS/(n-BuCp)_2ZrCl_2>SiO_2/1NCy/(n-BuCp)_2ZrCl_2>SiO_2/3NS/(n-BuCp)_2ZrCl_2$. The ethylene polymerization activity was increased as the surface treatment temperature of aminosilane on silica increased.