• Bulletin of the Korean Chemical Society
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• 제26권5호
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• pp.707-708
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• 2005

• Macromolecular Research
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• 제10권2호
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• pp.97-102
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• 2002

The mixtures of non-conjugated dienes, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene (MHD), were successfully synthesized by the reaction of isoprene with ethylene using Fe(III)-based catalyst in toluene. The conversion was over 96 mol% on the basis of the initial amount of isoprene used. The production yield for MHD was nearly 50 mol%, the other was polyisoprene. The mixtures were successfully copolymerized with ethylene by using zirconium-based metallocenes. The products were characterized by the combinations of gas chromatography, high temperature gel permeation chromatography, $^1$H NMR, $^{13}$ C NMR, high temperature $^1$H NMR, UV/visible spectroscopy, and differential scanning calorimetry. It was found that 5-methyl-1,4-hexadiene was active enough to be incorporated into the copolymer chain but the corresponding isomeric material,4-methyl-1,4-hexadiene, was inactive in metallocene-catalyzed copolymerizations. Specifically, in the zirconocene-catalyzed copolymerizations of ethylene with MHD, ansa-structure catalysts seem to be more efficient than non-bridged type zirconocene. The degree of incorporation of MHD in the resulting copolymers was able to be controlled by the amount of non-conjugated dienes used initially.

• 폴리머
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• 제24권4호
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• pp.437-444
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• 2000

본 연구는 metallocene 계열 촉매인 rac-Et(Ind)$_2$ZrCl$_2$촉매와 현재 상업용 공정에서 사용하고 있는 제3세대 Ziegler-Natta 촉매를 이용하여 반 회분식 반응기내에서 프로필렌 중합을 실시하였다. 이로부터 각 촉매계의 최적 중합 변수와 생성된 중합체의 각종 물성을 파악하였다. 두 촉매계로부터 생성된 중합체의 입자 크기 및 분포 결과와 중합 반응의 활성 측정 실험을 통해 Ziegler-Natta 촉매는 4$0^{\circ}C$에서, rac-Et(Ind)$_2$ZrCl$_2$는 5$0^{\circ}C$에서 각각 최적의 반응성을 나타냄을 알 수 있었다. 중합 온도는 추적의 중합 반응 활성 결과를 결정하는 중요한 인자이지만 과잉의 온도 조건에서는 중합체의 뭉침 현상이 현저함을 찰 수 있었다. 조촉매 농도 변화에 따른 중합 결과로부터 각 촉매계에서 조촉매의 농도 상한선을 구할 수 있었으며, 과량의 조촉매 농도는 오히려 중합 속도나 수율을 감소시킴을 알 수 있었다. Metallocene 촉매계에서 조촉매로 사용하는 methylaluminoxane (MAO)이나 triethylaluminum (TEAl)은 중합 활성에만 영향을 줄 뿐 중합체의 물성에는 영향을 주지 못하는 반면, Ziegler-Natta촉매계의 경우 para-ethoxyethylbenzoate (PEEB)는 중합 활성뿐 아니라 중합체의 입체 규칙성을 결정하는 중요한 인자로 작용함을 알 수 있었다. 본 실험에서는 단량체로 사용된 propylene의 분압과 중합체 수율간에는 1차의 선형관계가 성립됨을 발견할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제17권11호
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• pp.1040-1044
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• 1996

The catalytic dehydrocoupling of bis(1-sila-3-butyl)benzene, 1 by Cp2ZrCl2/Red-Al and Cp2ZrCl2/n-BuLi combination catalysts yielded a mixture of oily and solid polymers. While the catalytic dehydrocoupling of 2-phenyl-l,3-disilapropane, 2 by Cp2ZrCl2/n-BuLi combination catalyst produced a mixture of oily and solid polymers, the catalytic redistribution/dehydrocoupling of 2 by Cp2ZrCl2/Red-Al combination catalyst gave oily polymer. The dehydrocoupling of 1 and 2, unless the prior silane redistribution occurs, seems to initially produce a low-molecular-weight polymer, which then undergoes an extensive cross-linking reaction of backbone Si-H bonds, leading to an insoluble polymer.

• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.369-376
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• 2003

Coulson (ZINDO), Mulliken $(MP2/6-31G^*)$ and Natural $(MP2/6-31G^*)$ population analyses of several large molecules were performed by the Fragment Reassociation (FR) method. The agreement between the conventional ZINDO (or conventional MP2) and FR-ZINDO (or FR-MP2) charges of these molecules was excellent. The standard deviations of the FR-ZINDO net atomic charges from the conventional ZINDO net atomic charges were 0.0008 for $C_{10}H_{22}$ (32 atoms), 0.0012 for $NH_2-C_{16}O_2H_{28}-COOH$ (53 atoms), 0.0014 for $NH_3^+-C_{16}O_2H_{28}-COOH$ (54 atoms), 0.0017 for $NH_2-C_{16}O_2H_{28}-COO^-$ (52 atoms), 0.0019 for $NH_3^+-C_{16}O_2H_{28}-COO^-$ (53 atoms), 0.0024 for a conjugated model $(O=CH-(CH=CH)_{15}-C=O-(CH=CH)_{12}-CH=CH_2)$, 118 atoms), 0.0038 for aglycoristocetin $(C_{60}N_7O_{19}H_{52}^+$, 138 atoms), 0.0023 for a polypropylene model complexed with a zirconocene catalyst $(C_{68}H-{121}Zr^+$, 190 atoms) and 0.0013 for magainin $(C_{112}N_{29}O_{28}SH_{177}$, 347 atoms), respectively. The standard deviations of the FR-MP2 Mulliken (or Natural) partial atomic charges from the conventional ones were 0.0016 (or 0.0016) for $C_{10}H_{22}$, 0.0019 (or 0.0018) for $NH_2-C_{16}O_2H_{28}-COOH$ and 0.0033 (or 0.0023) for $NH_3^+-C_{16}O_2H_{28}-COO^-$, respectively. These errors were attributed to the shape of molecules, the choice of fragments and the degree of ionic characters of molecules as well as the choice of methods. The CPU time of aglycoristocetin, conjugated model, polypropylene model complexed with zirconocene and magainin computed by the FR-ZINDO method was respectively 2, 4, 6 and 21 times faster than that by the normal ZINDO method. The CPU time of $NH_2-C_{16}O_2H_{28}-COOH\;and\;NH_3^+-C_{16}O_2H_{28}-COO^-$ computed by the FR-MP2 method was, respectively, 6 and 20 times faster than that by the normal MP2 method. The largest molecule calculated by the FR-ZINDO method was B-DNA (766 atoms). These results will enable us to compute atomic charges of huge molecules near future.

• 통합자연과학논문집
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• 제4권3호
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• pp.177-181
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• 2011

The catalytic dehydrocoupling of bis(1-sila-3-butyl)benzene 1 and 2-phenyl-1,3-disilapropane 2 by $Cp_2ZrCl_2$/Red-Al and $Cp_2ZrCl_2$/n-BuLi was reported to compare their catalytic efficiency. The dehydrocoupling of monomeric silanes 1 with the $Cp_2ZrCl_2$/Red-Al and $Cp_2ZrCl_2$/n-BuLi combination catalysts produced two phases of polymers: one is a highly cross-linked insoluble solid, and the other is noncross-linked or slightly cross-linked soluble oil and could be a precursor for the solid polymer. The dehydrocoupling of 2 with the $Cp_2ZrCl_2$/n-BuLi combination catalyst similarly produced two phases of polymers. By contrast, the catalytic reaction of 2 with the $Cp_2ZrCl_2$/Red-Al combination catalyst produced a soluble polymer via redistribution/dehydrocoupling process.

• 폴리머
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• 제24권4호
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• pp.445-452
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• 2000

다양한 종류의 메탈로센 촉매와 공촉매인 개질-MAO (MMAO)을 이용한 에틸렌 (E)과 노르보르넨 (N)의 공중합에서 중합조건이 촉매 활성 및 공중합체의 구조와 성질 등에 미치는 영향을 조사하였다. 즉 $C_2$-대칭구조를 가지는 rac-Et(Ind)$_2$ZrC $l_2$, $M_2$Si(Ind)$_2$ZrC $l_2$, M $e_2$Si-(Cp)$_2$ZrC $l_2$ 및 $C_{s}$-대칭구조를 가지는 iPr(FluCp)ZrC $l_2$, 그리고 constrained geometry catalyst (CGC)와 이중다리 (di-bridged) 지르코노센 둥의 다양한 메탈로센 촉매를 사용하여 [N]/[E] 공급비에 따른 촉매 활성, 공중합체 (COC)의 열적 성질 및 N 함량을 조사하였다. rac-Et(Ind)$_2$ZrC $l_2$를 촉매로 사용한 경우에 공촉매의 몰비, 중합 온도 및 공촉매 종류 등의 중합조건을 조사한 결과 [Al]/[Zr]=3000, 4$0^{\circ}C$, MMAO 공촉매 등이 적합하였다. [N]/[E] 공급비가 증가됨에 따라 COC내의 N 함량이 증가하는 일반적인 경향을 보였으나, 촉매 활성은 사용된 메탈로센 촉매의 구조에 따라 달랐다. 즉 [N]/[E]가 증가할수록 $C_2$-대칭구조의 촉매 활성은 감소하였으나 $C_{s}$-대칭구조의 경우에는 증가하였다. 촉매활성과 N함량 등을 고려해 보면 rac-Et(Ind)$_2$ZrC $l_2$/MMAO계에서 비교적 높은 촉매 활성과 COC의 $T_{g}$제어가 용이한 결과를 얻을 수 있었다. 촉매종류에 따른 단량체의 반응성비를 Helen-Tudos 방법으로 구하였다.하였다.