• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.224-225
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• 2006

The Ethylene polymerization behavior of a series of polymethylene bridged dinuclear CGC $[Zr({\eta}^{5}:{\eta}^{1}-C_{9}H_{5}SiMe_{2}NCMe_{3})Me_{2}]_{2}[(CH_{2})_{n}]\;[_{n}=6(1),\;9(2),\;12(3)]$ in the cocatalytic activation with $Ph_{3}C^{+}B^{-}(C_{6}F_{5})_{4}\;(B_{1})\;or\;Ph_{3}C^{+}(C_{6}F_{5})_{3}B^{-}C_{6}F_{4}B^{-}(C_{6}F_{5})_{3}Ph_{3}C^{+}\;(B_{2})\;or\;B(C_{6}F_{5})_{3}\;(B_{3})$ were investigated to study the nuclearity effects as well as the counteranion effects. The ethylene polymerization and ethylene/1-hexene copolymerization were conducted at $30^{\circ}C$ It was found that both in ethylene polymerization and ethylene/1-hexene copolymerization, activities increased in the order of 1 < 2 < 3, which indicates the presence of longer bridge between two active sites contributes more efficiently to facilitate the polymerization activity.

• Bulletin of the Korean Chemical Society
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• 제20권11호
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• pp.1269-1276
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• 1999

Metallocenes, whether using a cocatalyst or not, act as catalysts in ethylene polymerization. The positive charge on the transition metal of a metallocene might have an important role in polymerization as an active site in our model approach. Using semiempirical calculations in the absence of cocatalyst, we show one of the possibilities that the positive charge on a metallocene might be more easily transferred through the Cp ring of a ligand to the ethylene than to transfer directly from the transition metal to the ethylene. In these calculations, the charge on titanium in an eight C2H4 system is transferred and a polymer chain is produced. This reaction takes place only when ethylenes are arranged in a particular direction with respect to the ring, but does not take place for ethylenes near Ti or Cl atoms. The same mechanism is shown for a metallocene ligand which is sterically hindered or where the Cp ring is replaced by fluorenyl. These results suggest an entirely new polymerization mechanism in the absence of a cocatalyst in which the Cp ring is the active site.

• 한국입자에어로졸학회지
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• 제11권4호
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• pp.107-113
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• 2015

SBA-16 (Santa Barbara Amorphous) was synthesized over supported $TiCl_4/MgCl_2$. Due to its high surface area and excellent morphological performance, it was expected to form the bi-supported catalytic system and be used for ethylene polymerization. Polymerization of ethylene was carried out at atmospheric pressure using hexane as solvent and triethylaluminium as cocatalyst. ICP, FTIR, DSC, TG-DTA were used to characterize polyethylene and catalyst product. Optimum conditions for ethylene polymerization were found to be 100 mL hexane, Al/Ti molar ratio of 160 and 1 h polymerization at $60^{\circ}C$. The activity of 396.76 kg PE/mol Ti.h.atm was achieved. Melting point of the obtained polymer was in the range of $132-135^{\circ}C$ and the highest degree of crystallization was 46%.

• Macromolecular Research
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• 제13권1호
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• pp.2-7
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• 2005

A series of ethylene polymerization catalysts based on tridentate bis-imine ligands coordinated to iron and cobalt was reported. The ligands were prepared through the condensation of sterically bulky anilines with allyloxy-and benzyloxy-substituted 2,6-acetylpyridines. The pre-catalyst complexes were penta-coordinate species of the general formula $\{[(ArN=C(Me))_2(4-RO-C_5H_3N)]MCl_2\}$ (Ar=ortho dialkyl-substituted aryl ring; R=allyl, benzyl; M=Fe, Co). In the presence of ethylene and methyl alumoxane cocatalysts, these complexes were active for the polymerization of ethylene, with activities lower than those of metal complexes of the general formula $\{[(2-ArN=C(Me)_2C_5H_3N]MCl_2\}$ (Ar=ortho dialkyl-substituted aryl ring; M=Co, Fe), containing no substituents in 2,6-acetylpyridine ring. The effects of the catalyst structure and temperature on the polymerization activity, thermal properties, and molecular weight were discussed.

• 한국전기전자재료학회논문지
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• 제17권6호
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• pp.608-614
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• 2004

The gel polymer electrolyte was prepared by radical polymerization using tetra(ethylene glycol) diacrylate and tri(ethylene glycol) dimethacrylate to investigate affect of the number of ethylene oxide. The gel polymer electrolyte showed good electrochemical stability up to 4.5 V vs. Li/Li and high ionic conductivity at various temperatures. The lithium-ion polymer batteries with the gel polymer electrolyte, tetra(ethylene glycol) diacrylate- and tri(ethylene glycol) dimethacrylate-based, also represented good electrochemical performances such as rate capability, low-temperature performances and cycleability. However, the cell with tri(ethylene glycol) dimethacrylate, which has three ethylene oxide, showed better electrochemical performance.

• 폴리머
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• 제33권5호
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• pp.458-462
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• 2009

본 연구에서는 순차적 음이온 및 개환중합반응을 통해 ABC 형태의 폴리스티렌-폴리에틸렌옥사이드-폴리락티드 블록공중합체를 성공적으로 합성하였다. 우선, 첫번째 블록인 폴리스티렌을 합성하기 위해서, 사이클로헥산 용매에서 스티렌/이차-부틸리튬을 각각 단량체/개시제로 사용하여 음이온중합(anionic polymerization)을 수행하였고, 이후 고분자 말단을 수산기로 전환시키기 위해, 에틸렌옥사이드를 첨가하였다. 다음 단계로 포타슘 나프탈레나이드(potassium naphthalenide)를 이용하여 폴리스티렌 말단 수산기의 수소를 제거하여, 거대개시제인 PS-$O^-K^+$를 제조하였다. 준비된 거대 개시제에 정량된 에틸렌옥사이드를 첨가하여, 음이온중합을 수행하였다. 폴리락티드 블록을 도입시키는 개환중합의 경우, THF 용매에서 트리에틸알루미늄(triethylaluminum)/피리딘(pyridine)시스템을 이용하여 PS-b-PEO-$AlEt_2$ 형태의 거대개시제를 형성한 후, $90^{\circ}C$에서 중합을 수행하였다. 합성된 블록공중합체를 수소핵자기공명법 및 겔침투크로마토그래피 방법을 통해 조사한 결과, 잘 정의된 분자량 및 낮은 분자량 분포를 나타냄을 확인할 수 있었다.

• Elastomers and Composites
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• 제48권1호
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• pp.2-9
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• 2013

rac-$Et(Ind)_2ZrCl_2$ 메탈로센 촉매와 메틸알루미늄옥산 공촉매를 이용하여 polyethylene, poly(ethylene-co-1-decene), poly(ethylene-co-p-methylstyrene) 및 poly(ethylene-ter-1-decene-ter-p-methystyrene)를 합성하였다. $^{13}C$ NMR과 $^1H$ NMR 및 FT-IR을 이용하여 삼원공중합체의 특성을 분석하였다. 삼원공중합의 최적조건을 확립하기 위해 동일한 중합조건을 유지한 채 촉매량, 공촉매/촉매 몰비, 중합 시간 및 중합 온도를 변경하여 실험하였다. 촉매량이 증가할수록 삼원공중합체의 촉매활성도 및 중량평균분자량은 증가하였으나, 중합시간이 30분을 초과하자 촉매활성도는 감소하였다. 공촉매/촉매 몰비를 증가시킨 결과 중량평균분자량은 감소하였고, 촉매활성도는 어느 정도 증가하였다. 촉매활성도는 중합온도가 증가함에 따라 상승하였으나 중량평균 분자량은 감소하였다.

• 대한화학회지
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• 제26권5호
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• pp.282-290
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• 1982

Montmorillonite가 주성분인 산성백토로부터 여러 양이온을 교환시켜 촉매를 제조하여 ethylene의 중합활성에 대하여 연구하였다. $Ni^{2+}$-Mont촉매상에서는 ethylene이 선택적으로 n-butene으로 이량화 되었으며, 그 활성은 150$^{\circ}$C 의 진공온도에서 최고로 나타났다. 그리고 촉매활성의 변화는 촉매의 산도와 밀접한 관계가 있었다. $Ni^{2+}$-Mont 촉매는 ethylene의 중합에 높은 활성을 나타내었으며, 그 활성은 450$^{\circ}C$의 진공온도에서 최고로 나타났다. 그리고 $Cr^{3+}$-Mont의 활성점은 $Cr^{3+}$이온으로 생각되었다.

• 응용화학
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• 제15권2호
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• pp.89-92
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• 2011

We synthesized ethylene-styrene copolymer using pyrazolato-type metallocene catalysts. We observed the effects of ethylene contents on the catalytic activity, yield molecular weight and molecular weight distribution. We could also confirm living polymerization behavior through the changes of the M_n and M_w/M_n according to the yield.

• Macromolecular Research
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• 제16권7호
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• pp.659-662
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• 2008

A new and useful poly(ethylene oxide)-based pH-sensitive block copolymer is introduced. Poly(ethylene oxide-b-N-phenylmaleimide) was first synthesized by anionic polymerization of N-phenylmaleimide (N-PMI) using mixed alkali metal polymeric alkoxide by sequential monomer addition method in the mixture of benzene/THF/DMSO (10/5/3, v/v/v) at room temperature. Reductive deimidation of the resulting block copolymer was performed using hydrazine monohydrate leading to the formation of the corresponding pH-sensitive poly(ethylene oxide-b-maleic acid).