• Advances in materials Research
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• 제6권3호
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• pp.303-316
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• 2017

In this article, novel olefin polymerization catalyst with lower cost and simple synthetic process were developed, $ArOTiCl_3$ complexes [$(2-OMeC_6H_4O)TiCl_3(C1)$, $(2,4-Me_2C_6H_3O)TiCl_3(C2)$, $TiCl_3(1,4-OC_6H_4O)TiCl_3(C3)$, $TiCl_3(1,4-OC_6H_2O-Me_2-2,5)$ $TiCl_3(C4)$] and corresponding $(ArO)_2TiCl_2$ complexes [$TiCl_2(OC_6H_4-OMe-2)_2(C5)$ and $TiCl_2(OC_6H_3-Me_2-2,6)_2(C6)$] have been synthesized by the reaction of $TiCl_4$ with phenol, all these complexes were well characterized with $^1H$ NMR, $^{13}C$ NMR, MASS and EA. When combined with methylaluminoxane (MAO), the $ArOTiCl_3/MAO$ system shows high activity for ethylene copolymerization with 1-octene and copolymer was obtained with broaden molecular weight distribution (MWD). The $^{13}C$ NMR result of polymer indicates that the 1-octene incorporation in polymer reached up to 8.29 mol%. The effects of polymerization temperature, concentration of polymerization monomer and polymerization time on the catalytic activity have been investigated.

• 공업화학
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• 제18권5호
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• pp.516-521
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• 2007

새롭게 합성된 $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ 촉매와 인디닐 리간드에 치환체가 붙어 있지 않는 상용촉매인 $rac-Me_2Si(Ind)_2ZrCl_2$ 촉매들을 조촉매인 methylaluminoxane (MMAO)를 사용하여 에틸렌/1-옥텐 공중합을 실시하였고, 반응물 내 1-옥텐의 농도를 변화시키며 얻어진 공중합체의 특성을 조사하였다. 촉매활성에 있어서 $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ 촉매를 이용하여 공중합을 실시한 경우 다리구조를 가진 다른 촉매들과 달리 촉매활성이 감소하여 comonomer의 첨가에 따라 활성이 증가하는 comonomer effect는 발견되지 않았다. $^{13}C$ NMR 분석에서 공중합체에 삽입된 1-옥텐의 양은 촉매 리간드에 붙은 치환체에 의존함을 보였으며, 2-p-tolyl 치환체가 붙은 촉매로 얻어진 공중합체에서 1-옥텐 삽입량이 더 높음을 보였다. DSC, GPC 분석에서 반응물 내 1-옥텐의 농도가 증가함에 따라 공중합체의 녹는점, 결정성, 분자량이 모두 감소하였으며 $rac-Me_2Si(Ind)_2ZrCl_2$ 촉매보다 $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ 촉매의 경우 녹는점, 결정성 및 분자량의 감소폭이 더 크게 나타났다.

• 대한화학회지
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• 제62권3호
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• pp.191-202
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• 2018

The aim of this work is to study Monte Carlo simulation of ethylene (co)polymerization over Ziegler-Natta catalyst as investigated by Chen et al. The results revealed that the Monte Carlo simulation was similar to sum square error (SSE) model to prediction of stage II and III of polymerization. In the case of activation stage (stage I) both model had slightly deviation from experimental results. The modeling results demonstrated that in homopolymerization, SSE was superior to predict polymerization rate in current stage while for copolymerization, Monte Carlo had preferable prediction. The Monte Carlo simulation approved the SSE results to determine role of each site in total polymerization rate and revealed that homopolymerization rate changed from site to site and order of center was different compared to copolymerization. The polymer yield was reduced by addition of hydrogen amount however there was no specific effect on uptake curve which was predicted by Monte Carlo simulation with good accuracy. In the case of copolymerization it was evolved that monomer chain length and monomer concentration influenced the rate of polymerization as rate of polymerization reduced from 1-hexene to 1-octene and increased when monomer concentration proliferate.

• 폴리머
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• 제25권4호
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• pp.468-475
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• 2001

$rac-Et(Ind)_2ZrCl_2,\;rac-Me_2Si(Ind)_2ZrCl_2,\;rac-Me_2Si(Cp)_2ZrCl_2,\;(n-BuCp)_2ZrCl_2$ 등의 메탈로센 촉매와 공촉매인 개질 메틸알루민옥산(MMAO)을 이용한 에틸렌과 노르보르넨의 공중합에서 1-헥센(H), 1-옥텐 및 1-데센 등과 같은 ${\alpha}$-올레핀을 제3단량체로 첨가할 때, 중합조건, 촉매의 구조 및 ${\alpha}$-올레핀의 종류와 첨가량이 촉매 활성, 생성 중합체의 열적 성질 및 조성 등에 미치는 영량을 조사하였다. ${\alpha}$-올레핀의 첨가량에 따른 촉매 활성 및 중합체의 열적 성질의 변화는 촉매구조 뿐만 아니라 ${\alpha}$-올레핀의 구조에도 의존하였다. $rac-Et(Ind)_2ZrCl_2/MMAO$계에서 촉매 활성이 높았고 중합체의 $T_g$ 제어가 용이하였으며, 제3단량체로 H를 첨가한 경우에 가장 높은 촉매활성의 증가를 확인하였다.