• 제목/요약/키워드: methylaluminoxane

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Methylaluminoxane을 이용한 L-lactide 중합 (Polymerization of L-lactide Using Methylalumionxane)

  • 임진형;김다희;고영수
    • 폴리머
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    • 제39권3호
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    • pp.365-369
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    • 2015
  • 본 연구에서는 Al 화합물인 methylaluminoxane(MAO)를 이용하여 L-lactide의 벌크중합 및 용액중합을 실시하였다. 촉매 투입량에 따른 벌크중합 결과, 투입량이 증가할수록 전환율이 증가하였다. 분자량은 촉매 투입량이 0.15 mmol일 때 60800 g/mol로 가장 높은 분자량을 얻었으며 그 이상의 투입량에서는 분자량이 감소하였다. Turnover frequency(TOF)값의 경우 촉매 투입량이 0.15 mmol일 때 가장 크고 촉매 투입량이 증가할수록 감소하였다. 용액중합에서는 30분 가량 induction time이 존재하였다. 중합 시간에 따라 3시간까지 전환율이 선형적으로 증가하였으며 6시간일 때 54700 g/mol로 가장 높은 분자량을 얻었다.

Kinetic Features of the Cobalt Dihalide/Methylaluminoxane Catalytic System in 1,3-Butadiene Polymerization

  • Nath Dilip Chandra Deb;Fellows Christopher M.;Shiono Takeshi
    • Macromolecular Research
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    • 제14권3호
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    • pp.338-342
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    • 2006
  • The kinetic features of polymerization with an active site comprising cobalt dihalides ($CoX_2$, where X=Cl, Br, I) activated by methylaluminoxane (MAO) were investigated in 1,3-butadiene polymerization. The catalytic system exhibited the characteristic features of living polymerization. The initiation ($k_i$) and propagation ($k_p$) rate coefficients were estimated using the kinetic model for slow initiation previously reported by Shiono et al. The energy of activation fur the propagation reaction was calculated to be 27-30 $kJmol^{-1}$. The marked changes in reaction rate observed with different halides could be adequately described in terms of variations in the initiation process, with the same Arrhenius curve fitting propagation rate coeffcients estimated from all three halides, suggesting that the halide does not participate in the growing chain end.

이민에 기초한 질소주개 리간드의 전이금속 착물 합성, 화학적 특성 및 촉매활성 (Synthesis, Chemical Characterization and Catalytic Activity of Transition Metal Complexes Having Imine Based Nitrogen Donor Ligand)

  • Hussain, Raja Azadar;Badshah, Amin;Asma, Maliha
    • 대한화학회지
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    • 제54권1호
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    • pp.23-26
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    • 2010
  • Schiff 리간드인 (Z)-N-((Z)-2-(sec-butylimino)-1,2-diphenylethylidene)butan-2-amine을 벤질과 sec-부틸아민과의 축합반응에 의해 합성하였다. 일 주기 전이금속인 망간(II) 및 니켈(II)과 리간드와의 착물반응을 시도하였다. 리간드 및 착물의 특성을 FTIR, 원소분석 및 열무게분석으로 고체 상태에서, 그리고 NMR ($^1H,\;^{13}C$)로 용액 상태에서의 각각 조사하였다. 두 착물 모두 온화한 조건에서 methylaluminoxane (MAO) 존재 하에 부타디엔 올리고화 반응의 조촉매로 좋은 촉매활성을 보였다.

Kaminsky 촉매계로 제조한 폴리프로필렌의 미세구조 (Microstructure of Polypropylene Prepared with Kaminsky Catalyst System)

  • 이철규
    • 분석과학
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    • 제9권2호
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    • pp.203-209
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    • 1996
  • 본 논문에서는 Kaminsky 촉매계 ($Et(Ind)_2ZrCl_2$와 MAO(methylaluminoxane))를 합성하여 $60^{\circ}C$에서 폴리프로필렌을 중합하였다. 본 연구에서는 중합한 폴리프로필렌의 미세구조를 $^{13}C$ NMR 분석 결과로부터 meso와 racemo I 구조가 나타난 것으로 보아 프로필렌의 2, 1-삽입은 Kaminsky 촉매에 의해 입체 특이적으로 조절됨을 알 수 있다. 그리고 2, 1-삽입후에 체인 말단에 1, 2-삽입되는 프로필렌은 입체 특이적인 조절이 덜 됨을 알수 있다.

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C2-Symmetric Dichloro[rac-ethylenebisindenyl] zirconium(IV)/Methylaluminoxane 시스템을 이용한 배위 중합에 관한 연구 (A Study on the Coordination Polymerization Using C2-Symmetric Dichloro[rac-ethylenebisindenyl] zirconium(IV)/Methylaluminoxane System)

  • 양동진;김현기;박노형;이준철;김동현
    • 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.

Polymerization with Dinuclear Metallocene Compounds

  • Lee, Dong-ho;Noh, Seok-Kyun
    • Macromolecular Research
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    • 제9권2호
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    • pp.71-83
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    • 2001
  • The metallocene compounds had been applied to the polymerizations of olefins and vinyl monomers with methylaluminoxane (MAO) cocatalyst, and they have usually one transition metal atom per molecule, i.e., mononuclear metallocene. Recently it has been found that the dinuclear metallocene compounds containing two transition metal atoms exhibit the peculiar polymerization behaviors for olefins and vinyl monomers. In this article, the dinuclear metallocenes are classified into four groups of dinuclear bent-metallocene, dinuclear ansa-metallocene, dinuclear constrained geometry catalyst and dinuclear half-metallocene, and then the synthesis of dinuclear metallocene of each group as well as the polymerization behaviors for ethylene, propylene, and styrene are described.

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Preparation of High Transparent Olefin Copolymer with Metallocene Catalyst

  • Lee, Dong-Ho;Choi, Yeon-Seok;Ha, Ki-Ryong
    • 한국정보디스플레이학회:학술대회논문집
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    • 한국정보디스플레이학회 2003년도 International Meeting on Information Display
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    • pp.1028-1029
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    • 2003
  • The copolymerization of ethylene and norbornene was carried out with ansa-metallocene and modified methylaluminoxane (MMAO) cocatalyst. The copolymerization behavior was changed with the structure of metallocene catalysts. In addition the catalyst activity was dependent on the structure of MMAO, i.e.. MMAO-4 which contains less i-butyl group compared to MMAO-3A exhibited higher catalyst activity than MMAO-3A. The glass transition temperature and the composition of the produced copolymer were not affected by MMAO type.

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Novel Nickel Catalysts Containing Tetradentate Chelating Ligands for the Polymerization of Norbornene

  • Lee, Dong Hwan;Lee, Jun Yong;Ryu, Ji Young;Kim, Youngmee;Kim, Cheal;Lee, Ik-Mo
    • Bulletin of the Korean Chemical Society
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    • 제27권7호
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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.

Polymerization of Methyl Methacrylate with Nickel $\alpha$-Diimine Catalysts: Effect of the Methyl Position in the Ligand

  • Kim, Il;Kim, Jae-Sung;Han, Byeong-Heui;Ha, Chang-Sik
    • Macromolecular Research
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    • 제11권6호
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    • pp.514-517
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    • 2003
  • In the solution polymerizations of methyl methacrylate with (${\alpha}$-diimine)nickel(II)/methylaluminoxane (MAO), we observed effects of the position of two methyl substituents in the ligand on both the activities of the catalysts and the polymer microstructure. ${\alpha}$-Diimine nickel(II) catalysts gave syndiotactic-rich poly(methyl methacrylate) with high molecular weight and narrow molecular weight distribution.