• Title/Summary/Keyword: Olefin

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Kinetic Investigation of Olefin Oxidation by Al(III)-Porphyrin Complexes (Al(lll)-Porphyrin착물에 의한 올레핀 산화반응 메카니즘 연구)

  • Na, Hun-Gil;Han, Man-So
    • Journal of the Korean Chemical Society
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    • v.50 no.1
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    • pp.46-52
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    • 2006
  • studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (p-X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and (p-X)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin.

Unusual Facilitated Olefin Transport through Polymethacrylate/Silver Salt Complexes

  • Kim, Jong-Hak;Joo, Seung-Hwan;Kim, Chang-Kon;Kang, Yong-Soo;Jongok Won
    • Macromolecular Research
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    • v.11 no.5
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    • pp.375-381
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    • 2003
  • Silver salt complex membranes with glassy poly(methyl methacrylate) (PMMA) unexpectedly showed higher propylene permeance than those with rubbery poly(butyl methacrylate) (PBMA) where as neat PMMA is much less permeable to propylene than that of neat PBMA. Such unusual facilitated olefin transport has been systematically investigated by changing the side chain length of polymethacrylates (PMAs) from methyl, ethyl to butyl. The ab initio calculation showed almost the same electron densities of the carbonyl oxygens in the three PMAs, expecting very similar intensity of the interaction between carbonyl oxygen and silver ion. However, the interaction intensity decreases with the length of the alkyl side chain: PMMA > PEMA > PBMA according to wide angle X-ray scattering and FT-Raman spectroscopy. The difference in the interaction intensity may arise from the difference in the hydrophilicity of the three PMAs, as confirmed by the contact angle of water, which determines the concentrations of the ionic constituents of silver salts: free ion, contact ion pair and higher order ionic aggregate. However, propylene solubilities and facilitated propylene transport vary with the side chain length significantly even at the same concentration of the free ion, the most active olefin carrier, suggesting possible difference in the prohibition of the molecular access of propylene to silver ion by the side chains: the steric hindrance. Therefore, it may be concluded that both the hydrophilicity and the steric hindrance associated with the side chain length in the three PMAs are of pivotal importance in determining facilitated olefin transport through polymer/silver salt complex membranes.

Spectroscopic Analysis on Hydroquinone Clathrates for an Application to Storage/Recovery of Olefin Compounds (올레핀 저장/회수 기술 응용을 위한 하이드로퀴논 크러스레이트의 분광학적 분석 연구)

  • Lee, Jong-Won;Pratik, Dotel;Kang, Seong-Pil
    • Transactions of the Korean hydrogen and new energy society
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    • v.24 no.5
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    • pp.437-443
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    • 2013
  • Clathrate samples, using hydroquinone as a host and ethylene or propylene as a possible guest, were prepared and analyzed by means of spectroscopic measurements. Obtained results showed that ethylene can form clathrate compounds with hydroquinone at 4.0MPa and room temperature, while propylene cannot form clathrate compounds. Different formation behaviors of these two olefin compounds can be applied to a clathrate-based storage/recovery of ethylene in a selective way, and can provide useful information on the cavity size of the formed clathrate compounds.

Permeation Behavior of Olefin/Nitrogen Gases through Siloxane based Polymeric Membranes (실록산계 고분자 막을 통한 올레핀/질소 기체 투과 거동)

  • 이수복;신효진;최승학;김정훈;박인준;노재성;강득주
    • Membrane Journal
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    • v.13 no.4
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    • pp.246-256
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    • 2003
  • For the olefin recovery from polyolefin off-gas, the permeation behaviors of olefins and nitrogen were investigated through three kinds of PDMS membranes - cross-linked PDMS membranes, a polysiloxaneimide membrane, and oligo-PDMS modified PDMS membranes. Their pure gas permeabilities were measured as a function of operation temperature(-20 to $50^{\circ}C$) and pressure(1 to 25 atm) with ethylene($C_2\;H_4$), propylene($C_3\;H_6$), butylene($C_4\;H_8$), and nitrogen($N_2$) gases. The permeabilities of olefins and nitrogen highly depended upon the nature of PDMS membranes. Among these membranes, cross-linked PDMS membranes showed stable and high olefin/nitrogen selectivities over a wide operation pressure range and further study in various test conditions. Their permeability of olefin and nitrogen were governed by the condensation temperature(solubility selectivity) and plasticization, not the order of the size(diffusivity selectivity) of gases, which matched well with the general permeation behavior of rubbery polymeric membranes for condensable and non-condensable gases. With increasing feed pressure or decreasing feed temperature, the permeabilities of more condensible olefins increase highly, presumably due to high solubility and plasticization, but that of non-condensible nitrogen decreases slightly and thus, the selectivities of olefin/nitrogen increase highly.

Olefin Separation Membranes Based on PEO/PDMS-g-POEM Blends Containing AgBF4/Al(NO3)3 Mixed Salts (AgBF4/Al(NO3)3 혼합염이 포함된 PEO/PDMS-g-POEM 블렌드 기반의 올레핀 분리막)

  • Kim, Sang Jin;Jung, Jung Pyu;Park, Cheol Hun;Kim, Jong Hak
    • Membrane Journal
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    • v.25 no.6
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    • pp.496-502
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    • 2015
  • Facilitated transport is one of the possible solutions to simultaneously improve permeability and selectivity, which is challenging in conventional polymer-based membranes. Olefin/paraffin separation using facilitated transport membrane has received much attention as an alternative solution to the conventional distillation process. Herein, we report olefin separation composite membranes based on the polymer blends containing $AgBF_4/Al(NO_3)_3$ mixed salts. Free radical polymerization process was used to synthesize an amphiphilic graft copolymer of poly(dimethyl siloxane)-graft- poly(ethylene glycol) methyl ether methacrylate (PDMS-g-POEM). In addition, poly(ethylene oxide) (PEO) was introduced to the PDMS-g-POEM graft copolymer to form polymer blends with various ratios. The propylene/propane mixed-gas selectivity and permeance reached up to 5.6 and 10.05 GPU, respectively, when the PEO loading was 70 wt% in polymer blend. The improvement of olefin separation performance was attributed to the olefin facilitating silver ions as well as the highly permeable blend matrix. The stabilization of silver ions in the composite membrane was achieved through the introduction of $Al(NO_3)_3$ which suppressed the reduction of silver ions to silver particles.

합성윤활유의 특성 및 개발현황

  • 이중용
    • Tribology and Lubricants
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    • v.6 no.2
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    • pp.16-26
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    • 1990
  • 고대 이집트시대에서부터 동식물 유지가 차축유 등에 쓰여진 것이 잘 알려져 있으며 유지는 화학적으로 일종의 에스테르이다. 현재 사용되는 윤활유는 그 대부분 원유를 원료로 하는 석유계 윤활유이고 그 외에 동식물유 및 합성 윤활유가 일부 쓰이고 있다. 각종 도구나 기계류의 윤활제로서 동식물 유지가 쓰여지기 시작한 것은 기원전 1500년경부터라 한다. 합성윤활유는 19세기 중엽부터 연구개발이 시작되어 1930년대부터 1940년 사이에 Standard oil of Indiana사이에 $\alpha$-Olefin Oligomer를 그리고 독일 IG 사에서는 Olefin Oligomer와 에스테르를 처음 공업생산하였다.

Synthesis of The Optically Active Bicyclo [4.2.0. ] octanone by Stereoselective Intramolecular [2+2] Cycloaddition (입체선택적인 분자내 [2+2] 환화반응을 이용한 광학활성 Bicyclo[4.2.0.]octanone의 합성)

  • Shim, Pil-Jong;Kim, Hee-Doo
    • YAKHAK HOEJI
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    • v.41 no.6
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    • pp.714-717
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    • 1997
  • Stereoselective synthesis of the optically active bicyclo [4.2.0] octanone 5 was accomplished using intramolecular olefin-keteniminium salt[2+2]cycloaddition of the amide 4 as a key step. This important chiral synthon was prepared starting from readily available L-glutamic acid via an efficient 8-step sequence.

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Photocycloaddition Reaction of 1,2-Bispyrazylethylene to Tetracyanoethylene

  • Shim, Sang-Chul;Shim, Hyun-Kwan
    • Bulletin of the Korean Chemical Society
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    • v.1 no.4
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    • pp.123-126
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    • 1980
  • Benzene solution of trans-1,2-bispyrazylethylene and electron deficient olefin, tetracyanoethylene, as a ${\pi}$-acceptor gave 1,2-bispyrazyl-3,3,4,4-tetracyanocyclobutane, a 2${\pi}$ + 2${\pi}$ cycloaddition product, on irradiation with 350 nm UV light. Fluorescence studies revealed the reaction to proceed through a singlet exciplex. The fluorescence of trans-1,2-bispyrazylethylene was quenched very efficiently by tetracyanoethylene with the quenching constant of 1.6 ${\times}$ 10$^{10}$M$^{-1}$s$^{-1}$ while electron rich olefin, tetramethylethylene, did not quench the fluorescence of bispyrazylethylene.