• Title/Summary/Keyword: $C_4$ Olefin

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Arylation of Styrene by Palladium Acetate-Phosphine Complexes

  • 황박영애;황성원
    • Bulletin of the Korean Chemical Society
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    • v.18 no.2
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    • pp.218-221
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    • 1997
  • When phenylation of styrene was carried out in the presence of Pd(OAc)2 and PPh3 in benzene, trans-stilbene was obtained in good yield (566%) with high selectivity (98%) under mild condition (55 ℃, 50 psi O2, 20 h). Since trans-stilbene could be produced not only from benzene but also from phenyl group of PPh3 by migration of its phenyl group to Pd, the competitiveness of benzene and the migratory aptitude of aryl group of triarylphosphine toward styrene has been investigated with various phosphines (PR3: P(p-C6H4CH3)3, P(p-C6H4OCH3)3, P(p-C6H4F)3, P(p-C6H4Cl)3, P(C6H5)3, P(C6H11)3, P(OC4H9n)3, P(CH2C6H5)3 and P(C6F5)3). The yield and selectivity toward trans-stilbene are increased as the basicity of the phosphines increases. The composition of arylated olefin from arylphosphine, in turn, increases as the electronegativity of the substituent on the aryl group of arylphosphines increases.

Olefin Metathesis Curing Reaction of Essential Oils in Korean Dendropanax Lacquer (Olefin Metathesis를 이용한 황칠 Essential Oil의 경화 반응에 관한 연구)

  • Kim, Mi Ri;Lee, Won Hwi;Yoo, Hye Jin;Kim, Jong Sang;Cheong, In Woo
    • Journal of Adhesion and Interface
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    • v.16 no.4
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    • pp.146-151
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    • 2015
  • Raw sap of essential oil in Korean Dendropanax lacquer was extracted with ethanol, and which was cured by using ROMP (ring opening metathesis polymerization, one of olefin metathesis). Curing behavior with subsequent film properties were studied and compared with conventional curing (under ambient conditions) and UV photo curing. The compositional changes of major ingredients in the lacquer before and after curing were studied by using GC-MS (gas chromatography mass spectrometry). ROMP-cured coating film showed higher gel contents (40%) as compared to those of conventional (8%) and UV curing (25%). ROMP curing with 2 wt% Grubbs' catalyst at $100^{\circ}C$ completed curing reaction within 2 h, which was much faster than that of conventional curing. The quality of coating film prepared with ROMP was more homogeneous and wrinkle-free as compared with that with UV curing. It was found that major ingredients of sesquiterpenes, such as ${\alpha}$-selinene, ${\beta}$-selinene, and ${\delta}$-cadinene were reacted in ROMP, as well as polyacetylenes.

Process Development of Pyrolysis Liquefaction for Waste Plastics (폐플라스틱의 열분해 유화기술 개발)

  • Nho Nam-Sun;Shin Dae-Hyun;Park Sou-Won;Lee Kyong-Hwan;Kim Kwang-Ho;Jeon Sang-Goo;Cho Bong-Gyu
    • New & Renewable Energy
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    • v.2 no.2 s.6
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    • pp.118-125
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    • 2006
  • The target of this work was the process development of demonstration plant to produce the high quality alternative fuel oil by the pyrolysis of mixed plastic waste. In the first step of research, the bench-scale units of 70 t/y and the pilot plant of 360 t/y had been developed. Main research contents in this step were the process performance test of pilot plant of 360 ton/year and the development of demonstration plant of 3,000 t/y, which was constructed at Korea R & D Company in Kimjae City. The process performance of pilot plant of 360 t/y showed about 80% yield of liquid product, which was obtained by both light gas oil(LGO) and heavy gas oil(HGO), The boiling point range distribution of LO product that was mainly consisting of olefin components in PONA group appeared at between that of commercial gasoline and kerosene. On the other hand, HO product was mainly paraffin and olefin components and also appeared at upper temperature distribution range than commercial diesel. Gas product showed a high fraction of $C_3\;and\;C_4$ product like LPG composition, but also a high fraction of $CO_2$ and CO by probably a little leak of process.

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Analysis of Facilitated Olefin Transport Through Polymer Electrolyte Membranes Containing Silver Salts (은염을 포함하는 고분자 전해질 막을 통한 올레핀 촉진수송의 해석)

  • Yong Soo Kang;Dongkyun Ko;Jong Hak Kim;Sung Taik Chung
    • Membrane Journal
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    • v.13 no.4
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    • pp.239-245
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    • 2003
  • The origin of large difference of selectivity of $C_3H_6$ over $C_3H_8$ between pure gas and mixed gas through silver polymer electrolyte membranes is investigated. Firstly, the effect of feed condition on the permeance of mixture gas ($C_3H_6/C_3H^8$) and the separation performance is examined. Upon decrease of the $C_3\;H_6$ concentration, the $C_3H_6$ permeance decreased whereas the permeance of $C_3H_8$ increased, resulting in the decrease of the selectivity of $C_3H_6/C_3H_8/.$ This result is ascribed to the $C_3H_6$-induced plasticization of membranes. Experimental results were validated by means of mathematical modeling, where pressure independent permeabilities were used.

Amine and Olefin Complexes of Pt(II) Having a PCP-Pincer Ligand

  • Park, Soon-Heum
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.132-136
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    • 2002
  • $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)\;(OTf=CF_3SO_3^-)$ readily reacts with various amines to afford cationic amine complexes $[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(amine)](OTf)\;(amine=NH_3,\;NHMe_2,\;NHC_4H_8,\;NH_2Ph,\;NH_2(Tol-p))$ in high yields. These complexes have been fully characterized by IR, $^1H-,\;^{19}F{^1H}-,\;and\;^{31}P{^1H}-NMR$ spectroscopy, and elemental analyses. Reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with acrylonitrile quantitatively produced the ${\pi}$-olefinic complex $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)](OTf)$ which is only stable in solution in the presence of acrylonitrile. Attempt at isolating this complex in the pure solid state was failed due to partial decomposition into $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ The equilibrium constants $(K_{eq}=[Pt(PCP)-(NH_2R)^+][CH_2=CHCN]/[Pt(PCP)(CH_2=CHCN)^+][NH_2R]:\;[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)]^++NH_2R{\rightleftarrows}[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(NH_2R)]^++CH_2=CHCN=Ph,\;p-tolyl)$ were calculated to be 0.28 (for R = Ph) and 3.1 (R = p-tolyl) at $21^{\circ}C$. The relative stability of the ${\sigma}$-donor amine versus the ${\pi}$-olefinic acrylonitrile complex has been found largely dependent upon the amine-basicity $(pK_b)$, implicating that acrylonitrile practically competes with amine in the platinum coordination sphere. On the contrary to the formation of the acrylonitrile complex, no reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with other olefins such as ethylene, styrene and methyl acrylate was observed.

Cross-Linked PGMA-co-PMMA/DAAB Membranes for Propylene/Nitrogen Separation (프로필렌/질소 분리를 위한 가교 구조의 PGMA-co-PMMA/DAAB 분리막)

  • Kim, Na Un;Park, Byeong Ju;Kim, Jong Hak
    • Membrane Journal
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    • v.30 no.4
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    • pp.252-259
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    • 2020
  • Olefins are industrially important materials used for the synthesis of various petrochemicals. During the polymerization process, unreacted olefin monomers are discharged together with a large amount of nitrogen. For economic benefits, these olefin gases should be efficiently separated from nitrogen. In this study, a poly(glycidyl methacrylate-co-methyl methacrylate) (PGM) comb-like copolymer was synthesized and 4,4'-diaminoazobenzene (DAAB) was introduced to the copolymer to prepare a cross-linked membrane for C3H6/N2 separation. PGM and DAAB were readily reacted at room temperature through an epoxide-amine reaction without additional thermal treatment. PGM-based membrane, which is a glassy polymer, showed a faster permeation of N2 compared to C3H6. The pristine PGM membrane exhibited the N2 permeability of 0.12 barrer and the high N2/C3H6 selectivity of 32.4. As DAAB was introduced as a cross-linker, the thermal stability of the membrane was significantly improved, which was confirmed by TGA result. The N2/C3H6 selectivity was decreased at 1 wt% of DAAB content, but the N2 permeability increased by approximately 4.7 times. We analyzed N2/C3H6 gas separation properties through a glassy polymer-based membrane, which has not been widely studied. Also, we proposed that thermal stability of the membrane can be greatly improved by the cross-linking method.

Studies on the Biodegradation Test Method of Sufactant (계면활성제 생분해도 측정방법에 관한 연구)

  • 김영환;정해권김은기윤태일
    • KSBB Journal
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    • v.8 no.4
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    • pp.364-369
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    • 1993
  • The biodegradability of some anionic surfactants were investigated using biological oxygen consumption measurement at different temperatures. As test surfactants, soap, alkyl sulfate (AS), alpha olefin sulfonate (AOS), alkyl polyoxyethylene sulfate (AES), linear alkylbezene sulfonate(LAS), microbial surfactants such as sophorose lipid (sopholipid) and spiculisporic acid (S-acid), were used. The test solution were incubated at $5^{\circ}C$, $18^{\circ}C$ and $32^{\circ}C$, respectively. The comparative rates of biodegradation were in accordance with the results obtained from the surface tension measurement and methylene blue method. The results of comparative blodegradabilities of the surfactants were as follows; soap, AS>AES>AOS>LAS at $18^{\circ}C$ and $32^{\circ}C$. However, at$ 5^{\circ}C$, the biodegradation rate of soap was better than other surfactants. Considering the actual environment of the river, it was concluded that the biological oxygen consumption rate method at lower temperature was more practical than the current method such as methylene blue assay with adapted shaking flask culture at $25^{\circ}C$

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Carbonylative Cyclization of Unsaturated Carboxylic Acids by Palladium Complexes with Phosphines(I) Synthesis and Structure of Palladium(O, II) Complexes with Unsaturated Carboxylic Acids (포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화고리 반응 (제 1 보). 불포화카르복실산이 배위된 팔라듐(0, Ⅱ) 착물의 합성과 구조)

  • Myung-Ki Doh;Maeng-Jun Jung;Dong-Jin Lee;Kohtaro Osakada;Akio Yamamoto
    • Journal of the Korean Chemical Society
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    • v.37 no.4
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    • pp.423-430
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    • 1993
  • New Palladium(0)-olefin complexes, $(PMe_3)_2Pd{CH_2=C(CH_3)COOH} \;and\;(PMe_3)_2Pd{(CH_3)CH=CHCOOH}$ have been prepared by treating $Pd(PMe_3)_2$(styrene) with methacrylic acid and trans-crotonic acid, respectively. These complexes were characterized by elemental analysis, IR and $^1H-,\;^{13}C-,\;and\;^{31}P$-NMR spectroscopy. The carboxylic acid entity was found non-bonded with palladium while ${\pi}$-bond is formed between the olefin double bond and Pd(0). The results are compared with the metallacycle formation the reaction of Pd(PMe3)2(styrene) with 3-butenoic acid.

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Migration of Alkylphenols from PVC Food Packaging Materials to Food Simulants and Foods (PVC 포장재에서 식품유사용매와 식품으로 이행되는 알킬페놀)

  • Lee, Sun-Hee;Lim, Heung-Youl;Shin, Hyo-Sun
    • Korean Journal of Food Science and Technology
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    • v.33 no.4
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    • pp.416-422
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    • 2001
  • The migration of alkylphenols from PVC packaging materials (wrap, sheet and gasket) into food simulants and foods were analyzed by reversed-phase high-performance liquid chromatography with fluorescence detection and gas chromatography with mass selective detection. Only seven nonyl phenol isomers were detected in three types of PVC food packaging materials and the content of nonyl phenol of wrap was higher than those of sheet and gasket. The contents of nonyl phenol migrated from fatty food simulants (n-heptane) were higher than those from aqeous food simulants (distilled water, 4% acetic acid and 20% ethanol) and increased with increase in temperature. Nonyl phenol in fruit juice, infant formula, and beverage was migrated from PVC gasket, olefin gasket, and olefin bottle cap, respectively. Nonyl phenol was also detected from foods even before contacting with the packaging materals.

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Isolation of Alkalopsychrotrophic Protease-Producing Pseudomonas sp. RP-222 and Properties of Its Crude Enzyme (저온.알칼리성 Protease를 생산하는 Pseudomonas sp. RP-222의 분리 및 조효소의 특성)

  • 노종수;정영철;성낙계;박석규
    • Microbiology and Biotechnology Letters
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    • v.19 no.4
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    • pp.383-389
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    • 1991
  • In order to produce alkaline protease, psychrotrophic bacterium which have high enzyme activity at low temperature, was isolated by using enrichment culture from various samples and identified as genus alkalopsychrotropic Pseudomonas sp. RP-222. The optimal culture conditions for enzyme production were pH- 10.0, temperature-$20^{\circ}C$ and culture time-4 days. The optimum pH and temperature for the enzyme activity were pH 10.5 and $40^{\circ}C$, respectively and the enzyme was relatively stable at pH 7.0~13.0 and below $50^{\circ}C$. The enzyme was inhibited by ethylenediaminetetraacetate and phenylmethylsulfonylfluoride, indicating that the enzyme was a serine metalloenzyme, but considerably stable in the presence of surface active agents. Activity of the enzyme was increased by the addition of 0.05% Na-$\alpha$-olefin sulfonate.

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