• Title/Summary/Keyword: Vinyl ether

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Polymeric Membrane Cesium-Selective Electrodes Based on Quadruply-bridged Calix[6]arenes

  • Choe, Eun Mi;O, Hye Jin;Go, Seung Hwa;Choe, Yong Guk;Nam, Gye Chun;Jeon, Seung Won
    • Bulletin of the Korean Chemical Society
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    • v.22 no.12
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    • pp.1345-1349
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    • 2001
  • New quadruply-bridged calix[6]arenes (I-V) have been studied as cesium selective ionophores in poly(vinyl chloride) (PVC) membrane electrodes. PVC membranes were prepared with dioctyl sebacate (DOS) or 2-nitrophenyl octyl ether (o-NPOE) as the sol vent mediator and potassium tetrakis(p-chlorophenyl)borate as the lipophilic salt additive. These ionophores produced electrodes with near-Nernstian slope. The selectivity coefficients for cesium ion with respect to alkali, alkaline earth and ammonium ions have been determined. The lowest detection limit (logaCs+ = -6.3) and the higher selectivity coefficient (logkpotCs+,Rb+ = -2.1 by SSM, -2.3 by FIM for calix[6]arene I) for Cs+ have been obtained for membranes containing quadruply-bridged calix[6]arenes (I, Ⅱ, Ⅲ), which have no para t-butyl substituents on the bridging benzene ring.

Steric Hindrance in the Free Radical Polymerization of Aryloxyethyl Vinyl Ethers Containing Electron-Deficient Olefin Groups$^{\dag}$

  • Lee, Ju Yeon;Jin, Mi Gyeong
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.613-617
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    • 2000
  • p-(2-Vinyloxyethoxy)benzylidenemalononitrile (4a), methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), 3,5-dimethoxy-4-(2'-vinyloxyethoxy)benzylidenemalononitrile (5a), methyl 3,5-dimethoxy-4-(2'-vinyloxy-ethoxy) benzylidenecyanoacetate (5 b), o-(2 -vinyloxyethoxy)benzylidenemalononitrile (6a), methyl o-(2-viny-Ioxyethoxy) benzylidenecyanoacetate (6b), 1,3-di-(2',2'-dicyanovinyl)-5-methyl-2-(2'-vinyloxyetioxy)benzene (7a), l,3-di-(2'-carbomethoxy-2'-cyanovinyl)-5-methyl-2-(2'-vinyloxyethoxy)benzene (7b), 2,3,4-tri-(2'-viny-Ioxyethoxy) benzylidenemalononitrile (8a), methyl 2,3,4-tri-(2'-vinyloxyethoxy)benzylidenecyanoacetate (8b), 2,4,6-tri-(2'-vinyloxyethoxy)benzylidenemalononitrile (9a), and methyl 2,4,6-tri-(2'-vinyloxyethoxy)benzyl-idenecyanoacetate(9b) were prepared by the condensation of the corresponding benzaldehyde 1-3 with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 4, 6, and 8 polymerized readily with radical initiators to yield crosslinked polymers 10, 12, and 14. However, compounds 5, 7, and 9 were inert to radical initiators due to the steric hindrance. The resulting polymers 10, 12, and 14 were not soluble in common solvents showing a thermal stability up to $300^{\circ}C$.

Synthesis and Cationic Polymerization of Multifunctional Vinyl Ethers Containing Dipolar Electronic Systems

  • 이주연;김지향;김민정
    • Bulletin of the Korean Chemical Society
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    • v.20 no.3
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    • pp.307-313
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    • 1999
  • 2,4-Di-(2'-vinyloxyethoxy)benzylidenemalononitrile (la), methyl 2,4-di-(2'-vinyloxyethoxy)benzylidenecyanoacetate (lb), 3,4-di-(2'-vinyloxyethoxy)benzylidene malononitrile (2a), methyl 3,4-di-(2'-vinyloxyethoxy)benzylidenecyanoacetate (2b), 2,5-di-(2'-vinyloxyethoxy)benzylidenemalononitrile (3a), methyl 2,5-di-(2'-vinyloxyethoxy)benzylidenecyanoacetate (3b), 2,3-di-(2'-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl 2,3-di-(2'-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of 2,4-di-(2'-vinyloxyethoxy)benzaldehyde, 3,4-di-(2'-vinyloxyethoxy)benzaldehyde, 2,5-di-(2'-vinyloxyethoxy) benzaldehyde, and 2,3-di-(2'-vinyloxyethoxy)benzaldehyde with malononitrile or methyl cyanoacetate, respectively. Trifunctional divinyl ether monomers 1-4 were polymerized readily with boron trifluoride etherate as a cationic initiator to give optically transparent swelling poly(vinyl ethers) 5-8 havina oxybenzylidenemalononitrile and oxycyanocinnamate, which is presumably effective chromophore for second-order nonlinear optical applications. Polymers 5-8 were not soluble in common organic solvents such as acetone and DMSO due to crosslinking. Polymers 5-8 showed a thermal stability up to 300 ℃ in TGA thermograms, which is acceptable for electrooptic device applications.

Stereoselective Reduction of Methyl Vinyl Ketone Dimer

  • Jun, Jong-Gab;Shin, Dong-Gyun;Lee, Chang-Kiu;Sin, Kwan-Seog
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.307-309
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    • 1990
  • The stereoselectivity of the reaction between methyl vinyl ketone dimer, which contains two possible sites of chelation, and zinc borohydride or diisobutylaluminum hydride has been studied in order to illuminate the factors involved in the high levels of asymmetric induction obtained in the bicyclic system. The conditions for the formation of the exo-5,7-dimethyl-6,8-dioxabicyclo[3.2.1]octane are DIBAH reduction of MVK dimer in ether at reflux followed by acidic cyclizatioan, and for the endo isomer are $Zn(BH_4)_2$ reduction with $ZnCl_2$ at $0^{\circ}C.$.

Preparation of Nonlinear Optical Poly(Alkyl Vinyl Ethers). 4.$^1$ Synthesis and Characterization of Poly[$3^{\prime},5^{\prime}-dimethoxy-4^{\prime}$-(2-vinyloxyethoxy)-4-nitrostilbene] and Poly[$3^{\prime},5^{\prime}-dimethoxy-4^{\prime}$-(2-vinyloxyethoxy)-2,4-dinitrostilbene]

  • 이주연
    • Bulletin of the Korean Chemical Society
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    • v.16 no.4
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    • pp.336-340
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    • 1995
  • 3',5'-Dimethoxy-4'-(2-vinyloxyethoxy)-4-nitrostilbene 2 and 3',5'-dimethoxy-4'-(2-vinyloxyethoxy)-2,4-dinitrostilbene 5 were prepared by the reactions of 2-iodoethyl vinyl ether with 3',5'-dimethoxy-4'-hydroxy-4-dinitrostilbene 1 and 3',5'-dimethoxy-4'-hydroxy-2,4-dinitrostilbene 4, respectively. Monomers 2 and 5 were polymerized with cationic initiators to obtain polymers with 3',5'-dimethoxy-4'-oxy-4-nitrostilbene and 3',5'-dimethoxy-4'-oxy-2,4-nitrostilbene, which are presumably effective chromophores for second-order nonlinear optical application in the side chain. The resulting polymers 3 and 6 were soluble in DMSO and DMF. The inherent viscosities of the polymers were in the range of 0.28-0.33 dL/g in DMSO. Polymers 3 and 6 showed a thermal stability up to 250 ℃ in TGA thermogram, and the Tg values obtained from DSC thermograms were in the range of 81-87°.

Synthesis and Cationic Polymerization of Vinyl Ethers Containing the NLO-chromophores Oxybenzylidenemalononitrile and Oxybenzylidenecyanoacetatate in the Side Chain

  • 이주연;김무용;김지향
    • Bulletin of the Korean Chemical Society
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    • v.19 no.2
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    • pp.155-159
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    • 1998
  • o-(2-Vinyloxyethoxy)benzylidenemalononitrile (4a), methyl o-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (5a), methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (5b), p-(2-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate (6b) were prepared by the condensation of o-(2-vinyloxyethoxy)benzaldehyde (1), m-(2-vinyloxyethoxy)benzaldehyde (2), and p-(2-vinyloxyethoxy)benzaldehyde (3) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 4a-b and 6a-b polymerized readily with cationic initiators to give polymers with the NLO-chromophores o- and p-oxybenzylidenemalononitrile or o- and p-oxybenzylidenecyanoacetate in side chain at -60 ℃, while meta-isomers 5a and 5b gave lower yields of polymers under the same conditions. The resulting polymers 7-9 were soluble in common organic solvents and the inherent viscosities of polymers were in the range of 0.20-0.30 dL/g in acetone. Solution-cast films were clear and brittle, showing Tg values in the range of 40-70 ℃.

Controlled Transdermal Delivery of Loxoprofen from an Ethylene-Vinyl Acetate Matrix

  • Ryu, Sang-Rok;Shin, Sang-Chul
    • Journal of Pharmaceutical Investigation
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    • v.41 no.6
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    • pp.347-354
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    • 2011
  • Repeated oral administration of loxoprofen can induce many side effects such as gastric disturbances and acidosis. Therefore, we considered alternative routes of administration for loxoprofen to avoid such adverse effects. The aim of this study was to develop an ethylene-vinyl acetate (EVA) matrix system containing a permeation enhancer for enhanced transdermal delivery of loxoprofen. The EVA matrix containing loxoprofen was fabricated and the effects of drug concentration, temperature, enhancer and plasticizer on drug release were studied from the loxoprofen-EVA matrix. The solubility of loxoprofen was highest at 40% (v/v) PEG 400. The release rate of drug from drug-EVA matrix increased with increased loading dose and temperature. The release rate was proportional to the square root of loading dose. The activation energy (Ea), which was measured from the slope of log P versus 1000/T, was 5.67 kcal/mol for a 2.0% loaded drug dose from the EVA matrix. Among the plasticizer used, diethyl phthalate showed the highest release rate of loxoprofen. Among the enhancers used, polyoxyethylene 2-oleyl ether showed the greatest enhancing effect. In conclusion, for the enhanced controlled transdermal delivery of loxoprofen, the application of the EVA matrix containing plasticizer and penetration enhancer could be useful in the development of a controlled drug delivery system.

Characterization and Performance of MEA for Direct Methanol Fuel Cell Prepared with PFA Grafted Polystyrene Membranes via Radiation-Grafting Method (방사선 그라프트 PFA-폴리스티렌 멤브레인으로 제조한 직접 메탄올 연료전지용 MEA의 성능과 특성)

  • Kang, Se-Goo;Peck, Dong-Hyun;Kim, Sang-Kyung;Lim, Seong-Yop;Jung, Doo-Hwan;Park, Young-Chul;Shin, Jun-Hwa;Kang, Phil-Hyun;Nho, Young-Chang;Shul, Yong-Gun
    • Journal of the Korean Electrochemical Society
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    • v.12 no.2
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    • pp.173-180
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    • 2009
  • In order to develop a novel polymer electrolyte membrane for direct methanol fuel cell (DMFC), styrene monomer was graft-polymerized into poly(tetrafluoroethylene perfluoropropyl vinyl ether) (PFA) film followed by a sulfonation reaction. The graft polymerization was prepared by the $\Upsilon$-ray radiation-grafting method. Subsequently, sulfonation of the radiation-grafted film was carried out in a chlorosulfonic acid/1,2-dichloroethane (2 v/v%) solution. The chemical, physical, electrochemical and morphological properties of the radiation-grafted membranes (PFA-g-PSSA) were characterized by fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The water uptake, ionic conductivity, and methanol permeability of the PFA-g-PSSA membrane were also measured. The cell performances of MEA prepared with the PFA-g-PSSA membranes were evaluated and the cell resistances were measured by an impedance analyzer. The MEA using PFA-g-PSSA membranes showed superior performance for DMFCs in comparison with the commercial Nafion 112 membrane.

Electro-conductive polymer by $\gamma$-ray irradiation ($\gamma$-선 조사방식에 의한 전도성 폴리머 제작 특성)

  • ;;;G.A. Mun;V.A. Kovtunets;Z.S. Nurkeeva;V.V. Khutoryanskiy
    • Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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    • 2003.05a
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    • pp.762-765
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    • 2003
  • 에틸렌글리콜(ethyleneglycol)을 이용한 폴리비닐에테르(polyvinyl ether)와 같은 고분자물질을 활용하여 Co$^{30}$ 방사선원으로부터 ${\gamma}$선을 조사시켜, 고분자 물질의 성질을 변화시킴으로써 화학, 전기전자, 환경 및 기타 여러 가지 응용분야에 적용하여 이용할 수 있는 기술을 개발하였다. 이를 바탕으로 관련재료의 단량체(monomer)로부터 중합체(polymer)를 합성하여 water swelling을 시키는 과정에서 각종 (금속) 이온을 흡입-제거하는 방법의 환경복원기술, 흡입 금속이온을 표면에 밀집시켜 금속막을 형성하는 응용기술, 생체조직의 대용물질로 활용하는 의용공학 및 열감지특성(thermal sensitive property) 또는 pH 감지특성(pH sensitive property)을 이용하여 의용기술에 적용하는 polymer 응용기술 등의 폭넓은 활용을 위하여 그 일환으로 전도성 고분자 제조기술로의 활용가능성을 연구하였다.

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Effect of Ionizing Radiation on Mechanical and Electric Properties of Polymer Composites Based on Polyvinyl ether of Ethyleneglycol

  • Mun G. A.;Nurkeeva Z. S.;Kovtunets V. A.;Kupchishin A. I.;Akhmetkalieva G. T.;Khutoryanskiy V. V.;Al-Sayed A. A.;Soh Dea-Wha
    • Transactions on Electrical and Electronic Materials
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    • v.4 no.3
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    • pp.25-28
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    • 2003
  • Radiation technology is an effective way for regulating polymeric materials to physicochemical and mechanical properties. New polymeric hydrogels based on vinyl ethers have been synthesized by the $\gamma$-initiated polymerization method. In this paper, we have studied the effect of radiation on mechanical and electrochemical properties of new rubber-like polymeric composite materials based on polyvinylether of ethyleneglycol (PVEEG).