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Ethyl Vinyl Ether (ethyl + vinyl_ether)
Selected AbstractsCycloadditions with Cyclic Seven-Membered Ketene Imines,,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2005Henry Giera Abstract The cyclic seven-membered ketene imines 8 , isolable despite ring strain , are available by reactions of thiocarbonyl ylides 3 with 2,3-bis(trifluoromethyl)fumaronitrile (4). In contrast to open-chain ketene imines, 8A,8C underwent (2+2) cycloadditions with ethyl vinyl ether at the C=N double bond; the diastereomeric cycloadducts 10 and 11 were characterized by their spectra, and 10A by X-ray analysis. The corresponding adduct 12 from 8A and 2-methoxypropene easily hydrolyzed to give 14. When 8A,8C were treated with diazomethane, (2+3) cycloadditions took place side by side to the C=C and C=N bond of 8. A supposed adduct at the C=C bond, 18A, lost N2, and 19A was formed which contained a cyclopropylideneamine group; at 50 °C, cheletropic elimination produced the isocyanide 22A. Diazomethane addition to the C=N bond of 8 gave rise to condensed 1,2,3-triazoles 21; the HF elimination from the pyrazolines 20 as primary adducts was probably induced by the excess of diazomethane. The structure of 21B was confirmed by X-ray. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] The mechanisms of the homogeneous, unimolecular, elimination kinetics of several , -substituted diethyl acetals in the gas-phaseJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 9 2010José R. Mora Abstract The rates of gas-phase elimination of several , -substituted diethyl acetals have been determined in a static system and seasoned with allyl bromide. The reactions, inhibited with toluene, are homogeneous, unimolecular, and follow first-order law kinetics. These elimination processes involve two parallel reactions. The first parallel reaction yields ethanol and the corresponding ethyl vinyl ether. The latter product is an unstable intermediate and further decomposes to ethylene and the corresponding substituted aldehyde. The second parallel reaction gives ethane and the corresponding ethyl ester. The kinetics has been measured over the temperature range of 370,441,°C and pressure range of 23,160,torr. The rate coefficients are given by the following Arrhenius equations: The differences in the rates of ethanol formation may be attributed to electronic transmission of the , -substituent. The comparative kinetic and thermodynamic parameters of the parallel reactions suggest two different concerted polar four-membered cyclic transition state types of mechanisms. Copyright © 2010 John Wiley & Sons, Ltd. [source] Synthesis of poly(vinyl ether) polyols with pendant oxyethylene chains and properties of hydrophilic, thermo-responsive polyurethanes prepared therefromJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2010Tamotsu Hashimoto Abstract Hydroxy-terminated telechelic poly(vinyl ether)s with pendant oxyethylene chains were synthesized by the reaction of the CH3CH(OCOCH3)O[CH2]4OCH(OCOCH3)CH3/Et1.5AlCl1.5/THF-based bifunctional living cationic polymers of 2-methoxyethyl vinyl ether (MOVE), 2-ethoxyethyl vinyl ether (EOVE), and 2-(2-methoxyethoxy)ethyl vinyl ether (MOEOVE) with water and the subsequent reduction of the aldehyde polymer terminals with NaBH4. The obtained poly(vinyl ether) polyols were reacted with an equimolar amount of toluene diisocyanates [a mixture of 2,4- (80%) and 2,6- (20%) isomers] to give water-soluble polyurethanes. The aqueous solutions of these polyurethanes caused thermally induced precipitation at a particular temperature depending on the sort of the thermosensitive poly(vinyl ether) segments containing oxyethylene side chains. These polyurethanes also function as polymeric surfactants, lowered the surface tension of their aqueous solutions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1641,1648, 2010 [source] Synthesis of amphiphilic copolymer brushes: Poly(ethylene oxide)-graft-polystyreneJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2006Zhongyu Li Abstract A well-defined amphiphilic copolymer brush with poly(ethylene oxide) as the main chain and polystyrene as the side chain was successfully prepared by a combination of anionic polymerization and atom transfer radical polymerization (ATRP). The glycidol was first protected by ethyl vinyl ether to form 2,3-epoxypropyl-1-ethoxyethyl ether and then copolymerized with ethylene oxide by the initiation of a mixture of diphenylmethylpotassium and triethylene glycol to give the well-defined polymer poly(ethylene oxide- co -2,3-epoxypropyl-1-ethoxyethyl ether); the latter was hydrolyzed under acidic conditions, and then the recovered copolymer of ethylene oxide and glycidol {poly(ethylene oxide- co -glycidol) [poly(EO- co -Gly)]} with multiple pending hydroxymethyl groups was esterified with 2-bromoisobutyryl bromide to produce the macro-ATRP initiator [poly(EO- co -Gly)(ATRP). The latter was used to initiate the polymerization of styrene to form the amphiphilic copolymer brushes. The object products and intermediates were characterized with 1H NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, Fourier transform infrared, and size exclusion chromatography in detail. In all cases, the molecular weight distribution of the copolymer brushes was rather narrow (weight-average molecular weight/number-average molecular weight < 1.2), and the linear dependence of ln[M0]/[M] (where [M0] is the initial monomer concentration and [M] is the monomer concentration at a certain time) on time demonstrated that the styrene polymerization was well controlled. This method has universal significance for the preparation of copolymer brushes with hydrophilic poly(ethylene oxide) as the main chain. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4361,4371, 2006 [source] Preparation of novel poly(ethylene oxide- co -glycidol)-graft-poly(,-caprolactone) copolymers and inclusion complexation of the grafted chains with ,-cyclodextrinJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2006Juan Huang Abstract A well-defined comblike copolymer of poly(ethylene oxide- co -glycidol) [(poly(EO- co -Gly)] as the main chain and poly(,-caprolactone) (PCL) as the side chain was successfully prepared by the combination of anionic polymerization and ring-opening polymerization. The glycidol was protected by ethyl vinyl ether to form 2,3-epoxypropyl-1-ethoxyethyl ether (EPEE) first, and then ethylene oxide was copolymerized with EPEE by an anionic mechanism. The EPEE segments of the copolymer were deprotected by formic acid, and the glycidol segments of the copolymers were recovered after saponification. Poly(EO- co -Gly) with multihydroxyls was used further to initiate the ring-opening polymerization of ,-caprolactone in the presence of stannous octoate. When the grafted copolymer was mixed with ,-cyclodextrin, crystalline inclusion complexes (ICs) were formed, and the intermediate and final products, poly(ethylene oxide- co -glycidol)- graft -poly(,-caprolactone) and ICs, were characterized with gel permeation chromatography, NMR, differential scanning calorimetry, X-ray diffraction, and thermogravimetric analysis in detail. The obtained ICs had a channel-type crystalline structure, and the ratio of ,-caprolactone units to ,-cyclodextrin for the ICs was higher than 1:1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3684,3691, 2006 [source] Fluorinated vinyl ethers as new surface agents in the photocationic polymerization of vinyl ether resinsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2003R. Bongiovanni Abstract The syntheses of fluorinated vinyl ethers (H2CCHOCH2CH2CnF2n+1, n = 6 or 8) and their copolymerizations with bis(4-vinyloxybutyl) isophthalate are reported. The fluorinated monomers were prepared by the transetherification of ethyl vinyl ether and fluorinated alcohols in a 75% yield. Added in low concentrations (0.1,3.0 wt %) to formulations containing bis(4-vinyloxybutyl) isophthalate, they did not affect the kinetics of the cationic photopolymerization. The cured films were transparent and showed interesting properties in terms of wettability, hardness, cross-cut adhesion, and chemical inertness. The fluoromonomers increased the hydrophobicity of the film surface, whereas the adhesion on various substrates such as glass and wood was unchanged. An increase in the methyl ethyl ketone resistance was also observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2890,2897, 2003 [source] Synthesis and hydrogel formation of fluorine-containing amphiphilic ABA triblock copolymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2001Kozo Matsumoto Abstract Fluorine-containing amphiphilic ABA triblock copolymers, poly(2-hydroxyethyl vinyl ether)- block -poly[2-(2,2,3,3,3-pentafluoropropoxy)ethyl vinyl ether]- block -poly(2-hydroxyethyl vinyl ether) [poly(HOVE- b -PFPOVE- b -HOVE)] (HFH), poly[2-(2,2,3,3,3-pentafluoropropoxy)ethyl vinyl ether]- block -poly(2-hydroxyethyl vinyl ether)- block -poly[2-(2,2,3,3,3-pentafluoropropoxy)ethyl vinyl ether] [poly(PFPOVE- b -HOVE- b -PFPOVE)] (FHF), and poly(n -butyl vinyl ether)- block -poly(2-hydroxyethyl vinyl ether)- block -poly(n -butyl vinyl ether) [poly(NBVE- b -HOVE- b -NBVE)] (LHL), were synthesized, and their behavior in water was investigated. The aforementioned polymers were prepared by sequential living cationic polymerization of 2-acetoxyethyl vinyl ether (AcOVE) and PFPOVE or NBVE, followed by hydrolysis of acetyl groups in polyAcOVE. FHF and LHL formed a hydrogel in water, whereas HFH gave a homogeneous aqueous solution. In addition, the gel-forming concentration of FHF was much lower than that of corresponding LHL. Surface-tension measurements of the aqueous polymer solutions revealed that all the triblock copolymers synthesized formed micelles or aggregates above about 1.0 × 10,4 mol/L. The surface tensions of HFH and FHF solutions above the critical micelle concentration were lower than those of LHL, indicating high surface activity of fluorine-containing triblock copolymers. Small-angle X-ray scattering measurements revealed that HFH formed a core-shell sperical micelle in 1 wt % aqueous solutions, whereas the other block copolymers caused more conplicated assembly in the solutions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3751,3760, 2001 [source] Photoinitiated alternating copolymerization of vinyl ethers with chlorotrifluoroethylenePOLYMER INTERNATIONAL, Issue 7 2002Manuel Gaboyard Abstract The photoinitiated copolymerization of chlorotrifluoroethylene (CTFE) with several vinyl ethers [ethyl vinyl ether (EVE), 2-chloroethyl vinyl ether (CEVE), cyclohexyl vinyl ether (CHVE), 4-hydroxybutyl vinyl ether (HBVE)] was studied. CTFE is an acceptor monomer (e,,,1.5) whereas vinyl ethers are donor monomers (e,,,,1.5), and therefore their copolymerization led to alternating copolymers, as indicated by elementary analysis. The equilibrium constant (KF) of the charge-transfer complex formation (CTC) was determined by 19F NMR spectroscopy. Under our experimental conditions, KF was low for CHVE/CTFE and HBVE/CTFE systems, 0.058 and 0.013,l mol,1 respectively. It can be assumed that the copolymerization involves the free monomers rather than propagation via the donor,acceptor complex. The alternating structure arises from the great difference in polarity between the two types of monomers. Several functional copolymers were prepared in good yield and with molecular weight close to 15,000,g,mol,1. © 2002 Society of Chemical Industry [source] | |||||||||||||