Showing papers on "Methanol published in 1969"
TL;DR: In this paper, the first success in using carbon dioxide as a direct starting material for synthesizing high polymers was reported, which was confirmed with the aid of IR, NMR and elemental analysis.
Abstract: Attempts to copolymerize carbon dioxide with epoxide led us to the first success in using carbon dioxide as a direct starting material for synthesizing high polymers. Some organometallic catalyst systems were found to catalyze the alternate copolymerization of carbon dioxide and epoxide, resulting in the formation of polycarbonates, the structures of which were confirmed with the aid of IR, NMR and elemental analysis. Diethylzinc-water system produced a methanol insoluble aliphatic polycarbonate of much higher molecular weight than that produced by polycondensation. Thermal properties of the methanol insoluble polycarbonate were studied by differential thermal analysis and thermogravimetric analysis.
521 citations
Patent•
06 Mar 1969TL;DR: A clear stable motor fuel composition having an improved octane rating comprising alcohol selected from the group consisting of methanol in the amount of about 2.0 to 5.0 vol. %, ethanol, and mixtures thereof, and water to provide a total water concentration of about 0.1 to 0.5 wt. % as discussed by the authors.
Abstract: A clear stable motor fuel composition having an improved octane rating comprising alcohol selected from the group consisting of methanol in the amount of about 2.0 to 5.0 vol. %, ethanol in the amount of about 2.0 to 10.0 vol. %, and mixtures thereof in the amount of about 3 to 9.0 vol. %; about 2.0 to 10 vol. % of a cosolvent alcohol selected from the group consisting of tertiary butyl alcohol, isopropanol, and mixtures thereof; water to provide a total water concentration of about 0.1 to 0.5 wt. % (basis weight of motor fuel composition); about 0.01 to 3.0 weight percent (basis weight of motor fuel composition) of a nonionic ethoxylated bisphenol surfactant; and the balance of said motor fuel composition comprising gasoline.
246 citations
TL;DR: In this paper, the kinetics of methanol oxidation over MoO3Fe2(MoO4)3 catalyst were studied by means of a differential flow reactor and a pulse reactor in the temperature range 180-280 °C.
86 citations
TL;DR: The mechanism of these carbonylation reactions is discussed in this paper, and the reactions described in this paper afford very useful synthetic methods for itaconic acid and their derivatives, such as diisopropylidenesuccinic anhydride as a main product in benzene.
50 citations
TL;DR: In this article, the reaction of methanol and ethanol to give water and the corresponding ether were obtained using a packed-bed flow reactor at 1 atm total pressure, as vapor-phase reactants contacted catalyst at temperatures from 80 ° to 120 °C.
49 citations
49 citations
TL;DR: In this article, the linear dimer of methanol is found to be more stable than the cyclic dimer, and the hydrogen bonds in the trimer are stronger than those in linear dimers.
Abstract: By both the EHT and the CNDO/2 calculations, the linear dimer of methanol is found to be more stable than the cyclic dimer. The hydrogen bonds in the trimer are stronger than those in linear dimers. The proton potential function, charge densities, and overlap populations in the linear dimer of methanol have been obtained. The CNDO/2 calculations show that the cis-form of formic acid is more stable than the trans-form, in agreement with experimental data. The cyclic dimer of formic acid is more stable than the open dimer. The β-form of formic acid trimer is more stable than the α-form. The proton potential function and the charge densities in the cyclic dimer of formic acid have been obtained. The CNDO/2 method gives more realistic proton potential functions for the dimers of methanol and formic acid. The O ... O stretching force constant in the dimers of methanol and formic acid have been estimated to be 0.13 × 105 dynes/cm and 0.27 × 105 dynes/cm, respectively, in agreement with experimental data.
46 citations
TL;DR: The thermal degradation of polyphenylenes and poly(phenylene oxides) was studied under vacuum at temperatures between 350 and 620°C as discussed by the authors, and the volatile and solid degradation products were analyzed by mass spectroscopy, infrared spectroscopic, and elemental analysis.
Abstract: The thermal degradation of polyphenylenes and poly(phenylene oxides) was studied under vacuum at temperatures between 350 and 620°C. The volatile and solid degradation products were analyzed by mass spectroscopy, infrared spectroscopy, and elemental analysis. Overall mechanisms for the thermal breakdown have been proposed. Polyphenylene decomposes to form polymer carbon, while hydrogen is the major volatile product. Some ring breakdown occurs with evolution of methane. Poly(phenylene oxide) forms mainly low molecular weight chain fragments, partially with hydroxyl endgroups. Some of the ether linkages decompose with ring breakdown, yielding carbon monoxide, water, and some carbon dioxide. Pendent groups on polyphenylenes and poly(phenylene oxides) are removed at the lower temperatures. The hydroxyl group yields essentially carbon monoxide and dioxide (the carbon being supplied by the rings), the methyl group methane, and the methoxy group methane and some methanol.
43 citations
41 citations
TL;DR: A mixed culture of methanol oxidizing bacteria has been cultivated on simple inorganic salts medium supplemented with methanoline as mentioned in this paper, and the maximum yield was 4.5 g dw/I and the mean generation time 3.2 hr.
Abstract: A mixed culture of methanol oxidizing bacteria has been cultivated on simple inorganic salts medium supplemented with methanol. Optimal growth occurred at 31°C, pH 6.0–6.3, and a methanol concentration between 1 and 2 ml/1, of medium. The maximum yield was 4.5 g dw/I and the mean generation time 3.2 hr.
It was estimated that 41% of methanol carbon was converted into cell-carbon, and that 73% of the inorganic nitrogen was converted to organic nitrogen.
40 citations
01 Jan 1969
TL;DR: The effect of methanol on the micellar behaviour of aqueous solutions of sodium dodecyl sulphate has been studied by light scattering measurements as discussed by the authors. But the effect of micelle formation was not investigated.
Abstract: The effect of addition of methanol on the micellar behaviour of aqueous solutions of sodium dodecyl sulphate has been studied by light scattering measurements At low alcohol concentration there is a small decrease in the critical micelle concentration but no change in micellar weight With increasing alcohol concentration the critical micelle concentration increases and the micellar weight decreases, and at about a mole fraction of alcohol of 025 there is no evidence of micelle formation Interpretation of the behaviour requires a knowledge as yet unknown of the part played by the changes in solvent structure and dielectric constant, and by the penetration of additive into the micelles
TL;DR: The active sites of alumina and silica-alumina catalysts for the dehydration of methanol, as well as the mechanisms of this reaction, were studied in a flow system at 228 °C by poisoning the catalyst during the run with nitrogen bases as discussed by the authors.
TL;DR: In this article, the relative importance of the McLAFFERTY and EMERY effects in the mass spectral degradation of methoxycarbonyl and methyl substituted phenols is discussed, and the formation of the methoxy carbonyl-hexadienes 18e and 18f upon photolysis of 9e and 17f in methanol supports the structure elucidation.
Abstract: The acid catalyzed isomerization of several substituted oxanorbornadienes 4 and oxepines 10 - easily available from 4 by a photochemical and a consecutive thermal step - allows the synthesis of several highly substituted phenols and 2,4-cyclohexadienones in a straightforward manner and with good to excellent yields. The formation of the methoxycarbonyl-hexadienes 18e and 18f upon photolysis of 9e and 17f in methanol supports the structure elucidation. The relative importance of the McLAFFERTY and EMERY effects in the mass spectral degradation of methoxycarbonyl and methyl substituted phenols are discussed.
Patent•
26 May 1969TL;DR: In this article, a process for heating an ORGANIC COMPOUND, a 1:1 COPOLYMER of an ALIPHATIC HYDROCARBON HAVING at LEAST three CARBON ATOMS, SUCH AS 1-HEXENE, and MALEIC ANHYDRIDE, was defined.
Abstract: A PROCESS IS DEFINED FOR HEATING AN ORGANIC COMPOUND CONTAINING AT LEAST ONE HALF-ESTER OF A DICARBOXYLIC ACID WHERE THE CARBONYL GROUPS ARE DIRECTLY CONNECTED TO ADJACENT INTERNAL ALIPHATIC CARBON ATOMS TO A TEMPERATURE IN EXCESS OF ABOUT 80*C. TO CONVERT THE HALF-ESTER GROUPS TO CYLIC ANHYDRIDE GROUPS AND A BY-PRODUCT ALCOHOL. THE ORGANIC COMPOUND IS A 1:1 COPOLYMER OF AN ALIPHATIC HYDROCARBON HAVING AT LEAST THREE CARBON ATOMS, SUCH AS 1-HEXENE, AND MALEIC ANHYDRIDE. THE ORGANIC COMPOUND PREPARED FROM AN OLEFIN HAVING FROM THREE TO TEN CARBON ATOMS CAN BE PRECIPITATED AS A SOLIC FROM ITS HOMOGENEOUS REACTION MEDIUM BY POURING THE REACTION SOLUTION INTO A MONOHYDROXY ALCOHOL HAVING ONE TO FOUR CARBON ATOMS, SUCH AS METHANOL. SOME METHYL HALF-ESTER FORMS CAN BE REMOVED BY HEATING THE SEPARATED SOLID PRODUCT AT A TEMPERATURE IN EXCESS OF 80*C. WHILE REMOVING THE MONOHYDROXY ALCOHOL. THUS, 1-HEXENE-MALEIC ANHYDRIDE COPOLYMERS FREE OF HALF-ESTER GROUPS CAN BE RECOVERED. IF THE ORGANIC COMPOUND CONTAINS BOTH HALF-ESTER AND DIESTER GROUPS, THE RESULTING COMPOUND AFTER HEATING TO A TEMPERATURE IN EXCESS OF 80*C. WILL CONTAIN ANHYDRIDE AND DIESTER LINKAGES.
TL;DR: The transferase activity of the enzyme was demonstrated by identification of methyl β-galactoside as one of the reaction products and it was demonstrated that low concentrations of n -propyl alcohol in the absence of added magnesium ions causes the tetramer to dissociate into inactive dimers.
TL;DR: In this paper, the authors show that the effect of a small amount of salt on 4.6kcal/g-mol can be significant, as shown in Figure 1.
Abstract: メタノールに対する炭酸ガス,硫化水素,水素および硫化水素と水素の混合物の溶解度を温度0,-15,-25,-30℃,圧力50atm以下で測定し,熱力学的解析によって次の結果をえた。(1)炭酸ガス,硫化水素,水素がメタノールに溶解する場合および水素が硫化水素に溶解する場合のヘンリー定数の値を各温度について求めた。(2)メタノールに対する炭酸ガスの無限希釈における溶解熱は4.1kcal/g-mol,硫化水素のそれは4.6kcal/g-molであった。(3)メタノールに対する炭酸ガス,硫化水素の溶解度は本実験の範囲ではvanLaarの2定数の式で工業的に満足すべき精度で表現できる。
TL;DR: In this article, the radical decomposition of eight kinds of alkyl α, α-azobisiso-butyrates in various solvents, such as cyclohexane, benzene, acetoni-trile, methanol, and acetic acid, was investigated.
Abstract: The radical decompositions of eight kinds of alkyl α, α′-azobisiso-butyrates in various solvents, such as cyclohexane, benzene, acetoni-trile, methanol, and acetic acid, and in methanol solution of stannic chloride or zinc chloride were investigated. It was found that the methyl α, α′-azobisisobutyrate decomposed through first-order kinetics in these solvents, but the resulting rate constants changed significantly with the kind of solvent or metal chloride used. These rate constants were also observed to correlate with the polarities and the proton-donating abilities (ET values) of the solvents used. The activation enthalpies and entropies at 60°C were determined; the former values were kept constant independent of the reaction medium, but the latter values were changed. It was found that the decompositions of alkyl α, α′-azobisisobuty-rates having methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and n-amyl ester groups in methanol also fit first-order kinetics, while the resulti...
TL;DR: In this article, the authors studied the mechanism of alcohol decomposition over alumina by means of infra-red techniques in the working condition, and they concluded that the adsorbates on the active surface behave uniformly in their working state.
Abstract: The mechanism of alcohol decomposition over alumina has been studied by means of infra-red techniques in the working condition. The decomposition of methanol (or ethanol) to ether, or that of isopropanol (or ethanol) to olefin, over alumina is zero order as to alcohol, the rate being independent of its pressure. When all the alcohol vapour was trapped out of the system, the evolution of ether or olefin first continued at the same rate through the decomposition of the adsorbed alkoxides. Consequently, the ether or olefin formation is the recombination reaction or the decomposition reaction of the alkoxide group on the surface: MeOH → MeO(ad.)+ H(ad.)→ MeOMe + H2O [graphic omitted] i-PrOH → i-PrO(ad.)+ H(ad.)→ C3H6+ H2O.
The evolution of ethylene from diethyl ether was also independent of ether pressure, and diethyl ether was adsorbed on alumina with dissociation to ethoxide groups. Consequently, diethyl ether and ethylene were formed from ethanol through the common intermediate, the ethoxide group on the surface.
Ether or olefin formation was retarded by the water produced. The decomposition rate decreased with the increasing amount of water adsorbed. The number of active sites for ether formation was estimated for the methanol decomposition. It was concluded that the adsorbates on the active surface behave uniformly in their working state.
TL;DR: In this paper, the kinetics of methanol oxidation were studied over manganese dioxide-molybdenum trioxide catalyst in an integral flow reactor between 250 and 460 °C, at space velocities of 9.6 × 103 to 8.4 × 104 hr−1.
TL;DR: The extent of hydration of three primary alcohols in aqueous solution was determined by means of the difference between the fluidities measured at various concentrations and calculated by the Kendall equation as mentioned in this paper.
Abstract: The extent of hydration of three primary alcohols in aqueous solution was determined by means of the difference between the fluidities measured at various concentrations and calculated by the Kendall equation. These differences went through a single, pronounced maximum for each of the three binary systems, at compositions corresponding approximately to molar water-alcohol ratios of 3 to 2, 4 to 1, and 5 to 1 for methanol, ethanol, and 1 -propanol, respectively. These are the compositions
TL;DR: In this paper, the salt effect at each infinite dilute concentration of acetone and methanol increases with the increasing solubility of each salt in the rich concentration component, and CaCl2, LiCl and CaBr2 are observed to shift the azeotropic composition from 8O.1 to 88.6, 91.0 and 94.0 mole % of the acetone, respectively.
Abstract: Vapor-liquid equilibrium data at atmospheric pressure of the system: acetone-methanol-salt are studied. The Salts, Kl, NaCl, MgCl2, CaCl2, LiCl, and CaBr2 are examined to observe the salt effect on the acetone-methanol system. Effective salts are CaCl2, LiCl and CaBr2, which are more soluble in methanol than Kl, NaCl and MgCl2. CaCl2, LiCl and CaBr2 are observed to shift the azeotropic composition from 8O.1 to 88.6, 91.0 and 94.0 mole % of acetone, respectively. The salt effect at each infinite dilute concentration of acetone and methanol increases with the increasing solubility of each salt in the rich concentration component.
TL;DR: In this article, the behavior and state of aggregation of barium dinonylnaphthalene sulfonate in toluene and methanol solutions were studied by ultracentrifugation and viscometry.
TL;DR: In this article, the reaction of methyl 4,6-O -benzylidene-α-D-glucopyranoside 2,3-carbonate with various nucleophines was investigated.
TL;DR: In this paper, the potential differences for the transfer from water to nonaqueous solvents have been calculated from the standard chemical potential differences in mixtures of water with methanol, ethanol, dioxane, acetone and acetic acid.
Abstract: Solubilities of some alkali and tetraalkylammonium perchlorates in mixtures of water with methanol, ethanol, dioxane, acetone and acetic acid have been determined conductometrically. From these solubilities the standard chemical potential differences for the transfer from water to the mixed or nonaqueous solvents have been calculated. In these calculations deviations from ideal behaviour caused by salt effects and ionic association have been taken into account.
TL;DR: In this article, steady state permeation rates and equilibrium sorption measurements were made as a function of temperature for a series of alcohols in a polybutylene adipate polyurethan.
Abstract: Steady-state permeation rates and equilibrium sorption measurements were made as a function of temperature for a series of alcohols in a polybutylene adipate polyurethan. The alcohol series included methanol; ethanol; n-propanol; n-, iso-, sec-, and t-butanol; n-pentanol, n-hexanol, and n-heptanol (all at unit activity). Calculated integral diffusivities of the various penetrants correlated well with effective penetrant size. The solubility coefficients for the various alcohols increased as the difference between the solubility parameters of the polymer and penetrant decreased for the normal alcohol series. The solubility coefficients for the branched alcohol isomers were characterized by values lower than those predicted by the correlation for the normal alcohols; possibly steric hindrance limits sorption on specific polymer sites. A detailed analysis of the system ethanol/poly(butylene adipate-polyurethan) revealed a sigmoidal increase of the diffusion coefficient with increasing penetrant conc...
TL;DR: In this paper, Gas chromatograpy at 120°, onn porous polymer beads, Porapak N, can be used to analyse formaldehyde solutions, and the results are the same or better than those obtained by classical methods for analiysis of technical formalin.