Abstract: Multistep process for the preparation of butanedicarboxylic acid by the hydrogenation of carbon monoxide under pressure in the presence of a cobalt carbonyl catalyst, the improvement of heating at a temperature of 250.degree. to 350.degree. C. under superatmospheric pressure the resulting aqueous solution of cobalt carbonyl hydride that has been extracted with butadiene or with mixtures thereof before using in a subsequent step of the multistep process.

Abstract: Water, primary alcohols or secondary alcohols together with carbon monoxide can be added across ethylenic or acetylenic bonds in a wide variety of organic compounds to form acids or esters. The reaction is conducted in the presence of a catalyst system consisting of an organophosphorus palladium halide compound and certain metal halide compounds.

Abstract: A process for preparing a diester of malonic acid which comprises reacting ketene and carbon monoxide with an ester of nitrous acid catalytically in the presence of metallic palladium or a salt thereof.

Abstract: In a process for the preparation of dimethyl butanedicarboxylates, wherein(a) butadiene or a hydrocarbon mixture containing butadiene is reacted with carbon monoxide and methanol in the presence of a tertiary nitrogen base and a cobalt carbonyl catalyst at from 80.degree. to 150.degree. C. under superatmospheric pressure,(b) the greater part of the tertiary nitrogen base and any excess hydrocarbons are removed and(c) the methyl pentenoate thus obtained is reacted with carbon monoxide and methanol, in the presence of a cobalt carbonyl catalyst and the residual amount of tertiary nitrogen base, at from 140.degree. to 200.degree. C. under superatmospheric pressure, to give the dimethyl butanedicarboxylate, the improvement that the reaction mixture obtained in stage (a) after reaction of the butadiene is cooled until it separates into two phases, and a part-stream of from 20 to 80% by volume of the lower phase is recycled to stage (a).

Abstract: There is provided an improved continuous homogeneous catalytic carbonylation process wherein a mixed gas stream is removed from the carbonylation reactor, condensable liquids separated from said gas stream and said gas stream vented, the improvement comprising contacting said gas stream with a plurality of hollow fiber membranes selectively permeable to hydrogen under conditions substantially non-degrading of the membranes to generate a non-permeated gas stream of higher carbon monoxide content and recycling said non-permeated gas stream to the carbonylation process reactor. There is also provided for the recovery and recycle to the process of carbonylation products such as acetic or propionic acids by adsorption and removal from a solid adsorbent or absorption in a liquid absorbent.

Abstract: A high molecular weight polyester is produced by a two stage process: a partial melt process until the intrinsic viscosity of the polyester prepolymer reaches from about 0.35 to about 0.62 dl/g, and a solid state polymerization in a static bed until the intrinsic viscosity of the polycondensed polymer reaches at least 0.70 dl/g. The melt process employs greater concentrations of initial acid in combination with a heel or the addition of make-up acid to achieve optimal carboxyl content for the polyester prepolymer capable of use in the static bed solid state polymerization. This prepolymer with an optimal carboxyl content achieves a maximum solid state polymerization rate in a static bed. The production of the high molecular weight polyester by the two stage process minimizes chemical instability and deleterious polymerization byproducts.

Abstract: Sebacic acid is produced from adipic acid by half esterifying adipic acid with methanol to produce monomethyl adipate, carrying out electrolytic condensation of the monomethyl adipate in a methanol solution containing an alkali metal salt of the monomethyl adipate to give an electrolytic solution containing dimethyl sebacate, treating the electrolytic solution by a combination of water treatment and anion exchange treatment or a combination of cation exchange treatment and anion exchange treatment to remove the monomethyl adipate and its alkali metal salt from the electrolytic solution, separating the dimethyl sebacate, and hydrolyzing the dimethyl sebacate to give sebacic acid.

Abstract: Oxygenated organic compounds, e.g. esters, aldehydes, and amides, are prepared by reacting an olefinically unsaturated compound with carbon monoxide and a compound containing a replaceable hydrogen atom in the presence of a catalyst comprising cobalt and/or ruthenium carbonyl and a polyamine promoter ligand. These reactions are carried out under relatively mild conditions of temperature and pressure.

Abstract: A process for preparing a diester of a dicarboxylic acid having two more carbon atoms than the unsaturated hydrocarbon used as the starting material, which comprises subjecting an unsaturated hydrocarbon, carbon monoxide and an alcohol to reaction in the presence of a platinum group metal or a salt thereof; a compound selected from the group consisting of nitric acid, a nitrogen oxide and an ester of nitrous acid; and a halogen compound.

Abstract: A method for the preparation of organic esters of oxalic acid by reaction of carbon monoxide under pressure with the corresponding alcohol is disclosed, the improvement consisting in the use of a quite particular catalyst system. The catalyst is a binary system in which the principal member is a palladium complex and the co-catalyst is a compound, preferably an organic compound having an acidic nature, no matter how weak.

Abstract: A process for preparing a diester of oxalic acid which comprises bringing carbon monoxide into contact with an ester of nitrous acid or with an alcohol and a nitrogen oxide or a hydrate of the nitrogen oxide in the gaseous phase in the presence of a solid catalyst containing metallic palladium or a salt thereof, a gas containing molecular oxygen being introduced into the reaction system in cases where said nitrogen oxide or a hydrate of the nitrogen oxide requires molecular oxygen together with the alcohol to form an ester of nitrous acid.

Abstract: A process for preparing a diester of oxalic acid which comprises bringing carbon monoxide into contact with an ester of nitrous acid in the liquid phase, in the presence of metallic palladium or a salt thereof, preferably with introduction of a gas containing molecular oxygen into the reaction system, more preferably with further incorporation of an alcohol in the reaction system.

Abstract: This invention is directed to a half ester characterized by the following empirical formula: ##STR1## wherein n is a number having an average value of 1.7 to 2, and m is equal to 2-n. Also described herein is a composition comprising said half ester, maleic anhydride and an ethylenically unsaturated monomer, wherein at least 75 mole percent of the half ester is in the maleate form.

Abstract: In a process for producing a carboxylic acid or its ester by reacting an alcohol or an ether with carbon monoxide, the improvement wherein the reaction is performed in the presence of, as a solvent, an aryl ester of an aliphatic carboxylic acid represented by the formula ##STR1## wherein n is an integer of 1 to 5, R.sub.1 represents hydrogen or C.sub.1 -C.sub.4 alkyl or alkenyl, and R.sub.2 represents hydrogen, alkyl, aryl, alkenyl, hydroxymethyl, acyl, acyloxy, formyl, carboxy, hydroxy, halogen, sulfo, nitro, nitroso, amino, acid amide or cyano, and two or more R.sub.2 groups may be the same or different, and the substituents R.sub.2 may be bonded to each other to form a penta- or hexa-carbocyclic or heterocyclic ring.

Abstract: An internally plasticized vinyl chloride copolymer composition having good low temperature flexibility and tensile properties is disclosed. It consists essentially of from about 45% to about 80%, by weight, vinyl chloride, from about 15% to about 54%, by weight, of a C.sub.2 -C.sub.10 alkyl acrylate, and from about 1% to about 15%, by weight, of one or more C.sub.8 -C.sub.22 dialkyl maleate and/or fumarate. The copolymer is formed using conventional suspension, emulsion, bulk and solution polymerization procedures.

Abstract: An improved process for producing an ester from a carboxylic acid and an alcohol which comprises reacting said carboxylic acid with said alcohol by the use of a 1-substituted-2-halopyridinium salt or a 1-substituted-2-haloquinolinium salt as a condensing agent in the presence of a hydrogen halide captor. According to this process, various esters, even if they have some steric hindrances, may be obtained in good yields.

Abstract: A process for the preparation of dimethyl adipate by the hydrogenation of dimethyl hex-3-endioate, having the formula CH.sub.3 O.sub.2 CCH.sub.2 CH.dbd.CHCH.sub.2 CO.sub.2 CH.sub.3, derived from the oxidative carbonylation of 1,3-butadiene with a mixture of carbon monoxide and oxygen at a temperature of from 60.degree. C. to 200.degree. C. and pressures of from 15 psig to 5000 psig in the presence of a catalytic mixture of a platinum group metal compound and a copper or iron oxidant salt compound with at least a stoichiometric amount of a dehydrating agent, which comprises subjecting the dimethyl hex-3-endioate to a liquid phase hydrogenation at temperatures of from about ambient to about 150.degree. C. under hydrogen pressures of from about 10 psig to 1000 psig in the presence of an effective amount of a hydrogenation catalyst to produce dimethyl adipate, and recovering the dimethyl adipate.

Abstract: A process for the manufacture of butanedicarboxylic acid esters, wherein(a) an aqueous cobalt salt solution is treated, at from 50.degree. to 200.degree. C. and under a pressure of from 50 to 500 bars, with excess carbon monoxide and hydrogen in the presence of active charcoal laden with cobalt carbonyl,(b) the resulting aqueous solution of cobalt carbonyl hydride is extracted with butadiene or with a hydrocarbon mixture containing butadiene and the aqueous phase is separated off,(c) the butadiene, or butadiene-hydrocarbon mixture, containing cobalt carbonyl hydride, cobalt carbonyl and butenyl-cobalt tricarbonyl is reacted with carbon monoxide and an excess of an alkanol of 1 to 4 carbon atoms in the presence of from 0.5 to 2 moles, per mole of butadiene, of a tertiary nitrogen base having a pK.sub.a of from 3 to 11, at from 80.degree. to 150.degree. C.

Abstract: A process for the preparation of an unsaturated diester having the formula ##STR1## wherein R is an alkyl group of from 1 to 8 carbon atoms or an aralkyl group containing 6 carbon atoms in the ring and from 1 to 4 carbon atoms in the alkyl substituent, and R.sub.1 to R.sub.4 is hydrogen, a halogen, an alkyl group of from 1 to 4 carbon atoms or an aryl group containing 6 carbon atoms in the ring, by reacting carbon monoxide and oxygen with a diolefin having the formula ##STR2## wherein R.sub.1 to R.sub.4 which may be the same or different is as hereinabove described, in the presence of a catalytic amount of a platinum group metal compound, a copper for iron oxidant salt compound and a stoichiometric amount of a dehydrating agent.Alternatively, a ligand or coordination complex compound of the metal salt compound, and catalytic quantities of an alcohol may be employed.

Abstract: A process for the manufacture of butanedicarboxylic acid esters, wherein(a) an aqueous cobalt salt solution is treated with carbon monoxide and hydrogen in the presence of active charcoal,(b) the resulting aqueous solution is extracted with butadiene or with a hydrocarbon mixture containing butadiene,(c) the butadiene, or butadiene/hydrocarbon mixture, containing cobalt carbonyl hydride, cobalt carbonyl and butenyl-cobalt tricarbonyl, is reacted with carbon monoxide and an excess of an alkanol of 1 to 4 carbon atoms in the presence of a tertiary nitrogen base,(d) the tertiary nitrogen bases contained in the resulting reaction mixture are removed from the latter to the extent of leaving from 0.1 to 0.

Abstract: A process for the preparation of an unsaturated diester having the formula ##STR1## wherein R is an alkyl group of from 1 to 8 carbon atoms or an aralkyl group containing 6 carbon atoms in the ring and from 1 to 4 carbon atoms in the alkyl substituent and R.sub.1 to R.sub.4 is hydrogen, a halogen, an alkyl group of from 1 to 4 carbon atoms or an aryl group containing 6 carbon atoms in the ring, by reacting carbon monoxide, oxygen, at least a stoichiometric amount of an enol ether or alkoxycycloalkene and at least an equal molar quantity of an alcohol based on the enol ether or alkoxycycloalkene, with a diolefin having the formula ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 which may be the same or different is as hereinabove described, in the presence of a catalytic amount of a platinum group metal compound and a copper or iron oxidant salt compound.Alternatively, a ligand or coordination complex compound of the metal salt compound may be employed as a co-catalyst.

Abstract: There is provided a process for the preparation of esters of oxalic acid comprising reacting at a temperature of between about 20.degree. and 200.degree. C. a copper (II) compound having the formula Cu(OR)X, where R is alkyl having from 1 to 8 carbon atoms and X is chlorine or bromine, with carbon monoxide in the presence of a catalyst selected from the group consisting of palladium salts, metallic palladium and zero valent palladium complexes.

Abstract: A process for preparing a diester of a dicarboxylic acid having two more carbon atoms than the unsaturated hydrocarbon used as a starting material, which comprises subjecting an unsaturated hydrocarbon, carbon monoxide and an alcohol to reaction in the presence of a platinum group metal in combination with one or more compounds selected from the group consisting of nitric acid, a nitrogen oxide and an ester of nitrous acid.

Abstract: A process for the preparation of dialkyl oxalates by reacting an aliphatic alcohol with carbon monoxide under pressure, which comprises carrying out the reaction in the presence of(a) a catalyst comprising a platinum group metal or a salt thereof, and(b) an accelerator composed of one or more compounds selected from the group consisting of nitric acid and nitrogen oxides.

Abstract: The present invention relates to a process for preparing oxalic acid and esters of oxalic acid. More particularly, this invention relates to a catalytic process for preparing oxalic acid and esters of same by the oxidative reaction, in a liquid phase, of carbon monoxide and water or alcohols with oxygen in the presence of redox systems.The catalyst systems used in accordance with this invention comprises a redox catalyst consisting essentially of a salt of Pd (II) and salts of a metal more electropositive than Pd having at least two oxidation states and, optionally, salts of alkaline metals, and co-catalytic amounts of at least one base having the formula R.sub.3 N in which the groups R which may be like or unlike and are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 10 carbon atoms.

Abstract: By-product or waste streams from adipic acid plants which contain adipic acid, glutaric acid, succinic acid, nitric acid and catalyst values of copper and vanadium are treated to substantially recover all the components thereof by esterifying the dibasic acids with an alcohol, such as normal butanol, which creates esters that are substantially immiscible in the aqueous solution, allowing the organic esters to form a separate layer from the aqueous phase in which the metal values are retained, recovering the organic layer containing the esterified dibasic acids and thereafter re-using the aqueous solution containing the catalyst values in the adipic acid process.

Abstract: A method is provided for the removal of contaminating alkanes from the vaporized carbonylation products of a process wherein carboxylic acids are produced by the reaction in the liquid phase of an alcohol or an ester, halide or ether derivative of said alcohol with carbon monoxide in the presence of a catalyst system containing a rhodium or iridium component and an iodine or bromine component. The method involves distillation of the alkane-containing vaporized carbonylation products, phase separation of the overhead from said distillation, further distillation of a slipstream of the resulting heavy phase using carbon monoxide as stripping gas and removal of the alkanes as the bottoms stream from the latter distillation.

Abstract: This invention relates to an improved process for the carbonylation of alcohols, esters, ethers and halide derivatives with carbon monoxide in the presence of a catalyst system comprising a Group VIII metal component and a halogen component. The improvement in the process resides in the use of a polydentate chelating phosphorus or arsenic ligand complexed with iridium as the Group VIII metal component.

Abstract: This invention relates to an improved process for the carbonylation of alcohols, esters, ethers and halide derivatives with carbon monoxide in the presence of a catalyst system comprising a Group VIII metal component and a halogen component. The improvement in the process resides in the use of a polydentate chelating phosphorus or arsenic ligand complexed with rhodium as the Group VIII metal component.

Abstract: Organic acids contained in aqueous solution are separated and/or recovered by a process comprising adding an alcohol to the aqueous solution to esterify the acids present, while preferably simultaneously contacting the alcoholic mixture with a water-immiscible solvent and separating layers into an aqueous phase and an organic phase, whereby extraction with the water-immiscible solvent shifts the equilibrium toward the formation of more esters. The esters of the acids may than be recovered as by distillation.

Abstract: A process for the preparation of oxalate esters by reacting an alcohol with a mixture of carbon monoxide and oxygen in the presence of a catalytic mixture of:(a) a palladium, rhodium, platinum, copper, or cadmium metal salt compound or mixture thereof,(b) an aliphatic, cycloaliphatic, aromatic or heterocyclic amine or ammonia,(c) a copper (I), copper (II), iron (II) or iron (III) oxidant salt compound, and(d) an ammonium or substituted ammonium salt compound or acid with a counterion other than a halide.Alternatively a ligand or coordination complex compound of the metal salt compound may be employed.

Abstract: Treatment of aqueous nitric acid solutions resulting from the nitric acid oxidation of cyclohexanol and/or cyclohexanone in the presence of metal compound oxidation catalysts for recovery of the valuable components contained therein, which comprises adding an alcohol to the aqueous nitric acid solution to esterify the acids present, contacting the resultant alcoholic mixture with a water-immiscible solvent, separating layers into an aqueous phase and an organic phase, treating the aqueous phase to recover the nitric acid and catalyst components and treating the organic phase to recover the acid derivatives.

Abstract: An ester of an unsaturated carboxylic acid is prepared by an ester exchange process which comprises reacting a lower alkyl ester of an unsaturated, 3-4 carbon atom carboxylic acid with an alcohol different than the alcohol fragment of said lower alkyl ester over a catalyst selected from the group consisting of (1) metallic barium, barium compounds and mixtures thereof, (2) metallic thallium, thallium compounds or mixtures thereof, (3) metallic molybdenum, molybdenum compounds or mixtures thereof, and mixtures thereof by an ester exchange reaction.

Abstract: A process for the preparation of oxalate esters by the catalytic oxidative carbonylation of an alkoxycycloalkene with carbon monoxide, an alcohol and oxygen or an oxygen-containing gas in the presence of a metal salt catalyst and an amine base. In addition, a catalytic amount of particular metal oxidizing salts is employed along with a catalytic amount of an acid or an amine salt compound. Alternatively various counterions and ligands of the metal salt catalysts may be employed.

Abstract: Esters are prepared by reaction of acyl halides and alcohols or hydroxyalkyl esters and acid halides in the presence of a tertiary amine and polar aprotonic solvents. Bis(2-methacrylatoethyl) phthalate is prepared by the reaction of phthaloyl chloride with 2-hydroxyethyl methacrylate in pyridine and acetone. Bis-phenol-A-bis(2-methacrylatoethyl)ether is prepared from 2,2-bis[4-(2-hydroxyethoxy)phenyl]-propane and methacryl chloride in acetone.

Abstract: A process for removing organic components from the waste water effluent obtained in the production of an ester plasticizer through esterification of a polybasic aliphatic or aromatic carboxylic acid with an aliphatic alcohol in the presence of a sulfuric acid catalyst, which waste water contains an alkyl hydrogen sulfate or a dialkyl sulfate, esterification reactants and esterification products, which comprises:A. heating said waste water to a temperature above 200.degree. C under the particular prevailing pressure; andB. thereafter thermally or mechanically removing an organic phase from an aqueous phase.

Abstract: A process for the preparation of oxalate esters by the catalytic oxidative carbonylation of an enol ether with carbon monoxide, an alcohol and oxygen-containing gas in the presence of a metal salt catalyst and an amine base. In addition, a catalytic amount of particular metal oxidizing salts is employed along with a catalytic amount of an acid or an amine salt compound. Alternatively various counterions and ligands of the metal salt catalysts may be employed.

Abstract: The present invention relates to a process for the preparation of dicarboxylic acids, specifically by the reaction of non-vicinal glycols; halogen containing derivatives in which the OH radical of the glycol is substituted by Cl, Br, or I; ester derivatives of glycols; and cyclic ether derivatives of glycols; with carbon monoxide in the presence of catalyst compositions essentially comprising rhodium or iridium compounds and complexes, together with a halide promoter.

Abstract: After acidification and separation of a concentrated aqueous solution of sodium sulfate, the water-containing organic phase that remains is first distilled to remove mainly water, then chilled to crystallize out the bulk of the dicarboxy acids, then esterified and distilled again to obtain monocarboxy acid esters in distillate fractions, after which the residue is further esterified to facilitate obtaining the remaining dicarboxy acids in usable form.