Chem Systems Inc.

John A Jung

Jimmy Y Peress

Robert Hansen

Arthur M Brownstein

The invention includes a process wherein an olefin is carbonylated with carbon monoxide to form carboxylic acid esters in the presence of a catalyst complex of one mole of BF.sub.3 and one mole of alcohol, and the catalyst is recovered from the desired reaction product and the reaction by-products and is recycled. The carbonylation is carried out until approximately one-half of the alcohol is consumed to form a reaction mass containing the BF.sub.3, the alcohol, and carboxylic acid esters in a 2:1:1 molar ratio. In the first step, the one mole of free BF.sub.3 is vaporized from the reaction mass. The remaining admixture is a 1:1:1 mixture of the aforesaid compounds. To this mixture additional alcohol is added and the mixture is subjected to distillation. An azeotrope of the product carboxylic acid ester and the alcohol and residual alcohol are removed by the distillation, leaving a residue containing a 1:2 BF.sub.3 / alcohol complex and the by-product carboxylic acid esters, which are heavier than the product carboxylic acid ester. The by-products are removed from the residue via solvent extraction and the remaining complex may be combined with an additional mole of BF.sub. 3 to form the 1:1:1 catalyst complex used in the carbonylation. The additional mole of BF.sub.3 is preferably that initially separated from the reaction mass; however, it may be obtained from an external source. The reconstituted catalyst is then preferably recycled to the carbonylation reaction. The carboxylic acid ester/alcohol mixture may be separated by azeotropic distillation using an azeotroping agent, such as octane, to recover the alcohol-octane as overhead product and the carboxylic acid ester as bottoms product.

Preparation of carboxylic acid esters with BF.sub.3 -alcohol complex

Propylene and ethylene may be carbonylated to form carboxylic acid esters or carboxylic acids in the presence of a catalyst complex containing 1 mole of BF.sub.3 and 1 mole of a second complexing component. The carboxylic acid product or acid portion of the ester product has one more carbon atom than the olefin reacted. High yields of these products are obtained. In the case of the formation of the ester, the second complexing component is an alcohol, while in the case of the preparation of carboxylic acid, the second complexing component is water. Methyl isobutyrate and methyl propionate formed by the carbonylation of propylene and ethylene, respectively, in the presence of a BF.sub.3.CH.sub.3 OH catalyst may be dehydrogenated to prepare methyl methacrylate and methyl acrylate, respectively. Similarly, the isobutyric acid and propionic acid formed from propylene and ethylene, respectively, in the presence of BF.sub.3.H.sub.2 O catalyst may be dehydrogenated to prepare methacrylic acid and acrylic acid, respectively.

Preparation of carboxylic acids using a BF.sub.3 catalyst complex

Epoxy compounds are produced by the vapor phase deacyloxylation of vicinal hydroxyesters in the presence of a basic material. The co-product carboxylic acid may be reacted with olefins to form additional hydroxyesters.

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East Hanover, NJ, United States of America

John A Jung