Method for separating high-boiling carboxylic acid vinyl ester/carboxylic acid mixtures

Patent metadata

Field	Value
Publication number	US-9822059-B2
Application number	US-201515315162-A
Country	US
Kind code	B2
Filing date	May 21, 2015
Priority date	Jun 6, 2014
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

The invention relates to a method for separating a mixture containing at least one carboxylic acid vinyl ester of general formula R′—C(O)O—CH═CH 2 and at least one carboxylic acid of general formula R′—COOH, wherein R′ in either case can be an aliphatic group having 12 to 22 C atoms or a cycloaliphatic group having 12 to 22 C atoms, or an aromatic group having 12 to 22 C atoms, and R′ can be identical or different, characterized in that the carboxylic acid is converted to its anhydride R′—C(O)—O—C(O)—R′ and the carboxylic acid vinyl ester is subsequently separated.

First claim

The invention claimed is:

1. A process for separating a mixture comprising at least one vinyl carboxylate ester of general formula R′—C(O)O—CH═CH 2 and at least one carboxylic acid of general formula R′—COOH, wherein in each case R′ may be an aliphatic radical having 12 to 22 carbon atoms or a cycloaliphatic radical having 12 to 22 carbon atoms or an aromatic radical having 12 to 22 carbon atoms and R′ may be identical or different, said process comprising the steps of converting the carboxylic acid into its anhydride R′—C(O)—O—C(O)—R′ and subsequently removing the vinyl carboxylate ester.

2. The process as claimed in claim 1 , wherein the conversion of the carboxylic acid R′—COOH into the corresponding anhydride R′—C(O)—O—C(O)—R′ is effected by reaction with an anhydride of general formula R*—C(O)—O—C(O)—R*, wherein R* is identical or different and represents an aliphatic radical having 1 to 10 carbon atoms or a cycloaliphatic radical having up to 10 carbon atoms or an aromatic radical having up to 10 carbon atoms.

3. The process as claimed in claim 2 , wherein 0.1 to 5 molar equivalents of the anhydride R*—C(O)—O—C(O)—R* relative to the carboxylic acid R′—COOH are employed and the reaction is effected at temperatures of 0° C. to 150° C., at a pressure of 0.001 to 10 bar abs., and with a reaction time of up to 5 hours.

4. The process as claimed in claim 2 , wherein the anhydride of general formula R*—C(O)—O—C(O)—R* employed is an anhydride selected from the group consisting of anhydrides of acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, 2-methylbutyric acid, 3-methylbutyric acid, pivalic acid, caproic acid, cyclohexanecarboxylic acid, n-heptanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, n-octanoic acid, n-nonanoic acid, isononanoic acid, neononanoic acid, n-decanoic acid, and neodecanoic acid.

5. The process as claimed in claim 1 , wherein the conversion of the carboxylic acid R′—COOH into the corresponding anhydride R′—C(O)—O—C(O)—R′ is effected by transition-metal-catalyzed reactive distillation with a vinyl carboxylate ester of general formula R—C(O)O—CH═CH 2 , wherein R may be an aliphatic radical having 1 to 10 carbon atoms or a cycloaliphatic radical having up to 10 carbon atoms or an aromatic radical having up to 10 carbon atoms.

6. The process as claimed in claim 5 , wherein the reactive distillation is performed in the presence of Ru compounds or Pd compounds as catalyst, with a molar ratio of vinyl carboxylate ester R—C(O)O—CH═CH 2 to carboxylic acid R′—COOH of 1:1 to 40:1 and at a temperature of 100° C. to 180° C.

7. The process as claimed in claim 5 , wherein the vinyl carboxylate ester R—C(O)O—CH═CH 2 employed is a vinyl carboxylate ester having an alkyl radical having 1 to 6 carbon atoms as radical R.

8. The process as claimed in claim 1 , wherein the vinyl carboxylate ester is removed by distillation.

9. The process as claimed in claim 1 , wherein the conversion of the carboxylic acid into its anhydride is preceded by a transvinylation of a carboxylic acid of general formula R′—COOH with a vinyl carboxylate ester of general formula R—C(O)O—CH═CH 2 .

10. The process as claimed in claim 9 , wherein the transvinylation comprises a transvinylation of vinyl acetate with stearic acid and/or palmitic acid which is catalyzed with a ruthenium or palladium catalyst.

11. The process as claimed in claim 7 , wherein the vinyl carboxylate ester is vinyl acetate.

Assignees

• Wacker Chemie Ag

Inventors

• Gigler Peter
• STOHRER JüRGEN

Classifications

• C07C51/54

  Preparation of carboxylic acid anhydrides (by oxidation C07C51/16) · CPC title

• C07C7/148

  by treatment giving rise to a chemical modification of at least one compound · CPC title

• C07C51/56

  from organic acids, their salts, their esters {or their halides, e.g. by carboxylation} · CPC title

• C07C51/573

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C07C7/14875

  with organic compounds (organo-metallic compounds C07C7/173) · CPC title