Process for preparing an unsaturated carboxylic acid salt

Patent metadata

Field	Value
Publication number	US-10774024-B2
Application number	US-201716090731-A
Country	US
Kind code	B2
Filing date	Apr 4, 2017
Priority date	Apr 11, 2016
Publication date	Sep 15, 2020
Grant date	Sep 15, 2020

Abstract

The present invention relates to a catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, comprising contacting an alkene and carbon dioxide with a carboxylation catalyst being a transition metal complex, an alkoxide, and an organic solvent, to obtain an α,β-ethylenically unsaturated carboxylic acid salt, the organic solvent being incompletely miscible with water at a pressure of 1 bar at at least one temperature T and selected from amides and ureas, T being a temperature in the range from 10° C. to 90° C.

First claim

The invention claimed is:

1. A catalytic process, suitable for preparing an α,β-ethylenically unsaturated carboxylic acid salt, the process comprising
contacting an alkene and carbon dioxide with a carboxylation catalyst to obtain an α,β-ethylenically unsaturated carboxylic acid salt, wherein the carboxylation catalyst comprises a nickel or palladium complex,
an alkoxide, and an organic solvent,
wherein the organic solvent is incompletely miscible with water at a pressure of 1 bar at at least one temperature T and is selected from the group consisting of an amide and a urea, T being a temperature in a range from 10° C. to 90° C. wherein the amide or the urea is linear or cyclic and comprises at least 5 carbon atoms and no nitrogen bound hydrogen atoms and wherein all of the at least 5 carbon atoms other than the carbonyl carbon atom are saturated.

2. The catalytic process according to claim 1 , wherein the organic solvent is an N,N-disubstituted formamide, an N,N-disubstituted acetamide, an N-substituted 2-pyrrolidone, or a 1,3-disubstituted 2-imidazolidinone.

3. The catalytic process according to claim 2 , wherein the organic solvent is selected from the group consisting of N-Methylpyrrolidone, N-Ethylpyrrolidone, 1,3-Dimethyl-2-imidazolidinone, N-Cyclohexylpyrrolidone, N,N-Dibutylformamide, N,N-Dihexylformamide, N,N-Dibutylacetamide, N,N-Dihexylacetamide, N-Cyclohexylpyrollidone, and N-Decylpyrollidone.

4. The catalytic process according to claim 1 , wherein the alkoxide comprises a secondary or tertiary carbon atom directly bound to an [O − ]group.

5. The catalytic process according to claim 1 , wherein the alkoxide is selected from the group consisting of an alkali metal alkoxide and an alkaline earth metal alkoxide.

6. The catalytic process according to claim 1 , wherein the alkene and the carbon dioxide are contacted with the carboxylation catalyst, the alkoxide, and the organic solvent at a temperature in a range from 105 to 170° C.

7. The catalytic process according to claim 1 , wherein the nickel or palladium complex comprises a bidentate P,X ligand,
wherein X is selected from the group consisting of P, N, O, and carbene, and
P and X are separated by a bivalent linker that comprises 2 to 4 bridging atoms.

8. The catalytic process according to claim 1 , wherein the alkene is ethene and the α,β-ethylenically unsaturated carboxylic acid is acrylic acid.

9. The catalytic process according to claim 1 , additionally comprising
contacting at least part of a crude reaction product with a polar solvent to obtain:
a first liquid phase in which the α,β-ethylenically unsaturated carboxylic acid salt is enriched, and
a second liquid phase in which the carboxylation catalyst is enriched.

10. The catalytic process according to claim 9 , additionally comprising
distilling off an alcohol byproduct from the first liquid phase, to obtain a recovered alcohol byproduct, contacting at least part of the recovered alcohol byproduct with an alkaline material to obtain a regenerated alkoxide, and
recycling at least part of the regenerated alkoxide into the catalytic process.

11. The catalytic process according to claim 10 , wherein the polar solvent has a boiling temperature of less than 150° C. at a pressure of 1 bar.

12. The catalytic process according to claim 11 , wherein the polar solvent is aqueous.

13. The catalytic process according to claim 12 , wherein at least a part of the polar solvent is distilled off from the first liquid phase.

Assignees

• Basf Se

Inventors

• Schaub Thomas
• Paciello Rocco
• Huguet Subiela Nuria
• Trapp Oliver
• Manzini Simone

Classifications

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J31/12

  containing organo-metallic compounds or metal hydrides · CPC title

• B01J2531/824

  Palladium · CPC title

• B01J2531/847

  Nickel · CPC title

• C07C51/15 Primary

  by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis · CPC title