Process for preparing an unsaturated carboxylic acid salt

Patent metadata

Field	Value
Publication number	US-10138196-B2
Application number	US-201615573276-A
Country	US
Kind code	B2
Filing date	May 9, 2016
Priority date	May 13, 2015
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

A catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt from an alkene, carbon dioxide and an alkoxide having a secondary or tertiary carbon atom directly bound to a [O−] group is described. The alcohol byproduct is distilled off after an intermediate phase separation. This provides pure β,β-ethylenically unsaturated carboxylic acid salt at minimum effort.

First claim

The invention claimed is:

1. A catalytic process for preparing an α, β-ethylenically unsaturated carboxylic acid salt, the process comprising:
a) contacting an alkene and carbon dioxide with a carboxylation catalyst and an alkoxide, the alkoxide having a secondary or tertiary carbon atom directly bound to a [O − ] group, to obtain a crude reaction product comprising the α,β-ethylenically unsaturated carboxylic acid salt and an alcohol byproduct which is a conjugate acid of the alkoxide,
b) contacting at least part of the crude reaction product with a polar solvent such that 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, are obtained, and
c) distilling an alcohol byproduct off from the first liquid phase.

2. The catalytic process according to claim 1 , further comprising:
d) contacting at least part of the alcohol byproduct recovered in c) with an alkaline material in order to regenerate the alkoxide.

3. The catalytic process according to claim 2 , wherein at least part of the alkoxide obtained in d) is recycled to a).

4. The catalytic process according to claim 1 , wherein at least part of the second liquid phase obtained in b) is recycled to a).

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

6. The catalytic process according to claim 1 , wherein the polar solvent comprises at least 90% by weight of water.

7. The catalytic process according to claim 5 , wherein, in c), at least a part of the polar solvent is distilled off from the first liquid phase.

8. The catalytic process according to claim 7 , wherein the polar solvent recovered in c) is used as the polar solvent in b).

9. The catalytic process according to claim 1 , wherein a) is carried out in an aprotic organic solvent.

10. The catalytic process according to claim 9 , wherein the aprotic organic solvent is octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, benzene, toluene, xylene, chlorobenzene, anisole, butyl-phenyl-ether, diphenylether, dibutylether, ethylenglcyoledibutlyether, diethylether, tetrahydrofuran, 2-methyl-tetrahydrofuran, or a mixture thereof.

11. The catalytic process according to claim 1 , wherein the partial pressure of carbon dioxide in a) is maintained above 1 bar.

12. 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.

13. The catalytic process according to claim 1 , wherein the alkoxide is sodium tert-butoxide.

14. The catalytic process according to claim 1 , wherein a) is carried out at a temperature ranging from 70 to 180° C.

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

16. The catalytic process according to claim 15 , wherein the P,X ligand is a P,P ligand of formula (IId-1)
R 16 R 17 P—(CR 18 H) e —PR 16 R 17    (IId-1)

wherein
R 16 and R 17 are each independently an unbranched or branched, acyclic or cyclic aliphatic residue having 1 to 20 carbon atoms,
e is 2, 3, or 4, and
R 18 is independently H, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkoxy, C 6 -C 10 -aryl, or C 6 -C 10 -aryloxy.

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

Assignees

• Basf Se

Inventors

• Schaub Thomas
• Huguet Subiela Nuria
• Paciello Rocco
• Fries Donata Maria
• Manzini Simone

Classifications

• C07C51/15 Primary

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

• C07C57/04

  Acrylic acid; Methacrylic acid · CPC title

• C07C51/48

  by liquid-liquid treatment · CPC title

• B01J31/24

  Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands} · CPC title

• C07C51/50

  Use of additives, e.g. for stabilisation · CPC title