Methods for the production of α,β-unsaturated carboxylic acids and salts thereof

Patent metadata

Field	Value
Publication number	US-9783478-B2
Application number	US-201615203844-A
Country	US
Kind code	B2
Filing date	Jul 7, 2016
Priority date	Oct 8, 2014
Publication date	Oct 10, 2017
Grant date	Oct 10, 2017

Abstract

Processes for producing an α,β-unsaturated carboxylic acid, such as acrylic acid, or a salt thereof, using solid promoters are disclosed. The solid promoters can be certain solid oxides, mixed oxides, and clays, illustrative examples of which can include alumina, zirconia, magnesia, magnesium aluminate, sepiolite, and similar materials.

First claim

We claim:

1. A process for performing a metallalactone elimination reaction, the process comprising:
(1) forming a reaction mixture consisting essentially of
(a) a metallalactone;
(b) a diluent; and
(c) a solid promoter selected from the group consisting of alumina, zirconia, magnesia, magnesium aluminate, sepiolite, sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, cesium carbonate, cesium hydroxide, magnesium carbonate, magnesium hydroxide, calcium carbonate, calcium hydroxide, aluminum carbonate, and aluminum hydroxide, or a combination thereof; and

(2) forming an α,β-unsaturated carboxylic acid, or a salt thereof;
wherein the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is at least 5%.

2. The process of claim 1 , wherein:
the α,β-unsaturated carboxylic acid, or the salt thereof, comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, sodium acrylate, magnesium acrylate, sodium methacrylate, or a combination thereof; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is from 5% to 95%.

3. The process of claim 2 , wherein the metallalactone contains nickel, palladium, or platinum.

4. The process of claim 2 , wherein the metallalactone comprises a nickelalactone.

5. The process of claim 1 , wherein in step (1), the metallalactone and the diluent contact a fixed bed of the solid promoter.

6. The process of claim 1 , further comprising a step of calcining the solid promoter prior to step (1).

7. The process of claim 1 , wherein the metallalactone comprises:

or a combination thereof, wherein Cy is cyclohexyl and t Bu is tert-butyl.

8. A process for producing an α,β-unsaturated carboxylic acid, or a salt thereof, the process comprising:
(1) contacting
(a) a metallalactone;
(b) a diluent; and
(c) a solid promoter comprising alumina, zirconia, magnesia, magnesium aluminate, sepiolite, sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, cesium carbonate, cesium hydroxide, magnesium carbonate, magnesium hydroxide, calcium carbonate, calcium hydroxide, aluminum carbonate, aluminum hydroxide, or a combination thereof; and

(2) forming an adduct of an α,β-unsaturated carboxylic acid adsorbed onto the solid promoter; and
(3) contacting the adduct adsorbed onto the solid promoter with an acid comprising HCl and/or acetic acid to produce the α,β-unsaturated carboxylic acid, or the salt thereof.

9. The process of claim 8 , wherein:
the α,β-unsaturated carboxylic acid, or the salt thereof, comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, sodium acrylate, magnesium acrylate, sodium methacrylate, or a combination thereof; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is from 5% to 95%.

10. The process of claim 9 , wherein the metallalactone comprises a nickelalactone.

11. The process of claim 8 , wherein in step (1), the metallalactone and the diluent contact a fixed bed of the solid promoter.

12. The process of claim 8 , further comprising a step of calcining the solid promoter prior to step (1).

13. A process for producing an α,β-unsaturated carboxylic acid, or a salt thereof, the process comprising:
(I) forming a reaction mixture consisting essentially of:
(i) a transition metal-ligand complex;
(ii) an olefin;
(iii) carbon dioxide (CO 2 );
(iv) a diluent; and
(v) a solid promoter selected from the group consisting of alumina, zirconia, magnesia, magnesium aluminate, and sepiolite, or a combination thereof; and

(II) forming the α,β-unsaturated carboxylic acid, or the salt thereof;
wherein the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the transition metal-ligand complex, is at least 5%.

14. The process of claim 13 , wherein:
the olefin comprises ethylene;
the α,β-unsaturated carboxylic acid, or the salt thereof, comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, sodium acrylate, magnesium acrylate, sodium methacrylate, or a combination thereof; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the transition metal-ligand complex, is from 5% to 95%.

15. The process of claim 14 , wherein in step (I), the transition metal-ligand complex, the olefin, the carbon dioxide, and the diluent contact a fixed bed of the solid promoter.

16. The process of claim 13 , wherein the transition metal of the transition metal-ligand complex is a Group 8-11 transition metal, and the ligand of the transition metal-ligand complex is a neutral electron donor group or Lewis base.

17. The process of claim 16 , wherein the transition metal is nickel, palladium, or platinum.

18. The process of claim 13 , wherein:
the transition metal of the transition metal-ligand complex is nickel;
the ligand of the transition metal-ligand complex is a neutral electron donor group or Lewis base; and
the olefin comprises ethylene.

19. The process of claim 13 , further comprising a step of calcining the solid promoter prior to step (I).

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Hlavinka Mark L
• Mcdaniel Max P

Classifications

• C07C51/15 Primary

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

• B01J31/2234 Primary

  Beta-dicarbonyl ligands, e.g. acetylacetonates · CPC title

• B01J2231/46

  C-H or C-C activation · CPC title

• B01J31/26

  containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 · CPC title

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title