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

Patent metadata

Field	Value
Publication number	US-9416087-B2
Application number	US-201414509082-A
Country	US
Kind code	B2
Filing date	Oct 8, 2014
Priority date	Oct 8, 2014
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

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, and sepiolite, 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 comprises acrylic acid.

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

4. The process of claim 1 , wherein the metallalactone is a nickelalactone.

5. 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 oxide;

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

6. The process of claim 5 , 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 at least 5%.

7. The process of claim 5 , wherein:
the metallalactone is a nickelalactone;
the solid oxide is a Bronsted base and a Lewis acid; and
the α,β-unsaturated carboxylic acid comprises acrylic acid.

8. The process of claim 5 , wherein:
the solid oxide comprises silica, alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, or a combination thereof; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is at least 5%.

9. The process of claim 5 , wherein:
the solid oxide comprises magnesium aluminate, calcium aluminate, zinc aluminate, zirconium aluminate, sodium aluminate, magnesium zirconium oxide, sodium zirconium oxide, calcium zirconium oxide, lanthanum chromium oxide, barium titanium oxide, or a combination thereof; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is at least 5%.

10. The process of claim 5 , wherein:
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is at least 5%;
the metallalactone is a nickelalactone; and
the α,β-unsaturated carboxylic acid comprises acrylic acid.

11. The process of claim 5 , wherein:
the solid oxide comprises alumina, zirconia, magnesia, magnesium aluminate, sepiolite, or a combination thereof; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is at least 10%.

12. The process of claim 5 , wherein the metallalactone comprises:

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

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 (CO2);
(iv) a diluent; and
(v) a solid promoter selected from the group consisting of magnesium aluminate, calcium aluminate, zinc aluminate, zirconium aluminate, sodium aluminate, magnesium zirconium oxide, sodium zirconium oxide, calcium zirconium oxide, lanthanum chromium oxide, barium titanium oxide, 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; and
the α,β-unsaturated carboxylic acid comprises acrylic acid.

15. 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.

16. The process of claim 13 , wherein
the solid promoter is a Lewis acid.

17. The process of claim 13 , wherein the solid promoter is magnesium aluminate, calcium aluminate, zinc aluminate, zirconium aluminate, sodium aluminate, magnesium zirconium oxide, sodium zirconium oxide, calcium zirconium oxide, lanthanum chromium oxide, barium titanium oxide, or a combination thereof.

18. The process of claim 13 , wherein the solid promoter is alumina, zirconia, magnesia, magnesium aluminate, sepiolite, or a combination thereof.

19. The process of claim 13 , 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.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Hlavinka Mark L
• Mcdaniel Max P

Classifications

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• B01J31/12

  containing organo-metallic compounds or metal hydrides · CPC title

• B01J2231/46

  C-H or C-C activation · CPC title

• B01J2531/847

  Nickel · CPC title

• C07C51/377 Primary

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title