Formation of α,β-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes

Patent metadata

Field	Value
Publication number	US-10160711-B2
Application number	US-201615377563-A
Country	US
Kind code	B2
Filing date	Dec 13, 2016
Priority date	Dec 15, 2015
Publication date	Dec 25, 2018
Grant date	Dec 25, 2018

Abstract

This disclosure provides for routes of synthesis of acrylic acid and other α,β-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the α,β-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

First claim

We claim:

1. A process for forming an α,β-unsaturated carboxylic acid or salt thereof, the process comprising
(1) contacting
(a) a metalalactone compound comprising a Group 8-10 metal;
(b) a diluent; and
(c) an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and

(2) applying conditions to the reaction mixture suitable to induce a metalalactone elimination reaction to form the α,β-unsaturated carboxylic acid or a salt thereof.

2. The process according to claim 1 , wherein the anionic polyaromatic resin with associated metal cations comprises a metallated phenol-formaldehyde resin, a metallated polyhydroxyarene-formaldehyde resin, or a metallated polyhydroxyarene- and fluorophenol-formaldehyde resin.

3. The process according to claim 1 , wherein the anionic polyaromatic resin with associated metal cations comprises a sodium phenol-formaldehyde resin, a potassium phenol-formaldehyde resin, a sodium resorcinol- and 2-fluorophenol-formaldehyde resin, or a potassium resorcinol- and 2-fluorophenol-formaldehyde resin.

4. The process according to claim 1 , wherein the anionic polyaromatic resin with associated metal cations is insoluble in the diluent or the reaction mixture.

5. The process according to claim 1 , wherein the reaction mixture comprises an adduct of the metalalactone compound and the anionic polyaromatic resin with associated metal cations.

6. The process according to claim 1 , wherein the associated metal cations are selected from a Group 1, 2, 12 or 13 metal cation.

7. The process according to claim 1 , wherein the associated metal cations are lithium, sodium, potassium, magnesium, calcium, zinc or aluminum cations.

8. The process according to claim 1 , wherein the contacting step comprises contacting the metalalactone compound, the diluent, and the anionic polyaromatic resin with associated metal cations in any order.

9. The process according to claim 1 , wherein the conditions suitable to induce a metalalactone elimination reaction comprise contacting the reaction mixture with a metal-containing base.

10. The process according to claim 9 , wherein the metal-containing base is selected from an alkali metal or an alkaline earth metal oxide, hydroxide, alkoxide, aryloxide, amide, alkyl amide, arylamide, or carbonate.

11. The process according to claim 9 , wherein the contacting step is carried out in the absence of sodium hydride.

12. The process according to claim 1 , wherein the metalalactone compound comprises Ni.

13. A process for producing an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising:
(1) contacting in any order
(a) a group 8-11 transition metal precursor;
(b) an olefin;
(c) carbon dioxide (CO 2 );
(d) a diluent; and
(e) an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and

(2) applying conditions to the reaction mixture suitable to produce the α,β-unsaturated carboxylic acid or a salt thereof.

14. The process according to claim 13 , wherein the reaction mixture comprises an adduct of a metalalactone compound and the anionic polyaromatic resin with associated metal cations.

15. The process according to claim 13 , wherein the anionic polyaromatic resin with associated metal cations comprises a metallated phenol-formaldehyde resin, a metallated polyhydroxyarene-formaldehyde resin, or a metallated polyhydroxyarene- and fluorophenol-formaldehyde resin.

16. The process according to claim 13 , wherein the anionic polyaromatic resin with associated metal cations comprises a sodium phenol-formaldehyde resin, a potassium phenol-formaldehyde resin, a sodium resorcinol- and 2-fluorophenol-formaldehyde resin, or a potassium resorcinol- and 2-fluorophenol-formaldehyde resin.

17. The process according to claim 13 , wherein the conditions suitable to produce the α,β-unsaturated carboxylic acid or a salt thereof comprise contacting the reaction mixture with a metal-containing base.

18. The process according to claim 17 , wherein the metal-containing base is selected from an alkali metal or an alkaline earth metal oxide, hydroxide, alkoxide, aryloxide, amide, alkyl amide, arylamide, or carbonate.

19. The process according to claim 17 , wherein the contacting step is carried out in the absence of sodium hydride.

20. The process according to claim 13 , wherein the olefin comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, or styrene.

21. The process according to claim 13 , wherein the olefin is ethylene, and the step of contacting the group 8-11 transition metal precursor with the olefin and carbon dioxide is conducted using from 10 psig (689 KPa) to 1,000 psig (6,902 KPa) of ethylene partial pressure.

22. The process according to claim 13 , wherein the olefin is ethylene, and the step of contacting the group 8-11 transition metal precursor with the olefin and carbon dioxide is conducted using a constant addition of the olefin and carbon dioxide to provide the reaction mixture.

23. The process according to claim 13 , wherein the olefin is ethylene, and the ethylene and carbon dioxide are added in a constant or a variable ethylene:CO 2 molar ratio of from 10:1 to 1:10, to provide the reaction mixture.

24. The process according to claim 13 , wherein the group 8-11 transition metal precursor comprises Ni.

25. The process according to claim 13 , wherein the associated metal cations are selected from a Group 1, 2, 12 or 13 metal cation.

26. The process according to claim 13 , wherein the associated metal cations are lithium, sodium, potassium, magnesium, calcium, zinc or aluminum cation.

27. The process according to claim 13 , wherein the diluent comprises a non-protic solvent, a weakly coordinating solvent, or a non-coordinating solvent.

28. The process according to claim 13 , wherein the diluent comprises an aromatic hydrocarbon solvent, an ether solvent, a carbonyl-containing solvent, a halogenated aromatic hydrocarbon solvent, or combinations thereof.

29. The process according to claim 13 , wherein a molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof based on the transition metal precursor compound is at least 100%.

30. The process according to claim 13 , wherein the conditions suitable to produce the α,β-unsaturated carboxylic acid or a salt thereof comprise at least one of the following conditions or any combination of the following conditions:
a) contacting the reaction mixture with a ketone, an ester, an amide, an alcohol, or water;
b) heating the reaction mixture to a temperature from 50 to 1000° C.;
c) conducting the contacting step at a total pressure of from 5 psig (34 KPa) to 10,000 psig (68,948 KPa);
d) conducting the contacting step at a temperature of from 0° C. to 250° C.; and/or
e) conducting the contacting step at a weight hourly space velocity (WHSV) of from 0.05 to 50 hr −1 , based on the amount of the anionic polyaromatic resin with associated metal cations.

31. A process for producing an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising:
(1) contacting in any order
(a) a group 8-11 transition metal catalyst;
(b) an olefin;
(c) carbon dioxide (CO2);
(d) a diluent; and
(e) an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and

( 2 ) contactin

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Iacono Pasquale
• Hlavinka Mark L

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

• B01J2531/847

  Nickel · CPC title

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title