Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide

Patent metadata

Field	Value
Publication number	US-10926247-B2
Application number	US-201916598199-A
Country	US
Kind code	B2
Filing date	Oct 10, 2019
Priority date	Jun 14, 2017
Publication date	Feb 23, 2021
Grant date	Feb 23, 2021

Abstract

This disclosure provides for catalyst systems and processes for forming an α,β-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO 2 ); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

First claim

The invention claimed is:

1. A catalyst system for forming an α,β-unsaturated carboxylic acid or a salt thereof, the catalyst system comprising:
a) a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand;
b) optionally, at least one second ligand;
c) an olefin;
d) carbon dioxide (CO 2 );
e) a diluent; and
f) an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations.

2. The catalyst system according to claim 1 , wherein the catalyst system further comprises a Group 8-11 transition metal metalalactone compound or an adduct of a Group 8-11 transition metal metalalactone compound and the oxoacid anion-substituted polyaromatic resin.

3. The catalyst system according to claim 1 , wherein the oxoacid anion-substituted polyaromatic resin has a) an average particle size from about 0.1 mm to about 1.0 mm, b) an average pore diameter from about 50 nm to about 250 nm, or c) both an average particle size from about 0.1 mm to about 1.0 mm and an average pore diameter from about 50 nm to about 250 nm.

4. The catalyst system according to claim 1 , wherein:
the oxoacid anion-substituted polyaromatic resin is formed into a bead, supported onto an inert inorganic support, supported onto an inert organic support, or used in the absence of a support; and
the oxoacid anion-substituted polyaromatic resin is arranged as a fixed bed, a bubbling bed, a moving bed, or a stirred bed.

5. The catalyst system according to claim 1 , wherein:
the metal of the transition metal precursor compound is Ni, and wherein the first ligand and the second ligand are selected independently from a diphosphine ligand, a diamine ligand, a diene ligand, a diether ligand, or dithioether ligand; and
the associated metal cations are selected from a Group 1, 2, 12, or 13 metal.

6. The catalyst system according to claim 1 , wherein the diluent comprises an ether diluent, a carbonyl-containing diluent, an aromatic hydrocarbon diluent, a halogenated aromatic hydrocarbon diluent, or an alcohol diluent.

7. The catalyst system according to claim 1 , wherein the olefin comprises ethylene, propylene, butene, pentene, hexene, heptane, octene, or styrene.

8. The catalyst system according to claim 1 , wherein the α,β-unsaturated carboxylic acid or the salt thereof is acrylic acid, methacrylic acid, 2-ethylacrylic acid, cinnamic acid, or a salt thereof.

9. A process for forming an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising:
a) contacting in any order
1) a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand;
2) optionally, at least one second ligand;
3) an olefin;
4) carbon dioxide (CO 2 );
5) a diluent; and
6) an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, further comprising associated metal cations, to provide a reaction mixture; and

b) applying reaction conditions to the reaction mixture suitable to form the α,βunsaturated carboxylic acid or the salt thereof.

10. The process according to claim 9 , wherein the reaction mixture comprises a Group 8-11 transition metal metalalactone compound or an adduct of a Group 8-11 transition metal metalalactone compound and the oxoacid anion-substituted polyaromatic resin, and wherein the reaction conditions suitable to form the α,βunsaturated carboxylic acid or the salt thereof induces a metalalactone elimination reaction to produce the α,β-unsaturated carboxylic acid or the salt thereof.

11. The process according to claim 9 , wherein the oxoacid anion-substituted polyaromatic resin has a) an average particle size from about 0.1 mm to about 1.0 mm, b) an average pore diameter from about 50 nm to about 250 nm, or c) both an average particle size from about 0.1 mm to about 1.0 mm and an average pore diameter from about 50 nm to about 250 nm.

12. The process according to claim 9 , wherein:
the oxoacid anion-substituted polyaromatic resin is formed into a bead, supported onto an inert inorganic support, supported onto an inert organic support, or used in the absence of a support; and
the oxoacid anion-substituted polyaromatic resin is arranged as a fixed bed, a bubbling bed, a moving bed, or a stirred bed.

13. The process according to claim 9 , wherein:
the metal of the transition metal precursor compound is Ni, and wherein the first ligand and the second ligand are selected independently from a diphosphine ligand, a diamine ligand, a diene ligand, a diether ligand, or dithioether ligand; and
the associated metal cations are selected from a Group 1, 2, 12, or 13 metal.

14. The process according to claim 9 , wherein the diluent comprises an ether diluent, a carbonyl-containing diluent, an aromatic hydrocarbon diluent, a halogenated aromatic hydrocarbon diluent, or an alcohol diluent.

15. The process according to claim 9 , wherein the contacting step and/or the applying step is/are conducted at a pressure from 5 psig (34 KPa) to 10,000 psig (68,948 KPa) and at a temperature from 0° C. to 250° C.

16. The process according to claim 9 , wherein the olefin comprises ethylene, propylene, butene, pentene, hexene, heptane, octene, or styrene.

17. The process according to claim 9 , wherein the α,β-unsaturated carboxylic acid or the salt thereof is acrylic acid, methacrylic acid, 2-ethylacrylic acid, cinnamic acid, or a salt thereof.

18. The process according to claim 9 , further comprising a step of regenerating the oxoacid anion-substituted polyaromatic resin and associated cations by contacting a by-product acid form of the oxoacid anion-substituted polyaromatic resin with a metal-containing base or a metal-containing salt.

19. The process according to claim 9 , wherein the olefin is ethylene, and the step of contacting a transition metal precursor compound with the olefin and carbon dioxide (CO 2 ) is conducted using a constant addition of the olefin and carbon dioxide in an ethylene:CO 2 molar ratio of from 3:1 to 1:3, to provide the reaction mixture.

20. A catalyst system for forming an α,β-unsaturated carboxylic acid or a salt thereof, the catalyst system comprising:
a) a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand;
b) optionally, at least one second ligand;
c) an olefin;
d) carbon dioxide (CO 2 );
e) a diluent; and
f) an oxoacid anion-substituted styrene-based polymer or copolymer comprising a sulfonated, a phosphonated, a sulfinated, a thiosulfonated, or a thiosulfinated styrene polymer or styrene-divinylarene copolymer, further comprising associated metal cations.

21. The catalyst system according to claim 1 , wherein the oxoacid anion-substituted polyaromatic resin comprises a sulfonated-, a phosphonated-, a sulfinated-, a thiosulfonated-, or a thiosulfinated-styrene polymer or styrene-divinylarene copolymer.

22. The catalyst system according to claim 1 , wherein the oxoacid anion-substituted polyaromatic resin comprises a crosslinked polystyrene sulfonate resin.

23. The catalyst system according to claim 1 , wherein the oxoacid anion-substituted polyaromatic resin comprises a sulfonated-, a phosphonated-,

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

• C07C51/09

  from carboxylic acid esters or lactones · CPC title

• B01J31/10 Primary

  sulfonated · CPC title

• B01J31/08

  Ion-exchange resins · CPC title

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title