Formation of alpha,beta-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes
This disclosure provides routes of synthesis of acrylic acid and other α,β-unsaturated carboxylic acids and their salts, including catalytic methods. In an aspect, 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 compound comprising at least one first ligand, at least one second ligand, an olefin, carbon dioxide, a diluent, and 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. Methods of regenerating the polyaromatic resin with associated metal cations are described.
1. A process for producing an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising:
a) contacting in any order
(i) a group 8-11 transition metal precursor compound comprising at least one first ligand;
(ii) at least one second ligand;
(iii) an olefin;
(iv) carbon dioxide (CO 2 );
(v) a diluent; and
(vi) an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and
b) applying conditions to the reaction mixture which produce 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:
a) the first ligand, the second ligand, or both the first ligand and the second ligand is a bidentate ligand; or
b) the first ligand, the second ligand, or both the first ligand and the second ligand comprise(s) at least one of a nitrogen, phosphorus, sulfur, or oxygen coordinating atom.
6. The process according to claim 1 , wherein the first ligand, the second ligand, or both the first ligand and the second ligand comprise(s) a diphosphine ligand, a diamine ligand, a diene ligand, a diether ligand, or dithioether ligand.
7. The process according to claim 1 , wherein the first ligand, the second ligand, or both the first ligand and the second ligand comprise(s) an ether ligand, an organic carbonyl ligand, a thioether ligand, an amine ligand, a nitrile ligand, a phosphine ligand, a diene ligand, or a carbene ligand.
8. The process according to claim 1 , wherein the first ligand is a diene ligand and the second ligand is a diphosphine ligand.
9. The process according to claim 1 , wherein the first ligand is 1,5-cyclooctadiene or TMEDA, and the second ligand is 1,2-bis(dicyclohexylphosphino)ethane or TMEDA.
10. The process according to claim 1 , wherein the first ligand or the second ligand is selected from trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, phenylphosphine, tolylphosphine, diphenylphosphine, ditolylphosphine, triphenylphosphine, tritolylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diethylphenylphosphine, tricyclohexylphosphine, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite and tricyclohexyl phosphite, 2-(di-t-butylphosphino)biphenyl, 2-di-t-butylphosphino-1,1′-binaphthyl, 2-(di-t-butylphosphino)-3,6-dimethoxy-2′,4′,6′-tri-i-propyl-1,1′-biphenyl, 2-di-t-butylphosphino-2′-methylbiphenyl, 2-(di-t-butylphosphinomethyl)pyridine, 2-di-t-butylphosphino-2′,4′,6′-tri-i-propyl-1,1′-biphenyl, 2-(dicyclohexylphosphino)biphenyl, (S)-(+)-(3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a′]dinaphthalen-4-yl)dimethylamine, 2-(diphenylphosphino)-2′-methoxy -1,1′-binaphthyl, 1,2,3,4,5-pentaphenyl-1′-(di-t-butylphosphino)ferrocene, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), 1,2-bis(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane, 1,2-bis(dipropylphosphino)-ethane, 1,2-bis(diisopropylphosphino)ethane, 1,2-bis(dibutyl-phosphino)ethane, 1,2-bis(di-t-butyl-phosphino)ethane, 1,2-bis(dicyclohexylphosphino)ethane, 1,3-bis(dicyclohexylphosphino)propane, 1,3-bis(diisopropylphosphino)propane, 1,3-bis(diphenylphosphino)propane, 1,3-bis(di-t-butylphosphino)propane, 1,4-bis(diisopropylphosphino)butane, 1,4-bis(diphenylphosphino)butane, 2,2′-bis[bis(3,5-dimethylphenyl)phosphino]-4,4′,6,6′-tetramethoxybiphenyl, 2,6-bis(di-t-butylphosphinomethyl)pyridine, 2,2′-bis(dicyclohexylphosphino)-1,1′-biphenyl, bis(2-dicyclohexylphosphinophenyl)ether, 5,5′-bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole, 2-t-butylphosphinomethylpyridine, bis(diphenylphosphino)ferrocene, bis(diphenylphosphino)methane, bis(dicyclohexylphosphino)methane, bis(di-t-butylphosphino)methane, or TMEDA.
11. The process according to claim 1 , wherein the first ligand or the second ligand is selected from
12. The process according to claim 1 , wherein the contacting step comprises contacting (i) the group 8-11 transition metal precursor compound comprising at least one first ligand with (ii) the at least one second ligand to form a pre-contacted mixture, followed by contacting the pre-contacted mixture with the remaining components (iii)-(vi) in any order to provide the reaction mixture.
13. The process according to claim 1 , wherein the reaction mixture comprises a metalalactone compound, the metalalactone compound comprising a group 8-11 transition metal metalalactone moiety and a) at least one first ligand or b) at least one second ligand.
14. The process according to claim 1 , 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 1 , wherein the associated metal cations are selected from a Group 1, 2, 12, or 13 metal cation.
16. The process according to claim 1 , wherein the associated metal cations are lithium, sodium, potassium, magnesium, calcium, zinc or aluminum cations.
17. The process according to claim 1 , wherein the conditions which produce the α,β-unsaturated carboxylic acid or a salt thereof comprise contacting the reaction mixture with a metal-containing base thereby producing a salt of the α,β-unsaturated carboxylic acid.
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 metal-containing base comprises Na 2 CO 3 , Cs 2 CO 3 , MgCO 3 , NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 , Al(O i Pr) 3 , Na(O t Bu), or Mg(OEt) 2 .
20. The process according to claim 1 , wherein the conditions which 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.
21. The process according to claim 1 , wherein the conditions which produce the α,β-unsaturated carboxylic acid or a salt thereof further produce a polyaromatic resin.
22. The process according to claim 21 , further comprising the step of:
c) regenerating the anionic polyaromatic resin with associated metal cations by contacting the polyaromatic resin with a metal-containing base following the formation of the α,β-unsaturated carboxylic acid or the salt thereof.
23. The process according to claim 1 , wherein a molar yield of the α,β-unsaturated carboxylic acid or a salt thereof based on the transition metal precursor compound is at least 100%.
24. The process according to claim 1 , wherein the group 8-11 transition metal precursor compound comprises Ni.
25. The process according to claim 1 , wherein the olefin comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, or styrene.
26. The process according to claim 1 , wherein:
a) the olefin is ethylene;
b) the diluent comprises a non-protic solvent, a weakly coordinating solvent, or a non-coordinating solvent; and
c) the step of contacting the group 8-11 transition metal precursor compound with the olefin and carbon dioxide is conducted by:
i) using from 10 psig (689 KPa) to 1,000 psig (6,902 KPa) of ethylene partial pressure, using a constant addition of the ethylene and carbon dioxide to provide the reaction mixture; or
ii) adding the ethylene and carbon dioxide in a constant or a variable ethylene:CO 2 molar ratio of from 10:1 to 1:10, to provide the reaction mixture.
27. The process according to claim 1 , wherein the diluent comprises an aromatic hydrocarbon solvent, an ether solvent, a carbonyl-containing solvent, a halogenated aromatic hydrocarbon solvent, or combinations thereof.
28. A process for producing an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising:
a) contacting in any order
(i) a metalalactone compound comprising a group 8-11 transition metal metalalactone moiety and at least one ligand in addition to the metalalactone moiety;
(ii) a diluent; and
(iii) an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and
b) applying conditions to the reaction mixture which induce a metalalactone elimination reaction to form the α,β-unsaturated carboxylic acid or a salt thereof.
29. A process for producing an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising:
a) contacting in any order
(i) a group 8-11 transition metal precursor compound comprising at least one first ligand selected from a diene ligand, an ether ligand, an organic carbonyl ligand, a thioether ligand, an amine ligand, a nitrile ligand, a phosphine ligand, or a carbene ligand;
(ii) at least one second ligand selected from a from a diene ligand, an ether ligand, an organic carbonyl ligand, a thioether ligand, an amine ligand, a nitrile ligand, a phosphine ligand, or a carbene ligand;
(iii) an olefin;
(iv) carbon dioxide (CO 2 );
(v) a diluent; and
(vi) an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and
(2) contacting the reaction mixture with a metal-containing base selected from an alkali metal or an alkaline earth metal oxide, hydroxide, alkoxide, aryloxide, amide, alkyl amide, arylamide, or carbonate to produce an α,β-unsaturated carboxylic acid salt;
wherein the contacting step is carried out in the absence of sodium hydride.
30. The process according to claim 22 , wherein the regenerating step is carried out in the absence of an alkali metal hydride.
31. The process according to claim 17 , wherein the contacting step is carried out in the absence of sodium hydride.
32. The process according to claim 28 , 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.
33. The process according to claim 28 , 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.