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Title:
METHODS OF PRODUCING ALPHA, BETA-UNSATURATED CARBOXYLIC ACID SALTS FROM ALKANES AND CARBON DIOXIDE
Document Type and Number:
WIPO Patent Application WO/2019/053540
Kind Code:
A1
Abstract:
Methods of producing α,β-unsaturated carboxylic acid salt are described. A method can include reacting an alkene and carbon dioxide with a composition that includes a carboxylation catalyst, an organic base that is solubilized in the composition, and an inorganic base that is not solubilized in the composition, under reaction conditions suitable to produce an inorganic base salt of an α,β-unsaturated carboxylic acid. The organic base can have a first pKa and the inorganic base has a second pKa that is greater than the first pKa.

Inventors:
BEETSTRA DIRK (SA)
PASHA FARHAN AHMAD (SA)
KOROBKOV ILIA (SA)
Application Number:
IB2018/056604
Publication Date:
March 21, 2019
Filing Date:
August 29, 2018
Export Citation:
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Assignee:
SABIC GLOBAL TECHNOLOGIES BV (NL)
International Classes:
C07C51/15
Domestic Patent References:
WO2015173277A12015-11-19
WO2015173295A12015-11-19
WO2011007559A12011-01-20
Other References:
YIN ET AL., COORDINATION CHEMISTRY REVIEW, vol. 181, 1999, pages 27 - 59
HENDRIKSEN ET AL., CHEMISTRY, EUROPEAN JOURNAL, vol. 20, 2014, pages 12037 - 12040
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Claims:
CLAIMS

A method of producing an α,β-unsaturated carboxylic acid salt, the method comprising: reacting an alkene and carbon dioxide with a composition comprising a carboxylation catalyst, an organic base that is solubilized in the composition, and an inorganic base that is not solubilized in the composition, under reaction conditions suitable to produce an inorganic base salt of an α,β-unsaturated carboxylic acid, wherein the organic base has a first pKa and the inorganic base has a second pKa that is greater than the first pKa.

The method of claim 1, wherein:

an organic base salt of an α,β-unsaturated carboxylic acid is formed between the organic base and produced α,β-unsaturated carboxylic acid; and

the organic base salt of an α,β-unsaturated carboxylic acid reacts with the inorganic base to produce the inorganic base salt of an α,β-unsaturated carboxylic acid.

The method of claim 1 wherein the difference between the organic base pKa and the inorganic base pKa is 0.2 to 20.

The method of claim 1, wherein the organic base comprises nitrogen-based compound, an ether, an ester, a carbonyl, a carboxylate, an alkoxide, a phenoxide, a carboxylate, a sulfate, a sulfonate, a phosphate, or a phosphonate, or mixtures thereof.

The method of claim 4, wherein the nitrogen based organic compound is an amine, an imine, an amide, an aromatic amine.

The method of claim 5, wherein the organic base has a structure of:

R90

\

N-R 91

R92

where R90 through R92 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heterocyclic or a heteroaryl group, a double bond, a phosphorus group, or where R90 and R91 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, aromatic heteroaryl, or heterocycle ring.

The method of claim 6, wherein the organic base has the structure of:

where R93 through R97 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heterocyclic or a heteroaryl group, or where R93 and R94, R93 and R94, R94 and R95, R95 and R96 and/or R96 and R97 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, aromatic heteroaryl, or heterocycle ring, or 2,6-dimethyl pyridine.

8. The method of claim 1, wherein the inorganic base is an alkali metal or an alkaline earth metal containing base or mixtures thereof.

9. The method of claim 8, wherein the inorganic base is an alkali metal or alkaline earth metal carbonate or mixtures thereof.

10. The method of claim 1, wherein the organic base is 2,6-dimethyl pyridine and the inorganic base is cesium, rubidium, potassium, sodium or lithium carbonate.

11. The method of claim 1, wherein the composition further comprises an organic solvent, and wherein the carboxylation catalyst and the organic base are each solubilized in the organic solvent.

12. The method of claim 1, wherein the composition further comprises an organic solvent, and wherein the carboxylation catalyst is not solubilized in the solvent and the organic base is solubilized in the solvent.

13. The method of claim 1, wherein the inorganic base is an aqueous inorganic base that is immiscible in the composition.

14. The method of claim 1, wherein the reaction conditions include:

(a) maintaining the composition at a temperature of 30 °C to 180 °C;

(b) an alkene pressure of 0.1 MPa to 5 MPa; and/or

(c) a carbon dioxide pressure of 0.1 MPa to 5 MPa, or 0.1 MPa to 0.5 MPa.

15. The method of claim 1, wherein the carboxylation catalyst comprises at least one transition metal of Columns 4, 5, 6, 7, 8, 9, or 10 of the Periodic Table.

16. The method of claim 15, wherein the carboxylation catalyst comprises at least one transition metal, or nickel (Ni) or palladium (Pd).

17. The method of claim 16, wherein the carboxylation catalyst comprises at least one coordinating ligand, or a coordinating ligand comprising at least two coordinating atoms selected from phosphorus (P), nitrogen (N), oxygen (O), sulfur (S), and carbene that coordinate with the transition metal. The method of claim 17, wherein the carboxylation catalyst is (Cy2PCH2CH2PCy2)Ni(C2H4C02) or (Cy2PCH2CH2CH2PCy2)Ni(C2H4), where Cy is cyclohexane.

The method of claim 1, wherein the composition does not include a Lewis acid.

The method of claim 1, wherein the alkene is ethylene and the produced inorganic base salt of an α,β-unsaturated carboxylic acid is an alkali metal or an alkaline earth metal aery late.

Description:
METHODS OF PRODUCING ALPHA, BETA-UNSATURATED CARBOXYLIC ACID SALTS FROM ALKANES AND CARBON DIOXIDE

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U. S. Provisional Patent Application No. 62/558,450 filed September 14, 2017, which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0002] The invention generally concerns methods of producing alpha, beta (α,β)- unsaturated carboxylic acid salts through coupling of an alkene and carbon dioxide. In particular, the invention concerns reacting an alkene and carbon dioxide with a composition that includes an organic base solubilized therein and an insoluble inorganic base not solubilized therein and having a pKa of greater than the pKa of the organic base.

B. Description of Related Art

[0003] α,β-Unsaturated carboxylic acids (e.g., acrylic acid or methacrylic acid) or salts thereof are commercially produced through a two-step oxidation of propylene process (shown below):

This process requires two reactors and two separate catalysts to oxidize the propylene to acrylic acid, which can be capital intensive and inefficient.

[0004] Various attempts to produce acrylic acid from ethylene and carbon dioxide through activation of the carbon dioxide through coordination with a transition metal center have been tried. In many of these reactions, a metallocycle shown below can be produced (See, for example Yin, et al. Coordination Chemistry Review , 1999, Vol 181, page 27-59):

where M is Ni and Ln is a phosphorus containing coordinating ligand. This metallocycle can then be degraded with strong base to form the corresponding α,β- unsaturated carboxylic acid:

[0005] Decomposition/decoupling of the metallocycle has proven challenging (e.g., formation of side products, and polymeric material), and various attempts have been made to improve the overall reaction by either eliminating the formation of or facilitating the decomposition of the metallocycle. By way of example Hendriksen et al. (Chemistry, European Journal, 2014, 20: 12037-12040) describes decoupling of the metallocycle using tertiary amines and lithium iodide as activators. In another example, International Patent Application Publ. No. WO 201107559 to Limbach et al. describes decomposing the metallocycle in the presence of an auxiliary base {e.g., tertiary amines) to give an auxiliary base salt of the α,β-unsaturated carboxylic acid. The auxiliary base salt is then removed from the solution and reacted with an alkali metal or alkaline earth metal base to form an alkali metal or alkaline earth metal salt of the α,β-unsaturated carboxylic acid. [0006] While there have been many attempts to produce α,β-unsaturated carboxylic acids from alkenes and carbon dioxide, these attempts use auxiliary bases or activating agents that are expensive and/or require regeneration Additionally, these processes are not commercially scalable {e.g., they can have inefficient conversion and selectivity rates).

SUMMARY OF THE INVENTION [0007] A discovery has been made that provides a solution to some of the problems discussed above. The solution is premised on the use of a biphasic composition that has an organic base solubilized therein {i.e., the "internal" or solubilized base) and an inorganic base that is dispersed/not-solubilized in the composition {i.e., the "external" or dispersed base). The organic base has a pKa that is less than the inorganic base. This biphasic composition can be used in a coupling reaction of an alkene with carbon dioxide to form an α,β-unsaturated carboxylic salt. Without wishing to be bound be theory, it is believed that an organic base salt of an α,β-unsaturated carboxylic acid is formed between the organic base and produced α,β- unsaturated carboxylic acid, and the organic base salt then reacts with the inorganic base to produce an inorganic base salt of an α,β-unsaturated carboxylic acid. The process of the present invention provides an elegant and cost-effect process to make α,β-unsaturated carboxylic salts {e.g., acrylates). Further, the process can be performed in a "one pot" manner, thereby avoiding the need to isolate and then react intermediate compounds to obtain the desired end product. Notably, specific combinations of bases can be utilized to push the equilibrium of the overall reaction to the formation of inorganic salts instead of acrylic acid, thus making the reaction more exergonic. [0008] In a particular aspect of the present invention, a method of producing an α,β- unsaturated carboxylic acid salt is described. The method can include reacting an alkene and carbon dioxide with a composition under reaction conditions suitable to produce an inorganic base salt of an α,β-unsaturated carboxylic acid. Reaction conditions can include: (a) maintaining the composition at a temperature of 30 °C to 180 °C; (b) an alkene pressure of 0.1 MPa to 5 MPa, preferably 0.5 MPa to 1.5 MPa, or about 1.0 MPa; and (c) a carbon dioxide pressure of 0.1 MPa to 5.0 MPa, preferably 0.1 MPa to 1.0 MPa, or 0.1 MPa to 0.5 MPa. In some instances, the alkene can ethylene and the produced inorganic base salt of an α,β- unsaturated carboxylic acid can be an alkali metal or an alkaline earth metal acrylate, preferably sodium or lithium acrylate. [0009] In certain aspects, the composition can be biphasic. It can include a carboxylation catalyst, an organic base that is solubilized in the composition, and an inorganic base that is not solubilized in the composition. In some embodiments, the composition can include 0.0001 wt. % to 1 wt. % of the carboxylation catalyst, 0.005 wt. % to 10 wt. % of the organic base and 0.1 wt. % to 100 wt. % of the inorganic base. In some embodiments, the organic base can be the solvent. The organic base can have a first pKa and the inorganic base can have a second pKa that is greater than the first pKa. By way of example, the difference between the organic base pKa and the inorganic base pKa can be 0.2 to 20, preferably 2 to 6. Non-limiting examples of organic bases can include nitrogen-based compound, an ether, an ester, a carbonyl, a carboxylate, an alkoxide, a phenoxide, a carboxylate, a sulfate, a sulfonate, a phosphate, or a phosphonate, or mixtures thereof. Non-limiting examples of nitrogen based organic compound is an amine, an imine, an amide, an aromatic amine, a phosphinimine (HN=PH), and the like. Amines can include primary, secondary or tertiary amines. In some embodiments, the organic base can have the structure of:

where R90 through R92 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heterocyclic or a heteroaryl group, a double bond, a phosphorus group, or where R90 and R91 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, aromatic heteroaryl, or heterocycle ring. In a particular embodiment, the organic base has the structure of:

where R93 through R97 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heterocyclic or a heteroaryl group, or where R93 and R94, R93 and R94, R94 and R95, R95 and R96 and/or R96 and R97 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, aromatic heteroaryl, or heterocycle ring, preferably 2,6-dimethyl pyridine. [0010] Non-limiting example of inorganic bases can include an alkali metal or an alkaline earth metal containing base, preferably, an alkali metal or alkaline earth metal carbonate, phosphate, nitrate, or halide, or mixtures thereof. Alkali metal or alkaline earth metal carbonates can include sodium carbonate, sodium bicarbonate, lithium carbonate, lithium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, cesium bicarbonate, magnesium carbonate, calcium carbonate, or mixtures thereof. In a preferred embodiment, the organic base can be 2, 6-lutidine (pKa of about 6.6) and the inorganic base can be sodium, lithium, or cesium carbonate (pKa of CCb = is about 10.3). In some embodiments, the composition can include an organic solvent. The carboxylation catalyst and the organic base can each be solubilized in the organic solvent. In some embodiments, the carboxylation catalyst is not solubilized in the solvent and the organic base is solubilized in the organic solvent. In some embodiments, the inorganic base can be an aqueous inorganic base solution. The aqueous inorganic base solution can be immiscible in the composition. The aqueous inorganic base solution can be dispersed in the composition such that a plurality of droplets of the inorganic base solution are present in the composition. In some instances, the composition does not include a Lewis acid.

[0011] The carboxylation catalyst can include at least one transition metal of Columns 4- 10 of the Periodic Table. Non-limiting examples of transition metals include nickel (Ni) or palladium (Pd). In some instances, the carboxylation catalyst includes at least one coordinating ligand. In a preferred embodiment, the coordinating ligand can include at least two coordinating atoms selected from nitrogen (N), oxygen (O), sulfur (S), and carbene that coordinate with the transition metal. In some instances, the carboxylation catalyst is (Cy 2 PCH2CH2PCy2)Ni(C2H4C0 2 ) or (Cy 2 PCH2CH2CH2PCy2)Ni(C2H 4 ), where Cy is cyclohexane.

[0012] In the context of this invention 20 embodiments are described. Embodiment 1 is a method of producing an α,β-unsaturated carboxylic acid salt, the method comprising: reacting an alkene and carbon dioxide with a composition comprising a carboxylation catalyst, an organic base that is solubilized in the composition, and an inorganic base that is not solubilized in the composition, under reaction conditions suitable to produce an inorganic base salt of an α,β-unsaturated carboxylic acid, wherein the organic base has a first pKa and the inorganic base has a second pKa that is greater than the first pKa. Embodiment 2 is the method of embodiment 1, wherein: an organic base salt of an α,β-unsaturated carboxylic acid is formed between the organic base and produced α,β-unsaturated carboxylic acid; and the organic base salt of an α,β-unsaturated carboxylic acid reacts with the inorganic base to produce the inorganic base salt of an α,β-unsaturated carboxylic acid. Embodiment 3 is the method of any one of embodiments 1 to 2, wherein the difference between the organic base pKa and the inorganic base pKa is 0.2 to 20, preferably 2 to 6. Embodiment 4 is the method of any one of embodiments 1 to 3, wherein the organic base comprises nitrogen-based compound, an ether, an ester, a carbonyl, a carboxylate, an alkoxide, a phenoxide, a carboxylate, a sulfate, a sulfonate, a phosphate, or a phosphonate, or mixtures thereof. Embodiment 5 is the method of embodiment 4, wherein the nitrogen based organic compound is an amine, an imine, an amide, an aromatic amine. Embodiment 6 is the method of embodiment 5, wherein the organic base has a structure of:

R90

\

N-R 91

R92

where R90 through R92 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heterocyclic or a heteroaryl group, a double bond, a phosphorus group, or where R90 and R91 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, aromatic heteroaryl, or heterocycle ring. Embodiment 7 is the method of embodiment 6, wherein the organic base has the structure of:

where R93 through R97 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heterocyclic or a heteroaryl group, or where R93 and R94, R93 and R94, R94 and R95, R95 and R96 and/or R96 and R97 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, aromatic heteroaryl, or heterocycle ring, preferably 2,6-dimethyl pyridine. Embodiment 8 is the method of any one of embodiments 1 to 7, wherein the inorganic base is an alkali metal or an alkaline earth metal containing base, preferably, an alkali metal or alkaline earth metal carbonate, phosphate, nitrate, or halide, or mixtures thereof. Embodiment 9 is the method of embodiment 8, wherein the inorganic base is an alkali metal or alkaline earth metal carbonate, preferably cesium, rubidium, potassium, sodium or lithium carbonate or bicarbonate, or mixtures thereof. Embodiment 10 is the method of any one of embodiments 1 to 9, wherein the organic base is 2,6-dimethyl pyridine and the inorganic base is cesium, rubidium, potassium, sodium or lithium carbonate. Embodiment 11 is the method of any one of embodiments 1 to 10, wherein the composition further comprises an organic solvent, and wherein the carboxylation catalyst and the organic base are each solubilized in the organic solvent. Embodiment 12 is the method of any one of embodiments 1 to 11, wherein the composition further comprises an organic solvent, and wherein the carboxylation catalyst is not solubilized in the solvent and the organic base is solubilized in the solvent. Embodiment 13 is the method of any one of embodiments 1 to 12, wherein the inorganic base is an aqueous inorganic base that is immiscible in the composition. Embodiment 14 is the method of any one of embodiments 1 to 13, wherein the reaction conditions include: (a) maintaining the composition at a temperature of 30 °C to 180 °C; (b) an alkene pressure of 0.1 MPa to 5 MPa, preferably 0.5 MPa to 1.5 MPa, or about 1.0 MPa; and/or (c) a carbon dioxide pressure of 0.1 MPa to 5 MPa, preferably 0.1 MPa to 1 MPa, or 0.1 MPa to 0.5 MPa. Embodiment 15 is the method of any one of embodiments 1 to 14, wherein the carboxylation catalyst comprises at least one transition metal of Columns 4, 5, 6, 7, 8, 9, or 10 of the Periodic Table. Embodiment 16 is the method of embodiment 15, wherein the carboxylation catalyst comprises at least one transition metal, preferably, nickel (Ni) or palladium (Pd). Embodiment 17 is the method of embodiment 16, wherein the carboxylation catalyst comprises at least one coordinating ligand, preferably a coordinating ligand comprising at least two coordinating atoms selected from phosphorus (P), nitrogen (N), oxygen (O), sulfur (S), and carbene that coordinate with the transition metal. Embodiment 18 is the method of embodiment 17, wherein the carboxylation catalyst is where Cy is cyclohexane. Embodiment 19 is the method of any one of embodiments 1 to 18, wherein the composition does not include a Lewis acid. Embodiment 20 is the method of any one of embodiments 1 to 19, wherein the alkene is ethylene and the produced inorganic base salt of an α,β-unsaturated carboxylic acid is an alkali metal or an alkaline earth metal acrylate, preferably sodium or lithium acrylate.

[0013] The following includes definitions of various terms and phrases used throughout this specification.

[0014] "pKa" refers to the negative base-10 logarithm of the acid dissociation constant (Ka) of a solution.

[0015] An "aliphatic group" is an acyclic or cyclic, saturated or unsaturated carbon group, excluding aromatic compounds. An aliphatic group can include 1 to 50, 2 to 25, or 3 to 10 carbon atoms. A linear aliphatic group does not include tertiary or quaternary carbons. A branched aliphatic group includes at least one tertiary and/or quaternary carbon. A cyclic aliphatic group includes at least one ring in its structure. Polycyclic aliphatic groups may include fused, e.g., decalin, and/or spiro, e.g., spiro[5.5]undecane, polycyclic groups. Non- limiting examples of linear, branched or cyclic, aliphatic group substituents include alkyl, halogen (e.g., fluoride, chloride, bromide, iodide), haloalkyl, haloalkoxy hydroxyl (— OH), alkyoxy (—OR 1 ), ether (R-O-R), carboxylic acid (RCO2H), ester (RCO2OR), amine (NH or NR), ammonium (N(R)3 + , NH(R)2 + , NH 2 (R)i + , NH 3 + ), amide, nitro, nitrile (CN), acyl (RCO), thiol (— SH), sulfoxides, sulfonates,, phosphine (— PRR"), phosphonium (P(R + , PH(R + , PH 2 (R)2 + , PH 3 (R)i + , PH 4 + ), thioether (— S— ), where R and R" is each independently an alkyl group or haloalkyl group.

[0016] An "alkyl group" is a linear or branched, substituted or unsubstituted, saturated hydrocarbon. In the context of the present invention, an alkyl group has 1 to 50, 2 to 30, 3 to 25, or 4 to 20 carbon atoms. Alkyl groups in the context of the present invention include all isomers and all substitution types unless otherwise stated. For example, butyl includes n-butyl, isobutyl, and tert-butyl; pentyl includes n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl. Non-limiting examples of alkyl group substituents include halogen, hydroxyl, alkyoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether.

[0017] An "alkene" or "alkenyl" is a linear or branched, unsubstituted or substituted, unsaturated hydrocarbon. In the context of this invention, an alkenyl group has 1 to 50, 2 to 30, 3 to 25, 4 to 20, 2 to 8, or 2 to 4 carbon atoms. When alkyl groups disclosed in this application, the term includes all isomers and all substitution types unless otherwise stated. Non-limiting examples of an alkene group substituents include alkyl, halogen, hydroxyl, alkyoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether. Non-limiting examples of alkenes are shown in Structure XIII and include ethylene, propene, butylene, and styrene. [0018] An "alkynyl" group refers to a linear or branched monovalent hydrocarbon radical of at least 2 carbon atoms with at least one triple bond. In the context of this invention, the alkenyl group has 1 to 50, 2 to 30, 3 to 25, 4 to 20, or 2 to 4 carbon atoms. The alkynyl radical may be optionally substituted independently with one or more substituents described herein. Non-limiting examples include ethynyl (-C≡CH), propynyl (propargyl, -CH2C≡CH), -C≡C- CH 3 , and the like.

[0019] An "alkylene" group refers to a saturated divalent hydrocarbon group derived from a straight or branched chain saturated hydrocarbon by the removal of two hydrogen atoms. In the context of this invention, an alkenyl group has 1 to 50, 2 to 30, 3 to 25, 4 to 20, or 1 to 4 carbon atoms. Non-limiting examples of alkylene groups include methylene (-CH2-), ethylene (-CH2CH2-), isopropylene (-CH(CH 3 )CH 2 -), and the like.

[0020] An "aryl group" or an "aromatic group" is a substituted or unsubstituted, mono- or polycyclic hydrocarbon with alternating single and double bonds within each ring structure. Non-limiting examples of aryl group substituents include alkyl, halogen, hydroxyl, alkyoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether. [0021] A "heteroatom" refers to unsubstituted or substituted atom that is not carbon unless otherwise specified. Non-limiting examples of heteroatoms are oxygen (O), nitrogen (N), phosphorus (P), or sulfur (S). Non-limiting examples of heteroatoms substituents include hydrogen, aliphatic, alkyl, alkynyl, and alkenyl.

[0022] A "heteroaryl group" or "hetero-aromatic group" is a mono-or polycyclic hydrocarbon with alternating single and double bonds within each ring structure, and at least one atom (heteroatom) within at least one ring is not carbon. Non-limiting examples of heteroaryl group substituents include alkyl, halogen, hydroxyl, alkyoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether.

[0023] The "heterocyclic" group is a mono-or polycyclic saturated or unsaturated hydrocarbon with at least one atom (heteroatom) within at least one ring is not carbon. Examples of heterocyclic rings include, but are not limited to, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, dihydropyranyl, tetrahydrothiopyranyl, piperidino, morpholino, thiomorpholino, thioxanyl, piperazinyl, homo-piperazinyl, azetidinyl, oxetanyl, thietanyl, homopiperidinyl, oxepanyl, thiepanyl, oxazepinyl, diazepinyl, thiazepinyl, 2-pyrrolinyl, 3-pyrrolinyl, indolinyl, 2H-pyranyl, 4H-pyranyl, dioxanyl, 1,3-dioxolanyl, pyrazolinyl, dithianyl, dithiolanyl, dihydropyranyl, dihydrothienyl, dihydrofuranyl, pyrazolidinylimidazolinyl, imidazolidinyl, 1,2,3,4-tetrahydro iso-quinolinyl. Some non- limiting examples of a heterocyclic group wherein 2 ring carbon atoms are substituted with oxo (=0) moieties are pyrimidindionyl and 1, 1-dioxo-thiomorpholinyl.

[0024] A "haloalkyl" or "haloalkoxy" refers to an alkyl or alkoxy substituted with one or more halogen atoms.

[0025] The terms "catecholate" or "catecholate ligand" refer to ligands that include a phenyl ring. In non-limiting example, two oxygen atoms or nitrogen atoms connected to the phenyl ring at the ring's 1 and 2 positions. The ligand connects to the metal center of the

, where R'" and R"" are each independently alkyl, aryl, or form a fused ring with the phenyl ring.

[0026] The terms "about" or "approximately" are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within

0.5%.

[0027] The terms "wt.%", "vol.%", or "mol.%" refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or total moles of a material, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0028] The term "substantially" and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0029] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0030] The term "effective," as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result. [0031] The use of the words "a" or "an" when used in conjunction with any of the terms "comprising," "including," "containing," or "having" in the claims, or the specification, may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one." [0032] The words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. [0033] The methods of the present invention can "comprise," "consist essentially of," or "consist of particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase "consisting essentially of," in one non- limiting aspect, a basic and novel characteristic of the methods of the present invention are their abilities to efficiently produce α,β-unsaturated carboxylic acids salts from an alkene and carbon dioxide.

[0034] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings. [0036] FIG. 1 is an energy diagram schematic depicting the energy levels and transition states for the decomposition of the metal lactone formed in a metal catalyzed alkene/C0 2 reaction. [0037] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION [0038] The currently available processes to make α,β-unsaturated carboxylic alkali metal or alkaline-earth metal salts use complex steps, expensive reagents, reagents that need regeneration, require isolation of an intermediate α,β-unsaturated carboxylic ammonium salt, or combinations thereof. A discovery has been made that provides a solution to some or all of these problems. The solution is premised on using an organic base and an inorganic base in a biphasic reaction mixture, where the inorganic base has a pKa greater than the organic base. Biphasic refers to the inorganic base and organic base being present in the reaction mixture in different phases (e.g., the inorganic base can be dispersed in the reaction mixture whereas the organic base can be solubilized in the reaction mixture). Selective base combinations provide the advantages of: 1) performing the reaction in one step (e.g., without isolation of an intermediate ammonium salt), 2) allows inexpensive reagents to be used, and/or 3) does not require regeneration of the bases or co-catalysts.

[0039] These and other non-limiting aspects of the present invention are discussed in further detail below with reference to the figures.

A. Methods of Producing α,β-Unsaturated Carboxylic Acids [0040] Methods of producing α,β-unsaturated carboxylic salts of the present invention can include reacting an alkene and carbon dioxide with a composition that includes a carboxylation catalyst, an organic base that is solubilized in the composition, and an inorganic base that is not solubilized in the composition, under reaction conditions suitable to produce an inorganic base salt of an α,β-unsaturated carboxylic acid. The organic base can have a first pKa and the inorganic base can have a second pKa that is greater than the first pKa. Reaction conditions can include temperature, alkene pressure, carbon dioxide pressure, or combinations thereof. The reaction temperature can be maintained from 30 °C to 180 °C, 50 °C to 70 °C, or 30 °C, 35 °C 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 1 10 °C, 1 15 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, or any value or range there between. An alkene pressure can range from 0.1 MPa to 5 MPa, 0.5 MPa to 1.5 MPa, or about 1.0 MPa or about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 MPa, or any value or range there between. A carbon dioxide pressure can range from 0.1 MPa to 5 MPa, 0.1 MPa to 1 MPa, or 0.1 MPa to 0.5 MPa, or about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 MPa, or any value or range there between. The reaction temperature and pressures can be adjusted to maintain the reaction conditions at temperatures that do not affect the catalyst stability. Without wishing to be bound by theory, it is believed that an organic base salt of an α,β-unsaturated carboxylic acid is formed between the organic base and produced α,β-unsaturated carboxylic acid and the organic base salt of an α,β-unsaturated carboxylic acid reacts with the inorganic base to produce the inorganic base salt of an α,β-unsaturated carboxylic acid. FIG. 1 depicts a diagram for the intermediates that can be formed during catalysis of an alkene with carbon dioxide. B. Composition

[0041] The composition can include a carboxylation catalyst, an organic base, an inorganic base, and optionally a solvent. The composition can have two phases. By way of example, the carboxylation catalyst and organic base can form a continuous phase of the composition and the inorganic base can form a discontinuous phase of the composition. The carboxylation catalyst can be solubilized, or substantially solubilized, in the organic base to form the continuous phase and the inorganic base can be dispersed throughout the continuous phase. In instances where an solvent is used, the carboxylation catalyst and the organic base are each solubilized, or substantially solubilized, in the solvent and the inorganic base is dispersed (not solubilized or substantially not solubilized) or is immiscible (e.g., an aqueous solution of organic base) in the solvent. In some embodiments, the solvent is an organic solvent. Non- limiting examples of organic include as halogenated aromatic compounds, polar solvents, such as monofluorobenzene (PhF), monochlorobenzene (PhCl), tetrahydrofuran (THF), dimethylformamide (DMF), hexamethylphosphorusamide (HMPA), monomethoxybenzene (anisole), 1,2-dimethoxy ethane (DME), di-«-butyl ether, methyl tert-butyl ether (MTBE). In some embodiments, a metallic co-reagent like metallic zinc, aluminum, iron, manganese (reducing metals) or an organic reducing agent. Organic reducing agents can include a benzene compound or substituted benzene groups that are include at least one hydroxyl group. Non- limiting examples of organic reducing agents include alkyl or aryl esters of 3,4dihydroxybenzoic acid, 3,4-dihydroxy-benzaldehyde, 3,4-dihydroxy-benzamide; an alkyl or aryl (3,4-dihydroxyphenyl) ketone; 1,4-dihydroxybenzene (hydroquinone) or a substituted hydroquinone; hindered phenols, pyrogallol, methyl gallate, leuco dyes or mixtures thereof can be added to facilitate regeneration of the metal of the carboxylation catalyst. 1. Bases

[0042] The inorganic and organic bases can be selected by the pKa values. The pKa value of the organic base can be less than the pKa of the selected inorganic base. The difference between the organic base pKa and the inorganic base pKa can be 0.2 to 20, preferably 2 to 6, or about 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, or any value or range there between. If conjugate bases of polyprotic acids are used, the pKa value for the completely ionized base is used. By way of example, if a bicarbonate is used the pKa 2 of 10.3 for the dissociation of HCO3 to CCb = is used instead of the pKai value of 3.6 for the dissociation of H2CO3 to HCO3 or the apparent pKa of 6.35.

[0043] Non-limiting examples of organic bases can include nitrogen-based compound, an ether, an ester, a carbonyl, a carboxylate, an alkoxide, a phenoxide, a carboxylate, a sulfate, a sulfonate, a phosphate, or a phosphonate, or mixtures thereof. Non-limiting examples of nitrogen based organic compound is an amine, an imine, an amide, an aromatic amine a phosphinimine (HN=PH). Amines can include primary, secondary or tertiary amines. In some embodiments, the organic base can have the structure of:

R90

\

/ N- 9 i

R92 (LV) where R90 through R92 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heterocyclic or a heteroaryl group, a double bond, or where R90 and R91 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, aromatic heteroaryl, or heterocycle ring. In a particular embodiment, the organic base has the structure of:

where R93 through R97 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heterocyclic or a heteroaryl group, or where R93 and R94, R93 and R94, R94 and R95, R95 and R96 and/or R96 and R97 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, aromatic heteroaryl, or heterocycle ring, preferably. Non-limiting examples of organic bases include pyridine (pKa of 5.2), 2,6-dimethyl pyridine (pKa of 6.6), substituted anilines having a pKa of 18 to 28, quinoline (pKa 4.9), isoquinoline (pKa of 5.5)

[0044] The inorganic base can be an alkali metal or an alkaline earth metal containing base, or mixtures thereof. The alkali metal or alkaline earth metal containing base can include a metal carbonate (CCb = ), a metal bicarbonate (HCCb ), a metal phosphates (H2PO4 , HP0 4 = , PC"4 3" ), a metal nitrate (NO2 ), or a metal halide (F , CI , Br , I , etc.), or mixtures thereof. Alkali alkali metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and/or cesium (Cs). Alkaline earth metals include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and/or barium (Ba). Non-limiting examples of metal carbonates orbicarbonates (pKa = about 10.3) include L12CO3, L1HCO3, Na 2 C0 3 , NaHC0 3 , Mg(HC0 3 ) 2 , MgC0 3 , Ca(HC0 3 ) 2 , CaCCb, Ba(HC0 3 ) 2 , BaCCb, and the like. Non-limiting examples of metal phosphates (pKa = about 7.2) include NaH 2 P0 4 , Na 2 HP0 4 , Na 3 P0 4 , KH 2 P0 4 , K 2 HP0 4 , K 3 P0 4 , CsH 2 P0 4 , Cs 2 HP0 4 , Cs 3 P0 4 , Mg 3 P0 4 , Ca 3 P0 4 , Ba 3 P0 4 , and the like. Non-limiting examples of metal nitrates (pKa = 9) include L1NO2, NaN0 2 , Mg(N0 2 ) 2 , Ca(N0 2 ) 2 , Ba(N0 2 ) 2 , and the like. Non-limiting examples of metal halides include Lil, Nal, KI, Csl, LiCl, LiBr, LiF, ZnCl 2 , CaCl 2 , MgCh, AlCh, FeCh, FeCh, VC1 3 , or the like. In some embodiments, metal halides {e.g., Lewis acids) are not used.

[0045] In some embodiments, phase transfer compounds can be used to assist in transferring the insoluble base into the solvent phase. Non-limiting examples of phase transfer agents include NaBF , NaPFe, NaSbFe, Na(B(C 6 F 5 ) 4 ), Na(B(CeH 3 (CF 3 ) 2 ) ) (here listed for sodium), quaternary ammonium salts, crown ethers and the like.

2. Carboxylation Catalyst

[0046] The carboxylation catalyst can be any carboxylation catalyst that promotes the reaction between an alkene and carbon dioxide and can be solubilized in the organic base or solvent of the composition. a. Metals

[0047] The metal carboxylation catalyst can include one or more transition metals from Columns 4 through 12 of the Periodic Table coordinating to one or more ligands. Non-limiting examples of transition metals include nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), cobalt (Co), iridium (Ir), and rhodium (Rh). The metals used to prepare the catalyst of the present invention can be provided in various oxidation states {e.g., 0, +1, +2, +3, etc.). The metal carboxylation catalyst can include a ligand L that can be displaced by the alkene. Alternatively, a metal carboxylation catalyst/coordination ligand/alkene complex can be obtained initially by reacting a transition metal source with a coordinating ligand and an alkene to give metal carboxylation catalyst/coordination ligand/alkene complex. The metal carboxylation catalyst can one or more ligands selected from halides, amines, amides, oxides, phosphides, carboxylates, acetylacetonate, aryl- or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, aromatics and heteroaromatics, ethers, PF 3 , phospholes, phosphabenzenes, and mono-, di- and polydentate phosphinite, phosphonite, phosphoramidite and phosphite ligands. Non-limiting examples of stabilizing ligands include cycloocta-1,3- diene (COD), bis(cyclooctatetraene), bis(cycloocta-l,3,7-triene), bis(o-tolylphosphito) metal (ethylene), tetrakis (triphenylphosphite) bis(ethylene), 4-butyl-naphthalene-l,2-bisolate, 1- methyl-naphthalene-l,2-bisolate, 4-ethyl catecholate, 3,5-di(butyl)-4-(bromo)catecholate, 4- (propyl)catecholate, halides (e.g., bromides and chlorides). The metal carboxylation catalyst can be prepared by known methods or purchased from a commercial supplier. Useful transition metal sources include commercial standard complexes, for example [M(p-cymene)Cl2]2, [M(benzene)Cl 2 ]n, [M(COD)2], [M(CDT)], [M(C 2 H 4 ) 3 ], [MC1 2 x H2O], [MC1 3 x H2O], [M(acetylacetonate) 3 ], [M(DMS0)4MC1 2 ], where M is the transition metal. In a particular embodiment, nickel(bis(cycloocta-l,5-diene) or bis(triphenylphosphine)(ethylene)nickel can be used as the metal carboxylation catalyst. A non-limiting example of a commercial source of the above mentioned metals or metal complexes is Sigma Aldrich® (U. S. A). b. Coordinating Ligands

[0048] The coordinating ligand may be polydentate, for example, a bidentate ligand. The bidentate ligand coordinates once to the metal center of the metal carboxylation catalyst. The coordination ligand can include 2, 3, 4, 5, 6 or more coordination atoms or carbenes. The coordinating atoms can be different or the same. Non-limiting examples of combinations of at least two different coordinating atoms are (P, P), (P, N), (P, O), (P, S), (P, carbene), (O, S), (N, S), (N, O), (N, carbene), (O, carbene), or (S, carbene). In other aspects, the ligand includes at least two of the same coordinating atoms (e.g., (P, P), (N, N), (O, O), (S, S), or (carbene, carbene). In some instances, the bidentate ligand can include two or more heteroatoms (e.g., N, O, and S) or a heteroatom and a carbene (C:) that together coordinate with the metal in the metal carboxylation catalyst. The ligand can be acyclic or cyclic. In some embodiments, the coordinating ligand can include a phosphorus atom in a non-coordinating position of the ligand. In other embodiments, the coordination ligand does not include a phosphorus atom. An amount of coordinating ligand used with the metal coordination catalyst can be determined by the number of coordinating atoms. In a non-limiting example, a 1 : 1 molar ratio of coordinating ligand to metal carboxylation catalyst can be used for a bidentate ligand. i. (N,N) Ligands [0049] In one aspect, the coordinating ligand can include two nitrogen atoms (N,N). Non- limiting examples of ligands that include nitrogen atoms include di-, tri- and polyamines, imines, diimines, pyridine, substituted pyridines, bipyridines, imidazoles, substituted imidazoles, pyrroles, substituted pyrroles, pyrazoles and substituted pyrazoles, or combinations thereof. These compounds can be used together (e.g., two pyridines in one ligand or a diimine) to form a ligand having 2 nitrogen compounds. In a preferred aspect, a bidentate ligand can have a 1,4-diaza- 1,3 -butadiene structure:

where Ri, R2, R3, and R 4 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a substituted heteroatom, a halogen, a heterocyclic or a heteroaryl group, or where Ri and R2, R2 and R3, and/or R3 and R 4 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, heteroaryl, or heterocycle ring. Ri and R 4 can each independently an alkyl, a branched alkyl, a cycloalkyl, an aryl, or a substituted aryl group. R2 and R3 can come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, heteroaryl, or heterocycle ring. Ri and R2 can come together to form a heteroaryl or heterocycle ring in combination with R3, and R 4 can be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heteroaryl group or coming together to with other atoms to form a heteroaryl or heterocyclic ring. Ri through R 4 can include from 1 to 50 carbon atoms. Non- limiting examples of Ri through R 4 groups include hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl, octacosyl, nonacosyl, triacontyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclodecyl, phenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 3- ethylphenyl, 4-ethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 3-propylphenyl, 4- propylphenyl, 2,6-dipropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2,6- diisopropylphenyl, 2,4,6-tri-isopropylphenyl, 3-butylphenyl, 4-butylphenyl, 2,6- dibutylphenyl, 2,4,6-tributylphenyl, 3-pentylphenyl, 4-pentylphenyl, 2,6-dipentylphenyl, 2,4,6-tripentylphenyl, 3-hexylphenyl, 4-hexylphenyl, 2,6-dihexylphenyl, 2,4,6-trihexylphenyl, 3-heptylphenyl, 4-heptylphenyl, 2,6-diheptylphenyl, 2,4,6-triheptylphenyl, 3-octylphenyl, 4- octylphenyl, 2,6-dioctylphenyl, 2,4,6-trioctylphenyl, 3-nonylphenyl, 4-nonylphenyl, 2,6- dinonylphenyl, 2,4,6-trinonylphenyl, 3-decylphenyl, 4-decylphenyl, 2,6-didecylphenyl, 2,4,6- tridecylphenyl, 3-undecylphenyl, 4-undecylphenyl, 2,6-diundecylphenyl, 2,4,6- triundecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl, 2,6-didodecylphenyl, 2,4,6- tridodecylphenyl and all isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl. In one instance, the Ri and R 4 are substituted phenyl groups and R2 and R3 are defined as above. Such a coordinating ligand can have the general structure of:

where R5, R 6 , R7, Rs, R9, Rio, R11, R12, R13, and R14 are independently H, alkyl, branched alkyl, aryl, substituted aryl, or substituted heteroatom groups. The alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3. In some instances, R5, R 6 , R7, Rs, R9, Rio, R11, R12, R13, and R14 can be selected from methyl, ethyl, and all isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl. R5, R9, Rio, and R14 can each independently be methyl (CH3) or isopropyl ((CH3)2CH) groups, or combinations thereof. In particular aspects, the R2 and R3 are methyl and the coordinating ligand can have the following specific structures with their corresponding names:

[l,4-bis{2,5-di(methyl)phenyl}-2-(methyl)-3-(methyl)-l,4-dia zabuta-l,3-diene];

[ 1 ,4-bi s { 2, 5 -di(i sopropyl)phenyl } -2-(methyl)-3 -(methyl)- 1 ,4-diazabuta- 1 , 3 -diene] ;

[l,4-bis{2,3,5-tri(methyl)phenyl}-2-(methyl)-3-(methyl)-l,4- diazabuta-l,3-diene]; or

[ 1 ,4-bisphenyl-2-(methyl)-3 -(methyl)- 1 ,4-diazabuta- 1 ,3 -diene] .

[0050] Non-limiting examples of Ri and R2 joined together with other atoms includes cyclic or aromatic rings that include 4 to 10 atoms, or 5 to 6 atoms (e.g., carbon, oxygen, or sulfur). In a particular instance, Ri and R2 can form a pyridine ring (Structure VII) where R3 and R 4 are as defined above. In some embodiments, R3 and R 4 form a pyridine or substituted pyridine ring.

[0051] Suitable coordinating ligands can have the following specific structures with their corresponding names:

[N-cyclohexyl- 1 -(2-{ 5-methyl }pyridinyl)ethanimine] .

N-cyclohexyl- l-(2-pyridinyl)ethanimine.

N-(2,5-diisopropyl)phenyl-l-(2-pyridinyl)ethanimine. Other suitable ligands are:

(XVI), and (XVII).

[0052] In a particular instance, Ri and R2 and R3 and R 4 can form a bi-pyridyl (e.g., 2,2'- bipyridyl, (Structure VIII)), or substituted bipyridyl type structures. In a particular instance, Ri, R2, R3, and R 4 can join together with other carbon atoms to form phenanthroline (e.g., Structure IX) or substituted phenanthroline type structures.

[0053] Other suitable (N,N) ligands can include an amine and an imine connected through a carbon bridge as depicted in the general structure (XVIII). (XVIII) where Ri, R2, R3, and R 4 area defined as above and R15 and Ri6 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heteroatom (e.g., O), a substituted heteroatom (e.g., OR), a halogen, a heterocyclic, or a heteroaryl group, or R 4 and R15 together with other atoms can form a heterocyclic or heteroaryl ring, or R 4 and Ri6 together with other atoms can form a heterocyclic or heteroaryl ring, or Ri6 is a chemical bond and R3 and R2 come together with other atoms to form a cyclic or heterocyclic ring. R15 and Ri6 can have 1 to 50 atoms (e.g., carbon atoms, or a mixture of carbon atoms and heteroatoms), 2 to 20 atoms or 3 to atoms. By way of example, the bidentate nitrogen ligand can have the following structures:

where R3, R 4 , R15, and Ri6 are as defined above, and R17, Ris, R19, and R20 can each independently be H, alkyl, or branched alkyl groups, or R17 and Ris, Ris and R19, or R19 and R20 can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R17, Ris, Ri9, and/or R20 come together with other atoms can form a fused cyclic, aryl, heterocyclic, or heteroaryl ring system, or Ri6 is a chemical bond and R3 and R17 come together with other atoms to form a cyclic or heterocyclic ring. The alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3. In some instances, Ri6 is a chemical bond and R3 and R17 come together to form a substituted quinoline ring system as shown in structure (XX).

where R 4 , R15, Ris, R19, and R20 are as previously defined. Other suitable ligands include pyrazole or substituted pyrazole compounds as shown in structure (XXI).

where R21, R22, R23, R24, R25, R26, R27, and R28 can each independently be H, alkyl, aryl, or branched alkyl groups, or R21 and R22, R21 and R23, and/or R23 and R24 can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R21, R22, R23, and/or R24 can come together with other atoms to form a fused ring system. In some instances, R23 can be an electron pair, when R24 is part of an aromatic ring. The alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3.

[0054] Other suitable (N,N) bidentate ligands can have the following generic structure:

where R40, R41, R42, R43, R44, and R45 can be each independently H, alkyl, or branched alkyl groups or R40 and R 41 , R41 and R42, R42 and R43, R43 and R44, or R44 and R45 can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R40, R41, R42, R43, R44, and/or R45 can come together with other atoms to form a fused ring system. The alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3. ii. (N, O) and (N, S) Ligands

[0055] In other instances, the coordinating atoms can be different. For example, the ligand includes at least two different coordinating atoms (e.g., (O, S), (N, S), (N, O), (N, carbene), (O, carbene), (S, carbene). By way of example, a (Ν,Ο) or (N,S) bidentate ligand can have the following generic structure: (XXIII) where Ri, R2, R3, R15, and Ri6 are as previously defined for structure (XIII) and X is oxygen or sulfur. Non-limiting examples of coordinating ligands having these structures are: (XXVII), where Rn, Ris, Ri9, R20, R21, R22, R23, R25, R26, and R27 are as previously defined and R25, R26, and R27 can be H, alkyl, aryl, or branched alkyl groups. It should be understood that while not shown as substituted, the ring structures in (XXVI) can be substituted as defined for structures (XXIV). In some instances, the (N, O) ligand (XXVII), where Ri is a hydrogen and R2 is 2, 4, 6-trimethylbenzene having the structure of:

(XXVIII). iii. (O, S), (O, O) and (S,S) Ligands

[0056] Suitable (O, S), (O, O) and (S,S) bidentate ligand can have the following generic structure:

where Y is oxygen or sulfur, X is oxygen or sulfur, R50 and R55 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a halogen, a heterocyclic, a heteroaryl group, or an electron pair, R51, R52, R53, and R54 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heteroatom (e.g., O), a substituted heteroatom (e.g., OR), a halogen, a heterocyclic, or a heteroaryl group, or R50 and R51 together with other atoms can form a heterocyclic or heteroaryl ring, or R51 and R53 together with other atoms can form a heterocyclic or heteroaryl ring, or R51 is chemical bond or are each independently chemical bonds and R50 and R51 come together with other atoms to form a heterocyclic ring, or R54 is a chemical bond and R54 through R55 come together with other atoms to form a heterocyclic ring. R50, R51, R52, R53, R54, and R55 can have 1 to 50 atoms (e.g., carbon atoms, or a mixture of carbon atoms and heteroatoms), 2 to 20 atoms or 3 to atoms. Non-limiting examples of specific structures include:

where Rso, Rsi, R52, and R53 are as previously defined, or

where Y and X are (Ο,Ο), (S,S), or (0,S) and R53 is as previously defined.

It should be understood that while not shown as substituted, the ring structures (XXX) and (XXXI) can be substituted as defined for structures (XXV) and (XXVII). In a particular instance, R53 in ligand (XXXI) is hydrogen and structures (XXXI) are as follows:

iv. (N, Carbene) Ligands

[0057] Suitable (N, carbene) bidentate coordinating ligands can include carbenes in a nitrogen heterocyclic ring (N, Ν,Ν-carbene) and/or sulfur heterocyclic ring(N, N,S-carbene). A (N, Ν,Ν-carbene carbene) bidentate coordinating ligand can have the following general structure:

where R 6 o, R 6 i, R 6 2, R 63 , R 6 4, R 65 , R 66 , R 6 7, andR 68 can each independently be H, alkyl, branched alkyl groups, substituted alkyl, aryl, substituted aryl, alkoxy, heterocyclic, or heteroaryl, and X is N or S, or R 6 o and Rei, R 6 2 and R 6 4, R 6 4 and R 6 7, R 6 6 and R 68 , or R 6 7 and R 68 , or any combination thereof can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R 6 o, Rei, R 6 4, R 6 7, and/or R 68 can come together to form a fused ring system, or R 68 is an electron pair and R 6 7 together with other atoms can form a heterocyclic or heteroaryl ring system, or R 68 is an electron pair and R 6 o, Rei, R 6 4 and/or R 6 7 together with other atoms can form a heterocyclic or heteroaryl ring system, and/or R 6 2 and R 6 4 form a chemical bond or R.62 R.63, R.64, and R 65 form a double bond. The alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3. Non-limiting examples of specific coordinating ligands are:

Rf39 (XLIII) where R 6 o, R 6 i, R 62 , R 63 , and R 6 4, are as defined above and R 66 , R 6 7, R 68 , and R 6 9, can each independently be H, alkyl, branched alkyl, substituted alkyl, aryl, substituted aryl, alkoxy, heterocyclic, or heteroaryl groups, or R 63 and R 6 9, R 6 6 and R 6 7, R 6 7 and R 68 , or R 68 and R 6 9, can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R 6 o, Rei, R 63 , and/or R 6 9 can come together to form a fused ring system. In a particular instance, structure (XLII) has the specific structure:

(XLIII).

[0058] In some instances, a bidentate carbene ligand is used. By way of example, a bidentate carbene can have the following generic structure:

where X and Y are each independently N, S, O, A is a hydrocarbon linking unit having 1 to 5 carbons, R 6 o, Rei, R 62 , R 63 , R 6 4, R 66 , R 6 7, are as defined above for structure (XL), and R70, R71, R72, R73, R74, R75, and R76 can each independently be H, alkyl, branched alkyl groups, substituted alkyl, aryl, substituted aryl, alkoxy, heterocyclic, or heteroaryl, or R 6 o and Rei, R 6 2 and R 6 4, R70 and R71, R72 and R74, R74 and R73, or any combination thereof, can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R 6 o, Rei, R 6 4, R77, and/or R73 can come together to form a fused ring system. The alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3. In a particular instance, structure (XLIV) can have the specific structure:

v. Monodentate Ligands

[0059] Monodentate ligands can include one coordinating heteroatom. Two monodentate ligands are typically used to coordinate with metal of the metal carboxylation catalyst as each ligand coordinates once to the metal center. Suitable monodentate ligands have the generic structure:

XR8oRsiR82 (XL VI) where X is a nitrogen (N), sulfur (S), or oxygen (O) atoms, and RsoR8iR82 can each be independently hydrogen, alkyl, cycloalkyl or aryl. vi. (P,P) Ligands

[0060] Suitable (P,P) bidentate coordinating ligands can include phosphorus. Non-limiting examples of (P,P) ligands for the catalyst can include bis(dicyclohexylphosphino)ethane (dcpe, structure XLVII), l,3-bis(dicyclohexlphosphino)propane (dcpp, structure XLVIII), 1,2- bis(diphenylphosphino)ethane (dppe, structure XLIX), l,3-bis(diphenylphosphino)propane (dppp, structure L), l,4-bis(diphenylphosphino)butane(dppb, structure LI), which are commercially available various suppliers such as Sigma-Aldrich® (U.S.A.).

(XLVII), (XLVIII),

[0061] The ligands and metals described above can be reacted with alkenes and carbon dioxide to form a metallocycle catalyst intermediate. By way of example, a nickel metal precursor, ligand XL VII can react with the alkene and CO2 to form metallocycle structure LII ((dcpe)Ni(CH 2 CH 2 COO)):

In other instances, a nickel metal precursor, ligand XL VIII can react with an olefin to form olefin complexed material shown as structure LIII ((dcpp)Ni(CH 2 CH 2 )), which then can react with C0 2 to form a metallocycle similar in structure to structure LII.

(LIII). C. Alkenes and Carbon Dioxide

[0062] Alkenes used in the context of the present invention can be obtained from various commercial or natural sources or be a by-product of a hydrocarbon process (e.g., hydrocracking, etc.). Suitable alkenes are those of the following structure:

where K a , K h , R c , and R rf are each independently hydrogen, Ci-12-alkyl, C2-i2-alkenyl, or K a and R* together with the other atoms to which they are bonded are a mono- or di-ethylenically unsaturated, 5- to 8-membered carbocycle, with the proviso that at least one R a , R*, R c , and K d is hydrogen. Non-limiting examples of alkenes include ethene, propene, isobutene, butadiene, piperylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, styrene, substituted styrene, or combinations thereof. The alkene to be used in the carboxylation can be in a gaseous or liquid phase under the reaction conditions. In one or more embodiments, the alkene is ethylene (ethene).

[0063] Carbon dioxide used in the present invention can be obtained from various sources. In one non-limiting instance, the carbon dioxide can be obtained from a waste or recycle gas stream (e.g., from a plant on the same site, like for example from ammonia synthesis) or after recovering the carbon dioxide from a gas stream. A benefit of recycling carbon dioxide by using it as a starting material in the process of the invention is that it can reduce the amount of carbon dioxide emitted to the atmosphere (e.g., from a chemical production site). The CO2 stream can be include other gases, preferably inert gases such as helium (He), argon (Ar), or nitrogen (N2), and other inert gases that do not negatively affect the reaction. The carbon dioxide stream can include the alkene. The amount of CO2 in the reactant stream can range from 2 vol.%, 3 vol.%, 4 vol.%, 5 vol.%, 10 vol.%, 15 vol.%, 20 vol.%, 25 vol.%, 30 vol.%, 35 vol.%, 40 vol.%, 45 vol.%, 50 vol.%, 55 vol.%, 60 vol.%, 65 vol.%, 70 vol.%, 75 vol.%, 80 vol.%), 85 vol.%), 90 vol.%, 95 vol.%, 98 vol.% or any range or value there between. The amount of alkene in the reactant stream can range from 2 vol.%, 3 vol.%, 4 vol.%, 5 vol.%, 10 vol.%, 15 vol.%, 20 vol.%, 25 vol.%, 30 vol.%, 35 vol.%, 40 vol.%, 45 vol.%, 50 vol.%, 55 vol.%, 60 vol.%, 65 vol.%, 70 vol.%, 75 vol.%, 80 vol.%, 85 vol.%, 90 vol.%, 95 vol.%, 98 vol.%) or any range or value there between. A volume ratio of CO2 to alkene can range from 0.02: 1 to 40: 1. 0.02. In some instances, the reactant feed stream can include 2.5 vol.% CO2 and 95.5 vol.% alkene, 25% vol.% CO2 and 75 vol.% alkene, 50 vol.% CO2 and 50 vol.% alkene, 75 vol.% C0 2 and 25 vol.% alkene or 97.5 vol.% CO2 and 2.5 vol.% alkene. In a particular instance, 4 vol.% CO2 and 96 vol.% ethylene, 50 vol.% CO2 and 50 vol.% ethylene, or 75 vol.%) CO2 and 25 vol.%> ethylene can be used.

EXAMPLES

[0064] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Materials

[0065] Catalyst and base structures are listed in Table 1. Li(OAC) » 2H20 was used as an internal standard.

Table 1

Cy is cyclohexyl

Example 1

(Transition State Calculations)

[0066] Energy calculations were performed using using DFT b31yp/6-3 lg** basis set while the metal center was defined using pseudo potential SDD. The final energies were computed with triple zeta quality (TZVP) basis sets along with pseudo potential SDD for metal center. The polar continuum model (PCM) was used to taken in account the effect of toluene and flourobenzene solvent environment. For four different catalytic systems, relative energies for all the intermediates and transition states (See, FIG. 1) are reported under Table 2. Table 2 lists the energetics of different catalysts in toluene (TOL) or flurobenzene (FBZ) solvent systems. Referring to FIG. 1, the reaction started with the catalyst/C02/C2H 4 adduct (Ml). The Ml overcame a transition state T 1-2 to form metallolactone M2. The M2 was determined to be the most stable intermediate of this series and was used as a reference to other calculated intermediate energies. M2 reacted to form products. A first probability reaction was determined to be a reductive elimination of lactone via transition state (T2-3A). The second probability reaction was a β-Hydride transfer to metal via transition state (T2-3B), which can extend the whole reaction as M3B- M4 via H transfer from metal to oxygen via transition state T3B-4. The third probability reaction was a keto-enol transformation (enolization) and concerted elimination of acrylic acid via transition state (T2-3C). From the data listed in Table 2, it was determined that the lowest productive barrier with the diphosphine ligand (dcpe) was the enolisation pathway (T2-3C) of about 45-50 kcal/mol (in presence of organic base), and about 62-67 kcal/mol in absence of internal base. Next, the formed ammonium salt of the acrylate then reacted with the inorganic base to form the alkali metal salt of the formed acrylate, and reforming the organic base. With Mes2-diimine (compound XIII), the β-hydrogen elimination (T2-3B, at 38-42 kcal/mol) route was determined to be more feasible, and the overall reaction was not productive to the acrylate (T2-3C at 47.10 kcal/mol). Nonetheless, the overall productive reaction (the endergonic formation of sodium acrylate and sodium bicarbonate) was still the thermodynamically most favored. For the Mes2-diimine however, the enolisation (through T2-3C at 47.10 kcal/mol) did not lead to the thermodynamically more stable product (M3C, at 11-13 kcal/mol, while M3B was at 16-17 kcal/mol). It was determined that for this ligand the reaction would be significantly slower as most of the catalyst was dormant in the 'acrylate-hydride' state M3B.

Table 2

Catalyst T2-3C M3A M3B M3C T3B-4 M4

DCPE 64.59 52.50 12.03 28.44 31.27 6.38

65.13 54.81 13.09 29.35 34.15 8.27

DCPE 48.09 49.69 11.56 24.44 29.36 6.12

+TEA 46.52 51.83 12.05 25.08 32.03 8.17

DCPE+ 48.57 49.27 11.96 24.33 26.64 1.73 LUITIDINE

47.92 51.82 12.53 25.14 29.33 3.62

Mes2_Amine 47.11 55.00 16.07 10.99 35.86 29.45

47.10 57.43 16.80 13.08 38.70 32.83

Total energy (AG) in kcal/mol

Example 2

(Comparative Method of Making Acrylic Salts with Organic Base) [0067] A solution of (dcpe)Ni(CH 2 CH 2 COO) or (dcpp)Ni(CH 2 CH 2 ), zinc, solvent, and organic base in the amounts listed in Table 3 was reacted at an ethylene pressure of 1 MPa, a C0 2 pressure of 0.1 MPa under the conditions listed in Table 3.

Table 3

TON = turn over number Example 3

(Method of Making Acrylic Salts with Organic Base and Na 2 C03)

[0068] A solution of catalyst, zinc, solvent, organic base, and Na 2 C0 3 as the inorganic base was reacted under the conditions listed in Table 4. Example 4

(Method of Making Acrylic Salts with Organic Base and NaHCOs)

[0069] A solution of catalyst, zinc, solvent, organic base, and NaHCCb as the inorganic base was reacted at an ethylene pressure of 1 MPa, a CO2 pressure of 0.2 MPa under the conditions listed in Table 5. Comparative samples were performed using triethylamine or no organic base.

Example 5

(Method of Making Acrylic Salts with Organic Base and L12CO3)

[0070] A solution of catalyst, zinc, solvent (monofluorobenzene, 2.5 g), organic base (2,6- lutidine), and L12CO3 as the inorganic base was reacted at an ethylene pressure of 1 MPa, a CO2 pressure of 0.2 MPa at 50 °C for 10 hours for the times listed in Table 6.

Table 6

*TON = turn over number, **TOF = turn over rate

Table 4

*TON = turn over number, **TOF = turnover rate

Table 5

*TON = turn over number, **TOF = turnover rate