1. A catalyst system for producing an α, β -unsaturated carboxylic acid or salt thereof, the catalyst system comprising:

(a) a metallolactone comprising a group 8-11 transition metal and at least one first ligand;

(b) a diluent;

(c) at least one second ligand; and

(d) an anionic polyaromatic resin having associated metal cations;

wherein the anionic polyaromatic resin with associated metal cations comprises a metallized phenol-formaldehyde resin, a metallized polyhydroxyarene-formaldehyde resin or a metallized polyhydroxyarene-and fluorophenol-formaldehyde resin.

2. The catalyst system of 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.

3. The catalyst system of claim 1, wherein:

a) the first ligand, the second ligand, or both the first ligand and the second ligand are bidentate ligands; or

b) The first ligand, the second ligand, or the first ligand and the second ligand independently comprise at least one of a nitrogen, phosphorus, sulfur, or oxygen coordinating atom.

4. The catalyst system of claim 1, wherein the first ligand, the second ligand, or the first ligand and the second ligand independently comprise a diphosphine ligand, a diamine ligand, a diene ligand, a diether ligand, or a disulfide ligand.

5. The catalyst system of claim 1, wherein the first ligand, the second ligand, or the first ligand and the second ligand independently comprise 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.

6. The catalyst system of claim 1, wherein the first ligand is a diene ligand and the second ligand is a diphosphine ligand.

7. The catalyst system of claim 1, wherein the first ligand is 1, 5-cyclooctadiene or TMEDA and the second ligand is 1, 2-bis (dicyclohexylphosphino) ethane or TMEDA.

8. The catalyst system of claim 1, wherein the first ligand or the second ligand is selected from the group consisting of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, phenylphosphine, tolylphosphine, diphenylphosphine, ditolylphosphine, triphenylphosphine, trimethylphenylphosphine, 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' -triisopropyl-1, 1' -biphenyl, tri-t-butylphosphino-3, 6-dimethoxy-2 ',4',6' -triisopropyl-1, 1' -biphenyl, 2-di-tert-butylphosphino-2 ' -methylbiphenyl, 2- (di-tert-butylphosphinomethyl) pyridine, 2-di-tert-butylphosphino-2 ',4',6' -triisopropyl-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-tert-butylphosphino) ferrocene, 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 (dibutylphosphino) ethane, 1, 2-bis (di-t-butylphosphino) 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' -bis [ bis (3, 5-dimethylphenyl) phosphino ] -4,4',6,6' -tetramethoxybiphenyl, 2, 6-bis (di-tert-butylphosphinomethyl) pyridine, 2 '-bis (dicyclohexylphosphino) -1,1' -biphenyl, bis (2-dicyclohexylphosphinophenyl) ether, 5 '-bis (diphenylphosphino) -4,4' -bi-1, 3-benzodioxole, 2-tert-butylphosphinomethylpyridine, bis (diphenylphosphino) ferrocene, bis (diphenylphosphino) methane, bis (dicyclohexylphosphino) methane, bis (di-tert-butylphosphino) methane or TMEDA.

9. The catalyst system of claim 1, wherein the first ligand or the second ligand is selected from the group consisting of

10. The catalyst system of claim 1, wherein the transition metal precursor compound comprises a group 8 transition metal.

11. The catalyst system of claim 1, wherein the transition metal precursor compound comprises a group 9 transition metal.

12. The catalyst system of claim 1, wherein the transition metal precursor compound comprises a group 10 transition metal.

13. The catalyst system of claim 1, wherein the transition metal precursor compound comprises a group 11 transition metal.

14. The catalyst system of claim 1, wherein the associated metal cation is selected from group 1,2, 12, or 13 metal cations.

15. The catalyst system of claim 1, wherein the associated metal cation is a lithium, sodium, potassium, magnesium, calcium, zinc, or aluminum cation.

16. The catalyst system of claim 1, wherein:

the transition metal precursor compound comprises Ni;

the first ligand or the second ligand is independently selected from a diphosphine ligand, a diamine ligand, a diene ligand, a diether ligand or a disulfide ligand; and is

The associated metal cation is a lithium, sodium, potassium, magnesium, calcium, zinc or aluminum cation.

17. The catalyst system of claim 1, wherein the diluent comprises an ether diluent, a carbonyl-containing diluent, an aromatic diluent, a halogenated aromatic diluent, an alcohol diluent, or a combination thereof.

18. The catalyst system of claim 1, wherein the catalyst system further comprises:

(d) an olefin; and

(e) carbon dioxide (CO)₂)。

19. The catalyst system of claim 18, wherein the catalyst system comprises a metallolactone compound comprising (a) a group 8-11 transition metal and (b) at least one of the first ligands and, when present, at least one of the second ligands.

20. The catalyst system of claim 19, wherein the catalyst system comprises an adduct of the metallolactone compound and the anionic polyaromatic resin having an associated metal cation.

21. The catalyst system of claim 18, wherein the olefin comprises ethylene, propylene, butene, pentene, hexene, heptane, octene, or styrene.

22. The catalyst system of claim 18, wherein the catalyst system further comprises a metal-containing base selected from an alkali or alkaline earth metal oxide, hydroxide, alkoxide, phenoxide, amide, alkylamide, arylamide, or carbonate.

23. The catalyst system of claim 18, wherein the catalyst system further comprises a metal-containing base selected from Na₂CO₃、Cs₂CO₃、MgCO₃、NaOH、KOH、Mg(OH)₂、Ca(OH)₂、Al(OⁱPr)₃、Na(O^tBu) or Mg(OEt)₂。

24. A catalyst system for producing an α, β -unsaturated carboxylic acid or salt thereof, the catalyst system comprising:

(a) a group 8-10 transition metal and at least one first ligand independently selected from a diene ligand, an ether ligand, an organocarbonyl ligand, a thioether ligand, an amine ligand, a nitrile ligand, a phosphine ligand or a carbene ligand;

(b) at least one second ligand independently 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;

(c) an anionic polyaromatic resin having associated metal cations, the anionic polyaromatic resin having associated metal cations comprising a metallized phenol-formaldehyde resin, a metallized polyhydroxyarene-formaldehyde resin or a metallized polyhydroxyarene-and fluorophenol-formaldehyde resin;

(d) an olefin;

(e) carbon dioxide (CO)₂) (ii) a And

(f) a diluent.

25. The catalyst system of claim 24, wherein the catalyst system comprises a metallolactone compound comprising (a) a group 8-10 transition metal and (b) at least one of the first ligand or at least one of the second ligand.

26. The catalyst system of claim 24, 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.

27. The catalyst system of claim 24, wherein the group 8-10 transition metal precursor compound comprises a group 8 metal.

28. The catalyst system of claim 24, wherein the group 8-10 transition metal precursor compound comprises a group 9 metal.

29. The catalyst system of claim 24, wherein the group 8-10 transition metal precursor compound comprises a group 10 metal.

30. The catalyst system of claim 24, wherein the catalyst system further comprises a metal-containing base selected from an alkali or alkaline earth metal oxide, hydroxide, alkoxide, phenoxide, amide, alkylamide, arylamide, or carbonate.

31. A process for producing an α, β -unsaturated carboxylic acid or a salt thereof, the process comprising:

(a) contacting in any order:

(i) a transition metal precursor compound comprising a group 10 transition metal and at least one first ligand;

(ii) at least one second ligand; and

(iii) an anionic polyelectrolyte with an associated metal cation, wherein the anionic polyelectrolyte comprises alkoxide, phenoxide, acrylate, (meth) acrylate, sulfonate, alkyl thiolate, aryl thiolate, alkyl amide, or aryl amine groups;

(iv) an olefin;

(v) carbon dioxide (CO)₂) (ii) a And

(vi) a diluent to provide a reaction mixture; and

(b) reacting the reaction mixture with a metal-containing base to produce an α, β -unsaturated carboxylic acid or salt thereof.

32. The process of claim 31, wherein the metal-containing base is selected from alkali or alkaline earth metal oxides, hydroxides, alkoxides, phenoxides, amides, alkylamides, arylamides, or carbonates.

33. The method of claim 31 wherein the anionic polyelectrolyte with associated metal cation is selected from the group consisting of a metallized poly (vinyl phenolate) resin or poly (vinyl alkoxide) resin with associated metal cation, respectively.

34. The method of claim 31 wherein the anionic polyelectrolyte with associated metal cation comprises a polyphenolate resin with associated metal cation.

35. The method of claim 31, wherein:

a) the first ligand, the second ligand, or both the first ligand and the second ligand are bidentate ligands; or

b) The first ligand, the second ligand, or the first ligand and the second ligand independently comprise at least one of a nitrogen, phosphorus, sulfur, or oxygen coordinating atom.

36. The method of claim 31, wherein the first ligand, the second ligand, or the first ligand and the second ligand independently comprise a diphosphine ligand, a diamine ligand, a diene ligand, a diether ligand, or a disulfide ligand.

37. The method of claim 31, wherein the first ligand, the second ligand, or the first ligand and the second ligand independently comprise 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.

38. The method of claim 31, wherein the first ligand is a diene ligand and the second ligand is a diphosphine ligand.

39. The method of claim 31, wherein the contacting step is performed in the absence of a metal hydride.

Background

Most industrially synthesized compounds are prepared from a limited set of precursors, the ultimate source of which is mainly fossil fuels. As these reserves diminish, it would be beneficial to use renewable resources, such as carbon dioxide, which is a non-toxic, abundant and economical C₁And (4) synthesizing a unit. Coupling of carbon dioxide to other unsaturated molecules is not related to CO for the current pass₂The direct preparation of molecules by conventional methods has great promise.

When carbon dioxide is coupled with an olefin, it is envisaged that the acrylate and carboxylic acid are produced directly by this process. Currently, acrylic acid is produced by a two-step oxidation of propylene. Because of the greater availability of ethylene and carbon dioxide relative to propylene, renewable materials (CO) are used in the synthesis₂) And as an alternative to the two-step oxidation process currently being practiced, the production of acrylic acid directly from carbon dioxide and ethylene would represent a significant improvement.

Accordingly, there is a need for improved processes, including catalytic processes, for the production of acrylic acid and other α, β -unsaturated carboxylic acids.

Disclosure of Invention

This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify required or essential features of the claimed subject matter, nor is it intended that this summary be used to limit the scope of the claimed subject matter.

In one aspect, the present disclosure provides methods, including catalytic methods, for making α, β -unsaturated carboxylic acids or salts thereof using soluble or insoluble anionic polyelectrolyte systems. These processes present improvements to homogeneous processes that have poor yields and involve challenging separation/isolation steps when the anionic polyelectrolyte system is insoluble or the reaction system is heterogeneous. Thus, conventional methods often have difficulty isolating the desired α, β -unsaturated carboxylic acid (e.g., acrylic acid). In contrast, the methods disclosed herein utilize anionic polyelectrolytes having associated metal cations that generally provide a heterogeneous reaction mixture. When combined with a catalyst such as a nickel catalyst, ethylene and carbon dioxide can couple to form a metallolactone, and the anionic polyelectrolyte can subsequently destabilize the metallolactone, which eliminates the metallic acrylate salt. By developing the disclosed heterogeneous system, it now offers the distinct advantage of easy separation of the desired product from the catalytic system. In addition, anionic polyelectrolytes may result in unexpectedly high yields of the desired α, β -unsaturated carboxylic acid (e.g., acrylic acid).

According to one aspect, the method for producing an α, β -unsaturated carboxylic acid or a salt thereof may comprise:

(1) contact with

(a) A metallolactone comprising at least one ligand;

(b) a diluent; and

(c) an anionic polyelectrolyte with associated metal cations to provide a reaction mixture; and

(2) conditions suitable to initiate the metalolactone elimination reaction are applied to the reaction mixture to produce the α, β -unsaturated carboxylic acid or salt thereof.

In another aspect, there is provided another such process for forming an α, β -unsaturated carboxylic acid or salt thereof, which may include:

(1) contact with

(a) A metallolactone comprising at least one ligand;

(b) a diluent; and

(c) an anionic polyelectrolyte with associated metal cations to provide a reaction mixture comprising adducts of the metallolactone and the anionic polyelectrolyte and its associated metal cations; and

(2) conditions suitable to form the α, β -unsaturated carboxylic acid or salt thereof are applied to the reaction mixture.

According to an additional aspect of the present disclosure, there is provided a method for producing an α, β -unsaturated carboxylic acid or a salt thereof, wherein the method may comprise:

(1) in any order

(a) A transition metal precursor compound comprising 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 insoluble anionic polyelectrolyte with associated metal cations to provide a reaction mixture; and

(2) conditions suitable to form the α, β -unsaturated carboxylic acid or salt thereof are applied to the reaction mixture.

This summary and the following detailed description provide examples and merely explain the present invention. Accordingly, the foregoing summary and the following detailed description are not to be considered limiting. Other features or variations may be provided in addition to those set forth herein, such as, for example, various combinations and subcombinations of these described in the detailed description.

Drawings

FIG. 1 illustrates one embodiment or aspect of the present disclosure showing the use of an anionic polyelectrolyte stationary phase in a column configuration where ethylene and CO may be formed₂The acrylate coupling reaction of (a) to form a metal lactone (e.g., a nickel lactone) in the mobile phase, and the resulting nickel lactone is destabilized by the polyelectrolyte stationary phase to form an acrylate product.

Detailed Description

Definition of

In order to more clearly define the terms used herein, the following definitions are provided. The following definitions apply to the present disclosure unless otherwise indicated. If a term is used in the present disclosure but is not specifically defined herein, a definition from the IUPAC compilation of chemical terms, 2 nd edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or that any claim to which the definition applies is not explicit or enabled. To the extent that any definition or use provided by any document incorporated by reference conflicts with the definition or use provided herein, the definition or use provided herein follows.

While the compositions and methods are described in terms of "comprising" various components and steps, the compositions and methods can also "consist essentially of" or "consist of" the various components and steps, unless otherwise specified.

The terms "a", "an" and "the" are intended to include a plurality of alternatives, such as at least one. For example, the disclosure of "anionic polyelectrolytes," "diluents," "catalysts," and the like is intended to include mixtures or combinations of one, or more than one, anionic polyelectrolyte, diluent, catalyst, and the like, unless otherwise specified.

The term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of a particular group in a hydrocarbon, for example, a halogenated hydrocarbon indicates the presence of one or more halogen atoms in place of an intermediate number of hydrogen atoms in the hydrocarbon.

As used herein, the term "α, β -unsaturated carboxylic acid" and derivatives thereof refers to carboxylic acids having a carbon atom with a carbon-carbon double bond attached to a carbonyl carbon atom (a carbon atom with a double bonded oxygen atom). Optionally, the α, β -unsaturated carboxylic acid may contain other functional groups, heteroatoms, or combinations thereof.

The term "polyelectrolyte" is used herein to refer to a polymeric (macromolecular) substance comprising a multiply-charged polyion and an equal amount of a counterion. Thus, an "anionic polyelectrolyte" refers to a polyelectrolyte that contains a multiply-charged polyanion and an equal amount of cation. The charge on the polyion is typically on a heteroatom such as oxygen, nitrogen or sulfur, or on a group such as a sulfonate. The moiety of the polyelectrolyte with a charged moiety may be a pendant group distal from the polymer backbone or may be part of the polymer backbone itself. The term "polyelectrolyte" is used to refer to both soluble and insoluble materials, such as some poly (vinylphenol) -based materials and phenol-formaldehyde-based materials described herein. The multiply-charged polyanion may also be referred to as a base, and the associated metal ion is referred to simply as a counterion, metal ion or lewis acid, as appropriate.

While the terms "polyphenol" and "polyaromatic" are used herein to describe anionic polyelectrolytes in which the phenolate moiety carries a negative charge in the polyelectrolyte, and while these terms may be used interchangeably where the context permits, these terms are generally used herein to describe some different specific types of anionic polyelectrolyte polymers, as described herein.

[1] The terms "polyphenol" and "polyphenolate" are used generically herein to describe specific types of anionic polyelectrolyte polymers, for example, polymeric materials such as poly (4-vinylphenol) and metallized poly (4-vinylphenolate) which typically include pendant phenols, phenolates or substituted analogs thereof bonded to the polymer backbone. Thus, the oxygen of the phenolate group has a negative charge.

[2] The term "polyaromatic" is also used herein generally to describe certain types of anionic polyelectrolyte resins or polymers, such as phenol-formaldehyde crosslinked resins and the like, in which the phenol aromatic groups and methylene moieties are part of an extended crosslinked network. Thus, the aromatic groups in the "polyaromatic" structure are hydroxylated, hydroxy-metallated, or functionalized with groups that carry a negative charge in the anionic polyelectrolyte (e.g., thiolates, alkylamides). Crosslinked networks prepared using various phenol or polyhydroxyarene comonomers are also included in this definition. The term "phenolic resin" may also be used to describe these materials.

"polyhydroxy aromatic hydrocarbon" is used herein for phenolic monomers containing more than one hydroxyl group. Resorcinol (also known as benzenediol or m-dihydroxybenzene) is a typical polyhydroxyaromatic hydrocarbon.

For any particular compound or group disclosed herein, unless otherwise specified, any name or structure given is intended to encompass all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that may result from a particular set of substituents. Unless otherwise indicated, the names or structures also encompass all enantiomers, diastereomers, and other optical isomers (if any), whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as will be appreciated by those skilled in the art. For example, general references to pentane include n-pentane, 2-methyl-butane, and 2, 2-dimethylpropane; and general references to butyl include n-butyl, sec-butyl, isobutyl, and tert-butyl.

Various numerical ranges are disclosed herein. When applicants disclose or claim a range of any type, it is the intention of applicants to disclose or claim individually each possible value that such range can reasonably encompass, including the endpoints of such range, and any subranges and combinations of subranges subsumed therein, unless otherwise specified. Moreover, all numerical endpoints of the ranges disclosed herein are approximate. As a representative example, in one aspect of the present invention, applicants disclose that one or more steps in the methods disclosed herein can be performed at a temperature in the range of 10 ℃ to 75 ℃. This range should be construed to encompass temperatures in the range of "about" 10 ℃ to "about" 75 ℃.

Applicants reserve the right to exclude or exclude any individual member of any such group (including any subrange or combination of subranges within a group) that may be claimed either by range or in any similar manner, if for any reason applicants choose to claim less than all of the measures of the disclosure, for example to state a reference that applicants may not be aware at the time of filing the application. Further, applicants reserve the right to exclude or exclude any individual substituent, analog, compound, ligand, structure, or group thereof or any member of a claimed group if, for any reason, applicants choose to require less than all of the measures of the disclosure, for example to account for a reference that applicants may not be aware of at the time of filing the application.

When used to describe a group, for example when referring to a substituted analog of a particular group, the term "substituted" is intended to describe the compound or group in which any non-hydrogen moiety formally replaces a hydrogen in the group or compound, and is intended to be non-limiting. A compound or group may also be referred to herein as "unsubstituted" or by equivalent terms such as "unsubstituted," which refers to the original group or compound. "substituted" is intended to be non-limiting and includes inorganic substituents or organic substituents, as specified and understood by those of ordinary skill in the art.

Unless otherwise indicated, the terms "contacting a product," "contacting," and the like are used herein to describe compositions and methods, in which components are contacted for any length of time, in any order, in any manner. For example, the components may be contacted by blending or mixing. Further, unless otherwise specified, contact of any component may occur in the presence or absence of any other component of the compositions and methods described herein. Incorporation of additional materials or components may be carried out by any suitable method. Further, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. While the "contact product" may, and typically does, comprise the reaction product, the individual components need not react with one another. Similarly, "contacting" two or more components can result in a reaction product or reaction mixture. Thus, the "contact product" may be a mixture, a reaction mixture or a reaction product, as the case may be.

Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, typical methods and materials are described herein.

All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the structures and methodologies described in the publications, which might be used in connection with the presently described invention. The publications discussed herein are solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

The present disclosure generally relates to processes for forming α, β -unsaturated carboxylic acids or salts thereof. An illustrative example of a suitable α, β -unsaturated carboxylic acid is acrylic acid.

According to one aspect, the present disclosure provides the formation of α, β -unsaturated carboxylic acids and salts thereof from metallolactones and anionic polyelectrolytes. One example of the formation of an α, β -unsaturated carboxylate from an exemplary metallolactone and an anionic polyelectrolyte is illustrated in scheme 1, which provides an olefin and CO₂Nickel catalyzes the coupling reaction and the formation of acrylate. As explained herein, scheme 1 is not limiting but exemplary and each reactant, catalyst, polymer, and product is provided for illustration.

Scheme 1

In scheme 1, the transition metal catalysts disclosed herein are illustrated generally by nickel (O) catalysts at compound 1, and the olefins disclosed herein (typically α -olefins) are illustrated generally by ethylene. In the presence of catalyst 1, olefins are reacted with CO₂Coupling to form the metal lactone 2. The metallolactone 2 is destabilized by its interaction with the anionic polyelectrolyte, an example of which is shown in scheme 1 as metallic poly (4-vinylphenolate) 3. Without being bound by theory, the metallic poly (4-vinylphenolate salt) 3 is believed to interact with the metallolactone 2 in some way, for example to form some type of adduct, such as that shown as adduct 4. Reaction of the combined metallic poly (4-vinylphenolate) 3 and metallic lactone 2 (or some type of adduct, generally indicated as 4) with base 5 eliminates or releases the metallic acrylate 6 from the adduct 4 and regenerates the catalyst compound 1 and byproduct neutral polymer, here poly (4-vinylphenol), which upon reaction with base 5 is regenerated into an anionic polyelectrolyte reactant, such as metallic poly (4-vinylphenolate) 3. In other words, the metal acrylate is eliminated from 4 to regenerate catalyst compound 1 and the byproduct neutral polymer (here poly (4-vinylphenol)), which is in contact withThe alkali 5 is reacted to regenerate the anionic polyelectrolyte reactant 3. In the presence of additional ethylene and CO₂In the presence of this catalyst 1 is converted into a metallolactone 2.

One exemplary base shown in scheme 1 is a hydroxide base, but carbonate bases, similar inorganic bases, and various other bases, particularly metal-containing bases, can be used. The metal-containing base can include any basic inorganic metal compound or mixture of compounds containing a metal cation or cation source, for example, alkali metal and alkaline earth metal compounds, such as oxides, hydroxides, alkoxides, phenoxides, amides, alkylamides, arylamides, and carbonates (e.g., calcium hydroxide). In one aspect, the reaction of scheme 1 can be carried out using certain bases disclosed, but other organic bases can be excluded if desired, such as some alkoxide, phenoxide, amide, alkylamide, arylamide bases, and the like. Generally, inorganic bases (such as alkali metal hydroxides) have been found to work well.

Generally, the anionic polyelectrolytes and associated cations used in the methods disclosed herein may comprise (or consist essentially of or consist of) insoluble anionic polyelectrolytes, soluble anionic polyelectrolytes, or combinations thereof. That is, the anionic polyelectrolyte material may be soluble, insoluble, or only partially soluble or slightly soluble in the diluent or reaction mixture. It is further contemplated that mixtures or combinations of two or more anionic polyelectrolytes may be used in certain aspects of the present disclosure. Thus, an "anionic polyelectrolyte" is a polymeric material that contains a multiply-charged polyanion and an equal amount of counter cations and is commonly used to refer to both soluble and insoluble materials.

In one aspect, the anionic polyelectrolyte (and associated cation) can be used in the absence of alkoxide or phenoxide base. Further, the reactions and methods disclosed herein can be carried out in the absence of alkoxides, phenoxides, alkylamides, arylamides, and/or substituted analogs thereof. That is, no additional base with its associated counter ion is required to perform the methods disclosed herein.

According to one aspect, the anionic polyelectrolyte and associated cation used in the method can be used in the absence of a solid support. That is, the anionic polyelectrolyte may be used in its natural polymeric form without being bound or supported on any insoluble support, such as an inorganic oxide or mixed oxide material.

In one aspect, the term anionic polyelectrolyte is used to refer to and include polyelectrolytes comprising alkoxide, phenoxide, acrylate, (meth) acrylate, sulfonate, alkylthiolate, arylthiolate, alkylamide or arylamine groups and associated metal cations, such as any alkali metal cation, alkaline earth metal cation or metal cations having different lewis acidity. While aspects of the present disclosure are exemplified with anionic polyelectrolytes having a phenolate (or "phenolate") anionic group, these are considered examples of any anionic polyelectrolyte provided herein. Thus, terms such as poly (vinylphenoxide), poly (hydroxystyrene), and the like are generally used interchangeably unless context dictates otherwise.

Thus, the term anionic polyelectrolyte is generally used to include anionic polyelectrolytes such as poly (vinyl phenolate), poly (vinyl alkoxide), poly (acrylate), poly ((meth) acrylate), poly (styrene sulfonate), phenol-formaldehyde resins, polyhydroxyarene-formaldehyde resins (e.g., resorcinol-formaldehyde resins), polyhydroxyarene-and fluorophenol-formaldehyde resins (e.g., resorcinol-and 2-fluorophenol-formaldehyde resins), poly (vinyl aryl amides), poly (vinyl alkyl amides), or combinations thereof, as well as associated metal cations. Polymers which are generally crosslinked resins of the phenol-formaldehyde type may be referred to as polyaromatic resins. Copolymers of these specific types of anionic polyelectrolytes are also included in the present disclosure. The polyelectrolyte core structure may be substituted on the polymer backbone or on side groups that also contain typical oxygen, nitrogen, or sulfur heteroatoms, and variations of such substitutions are included in the present disclosure and use of the term anionic polyelectrolyte. For example, any anionic polyelectrolyte may be substituted with electron withdrawing or electron donating groups or even combinations thereof.

Anionic polyelectrolytes, such as those used herein, include associated cations, particularly associated metal cations, including lewis acidic metal cations and cations having low lewis acidity. According to one aspect, the associated metal cation may be an alkali metal, an alkaline earth metal, or any combination thereof. Typical associated metal cations may be, may comprise or may be selected from lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminium or zinc and the like. In general, sodium or potassium associated metal cations have been found to work well. Thus, cations having a range of lewis acidity in a particular solvent may be useful in accordance with the present disclosure.

One aspect of the disclosed methods provides for the use of an anionic polyelectrolyte comprising, consisting essentially of, or consisting of sodium (polyvinylphenol), including sodium (poly-4-vinylphenol). Other salts of poly-4-vinylphenolate salts, such as the potassium salt, are also useful.

In another aspect, useful anionic polyelectrolytes may include phenol-formaldehyde resins, which are crosslinked materials derived from the condensation reaction of phenol and formaldehyde, which are treated with a source of alkali or metal cations. Advantages of using a treated phenol-formaldehyde resin include its insolubility (which allows these materials to use a range of solvents), and its relatively high phenol concentration (which can be functionalized using a metal base such as an alkali metal hydroxide). An early version of thermosetting phenol-formaldehyde resins formed by the condensation reaction of phenol with formaldehyde was Bakelite^TMAnd the various phenol-formaldehyde resins used herein may be collectively referred to as "bakelite" resins. In the context of the present disclosure, the use of terms such as bakelite or generic terms such as phenol formaldehyde resin contemplates that these materials will be treated with a metal-containing base or metal cation source (e.g., sodium hydroxide) prior to their use in the disclosed methods.

In addition, other useful anionic polyelectrolytes include substituted phenol-formaldehyde resins which are also typically crosslinked to insoluble resins. These resins may be formed from the condensation reaction of a phenol, such as one or more of a polyhydroxyaromatic hydrocarbon of resorcinol (also known as benzenediol or m-dihydroxybenzene) and/or substituted analogs thereof, with formaldehyde. Thus, these materials include resins made using more than one phenol as a comonomer. Treatment with a base (e.g., NaOH or KOH) also provides a ready method of functionalizing polyaromatic polymers to achieve the reactivity described herein.

In one example, a resin can be prepared using a monomer combination of resorcinol (m-dihydroxybenzene) and fluorophenol monomers with formaldehyde and sodium treated to produce an anionic polyelectrolyte. While not intending to be bound by theory, it is believed that the m-dihydroxybenzene adds additional ion-chelating functionality to the resin. Subsequent treatment with a base (e.g., sodium hydroxide) can be used to produce the anionic polyelectrolyte.

Finally, this aspect is not limiting. Thus, other suitable anionic polyelectrolytes that may be used include many anionic polyelectrolytes that include carboxylic acid/carboxylate groups. Examples include, but are not limited to, polyacrylic acid, polymethacrylic acid, poly (D, L-glutamic acid), polyuronic acids (alginic acid, galacturonic acid, glucuronic acid, etc.), glycosaminoglycans (hyaluronic acid dermatan sulfate, chondroitin sulfate, heparin sulfate, and keratan sulfate), poly (D, L-aspartic acid), poly (styrene sulfonate), poly (phosphate), polynucleic acids, and the like.

In those aspects and embodiments in which a polymeric support variant is used and/or in which the polyelectrolyte itself is a solid that is insoluble in the diluent of the reaction, embodiments of such solid polyelectrolytes may have any suitable surface area, pore volume, and particle size, as will be appreciated by those skilled in the art. For example, the solid polyelectrolyte may have a pore volume in the range of 0.1 to 2.5mL/g, or alternatively 0.5 to 2.5 mL/g.

In another aspect, the solid polyelectrolyte can have a pore volume of 1 to 2.5 mL/g. Alternatively, the pore volume may be from 0.1 to 1.0 mL/g. Additionally or alternatively, the solid polyelectrolyte may have a thickness of 10 to 750m²(ii)/g; alternatively, 100 to 750m²(ii)/g; or alternatively, 100 to 500m²(iv)/g or alternatively 30 to 200m²BET surface area in g. In a further aspect of the present invention,the solid polyelectrolyte may have a thickness of 100 to 400m²(ii)/g, 200 to 450m²G or from 150 to 350m²Surface area in g. The average particle size of the solid polyelectrolyte may vary widely depending on the process characteristics, however, average particle sizes in the range of 5 to 500 μm, 10 to 250 μm, or 25 to 200 μm are generally used. Alternatively, particles or beads of 1/8 inches (3.2mm) to 1/4 inches (6.4mm) may also be used.

The present disclosure also provides for various modifications of the polymeric anionic stationary phase (anionic polyelectrolyte), for example, in a column or other suitable solid state configuration. Other various modifications of the polymeric anionic stationary phase (anionic polyelectrolyte), for example in a column or other suitable solid state configuration, may be used in the methods disclosed herein. For example, the acid-base reaction to produce an anionic polyelectrolyte from a neutral polymer can be accomplished using a wide range of metal bases including alkali metals and basic hydroxides, alkoxides, phenoxides, amides, alkyl or aryl amides, and the like, such that various electrophiles can be used for nickel lactone destabilization, as described herein for polyvinyl phenol.

Polymer modification may also include the use of a variant of poly (vinylphenol) which may be prepared by polymerizing protected hydroxy-substituted styrenes (e.g., acetoxystyrene) with a variety of organic and inorganic substituents (e.g., alkyl, halogen, and heteroatom substituents), usually followed by hydrolysis. Such adjustments may be provided as desired with respect to CO₂The particular olefin coupled, the reaction rate, the catalytic conversion, and additional reaction parameters and combinations of reaction parameters provide flexibility in adjusting the reaction.

In another aspect, polymer modification can also include the use of copolymers based on, for example, the copolymerization of protected hydroxy-substituted styrene with other monomers (e.g., styrene and/or (meth) acrylates) to make a library of polymeric electrophiles. Such libraries can be utilized to test and match specific anionic polyelectrolytes with specific olefins to improve or optimize reaction rates, catalytic conversions, reaction selectivities, and the like. Other polymer carrier variations may also be used, for example, the polymer may be loaded onto beads or other surfaces. Alternatively, one class of polymer support variants that can be used with this technology is cast polymers that can be used as ion exchange membranes. Alternatively, the anionic polyelectrolyte may be unsupported and used without any carrier.

The disclosed method may further include the step of reacting the adduct 4 of the metallolactone 2 and the anionic polyelectrolyte 3 with a base 5 (also referred to as a regenerated base). The regenerated base 5 may comprise a metal ion or a source of metal ions. In the example of scheme 1, the anionic polyelectrolyte can be a metallic poly (4-vinylphenolate salt) formed by the reaction of a neutral polymer, such as poly (4-vinylphenol), with a base, such as a metal-containing base. For example, the metal in the metal-containing base can be, but is not limited to, a group 1,2, 12, or 13 metal, such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, zinc, aluminum, or gallium. As shown in scheme 1, the reaction of a combination (or some type of adduct, generally indicated at 4) of a base 5 with an anionic polyelectrolyte 3 and a metallolactone 2 utilizing a metal base 5 eliminates or releases the metal acrylate 6 from 4 and regenerates the catalyst compound 1 and a byproduct neutral polymer (e.g., poly (4-vinylphenol) in scheme 1) which is regenerated as an anionic polyelectrolyte reactant after reaction with the regenerated base 5. Various bases 5 may be used in accordance with the present disclosure.

The step of regenerating the anionic polyelectrolyte may be accomplished by contacting the anionic polyelectrolyte with a regenerating base 5 comprising metal cations after the formation of the α, β -unsaturated carboxylic acid or salt thereof. Various bases 5 can be used for this regeneration step. For example, the regenerated base 5 can be or can comprise a metal-containing base that can include any reactive inorganic basic metal compound or mixture of compounds containing a metal cation or cation source, such as alkali metal and alkaline earth metal compounds, e.g., oxides, hydroxides, alkoxides, phenoxides, amides, alkylamides, arylamides, and carbonates. Suitable bases include or include, for example, carbonates (e.g., Na)₂CO₃、Cs₂CO₃、MgCO₃) Hydroxides (e.g., Mg (OH))₂、Ca(OH)₂NaOH, KOH), alkoxides (e.g., Al (O)ⁱPr)₃、Na(O^tBu)、Mg(OEt)₂) Phenolate (e.g., Na (OC)₆H₅) Sodium phenate), and the like. Typically, the regeneration step further comprises or is followed by a step of washing the anionic polyelectrolyte with a solvent or diluent.

According to one aspect, the regenerating base 5 may be or may comprise a nucleophilic base, such as a metal hydroxide or metal alkoxide. Although the regeneration base 5 may comprise a non-nucleophilic base, the methods disclosed herein are carried out in the absence of a non-nucleophilic base, such as alkali or alkaline earth metal hydrides, alkali or alkaline earth metal dialkylamides and diarylamides, alkali or alkaline earth metal hexaalkyldisilazanes, and alkali or alkaline earth metal dialkylphosphides and diarylphosphides.

Generally, inorganic bases (e.g., alkali metal hydroxides or alkali metal alkoxides) have been found to work best. However, in one aspect, the reaction of scheme 1 can be carried out using some bases but in the absence of certain other organic bases (e.g., alkoxides, phenoxides, amides, alkylamides, arylamides, etc.). In another aspect, the anionic polyelectrolytes (and associated cations) may be used and regenerated in the absence of alkoxides or phenoxides. Further, the reactions and methods disclosed herein can be carried out in the absence of alkoxides, phenoxides, alkylamides, arylamides, amines, hydrides, phosphazenes, and/or substituted analogs thereof. For example, the processes disclosed herein can be carried out in the absence of sodium hydride, phenolates (e.g., sodium phenolate), alkoxides (e.g., sodium tert-butoxide), and/or phosphazenes.

The processes disclosed herein are typically carried out in the presence of a diluent. Mixtures and combinations of diluents can be used in these methods. Unless otherwise specified, the diluent may comprise, consist essentially of, or consist of any suitable solvent or solvents disclosed herein. For example, the diluent may comprise, consist essentially of, or consist of an aprotic solvent, a protic solvent, a non-coordinating solvent, or a coordinating solvent. For example, according to one aspect of the present disclosure, the diluent may comprise an aprotic solvent. Representative and non-limiting examples of aprotic solventsExamples may include Tetrahydrofuran (THF), 2,5-Me₂THF, acetone, toluene, chlorobenzene, pyridine, carbon dioxide, olefins, and the like, and combinations thereof. According to another aspect, the diluent may comprise a weakly coordinating or non-coordinating solvent. Representative and non-limiting examples of weakly coordinating or non-coordinating solvents may include toluene, chlorobenzene, paraffins, halogenated paraffins, and the like, as well as combinations thereof.

According to yet another aspect, the diluent may comprise a carbonyl-containing solvent, such as a ketone, ester, amide, and the like, and combinations thereof. Representative and non-limiting examples of carbonyl-containing solvents can include acetone, ethyl methyl ketone, ethyl acetate, propyl acetate, butyl acetate, isobutyl isobutyrate, methyl lactate, ethyl lactate, N-dimethylformamide, and the like, and combinations thereof. In yet another aspect, the diluent may comprise THF, 2,5-Me₂THF, methanol, acetone, toluene, chlorobenzene, pyridine, anisole or combinations thereof; alternatively, 2,5-Me₂THF; alternatively, methanol; alternatively, acetone; alternatively, toluene; alternatively, chlorobenzene; or alternatively, pyridine.

In one aspect, the diluent may comprise (or consist essentially of) an aromatic hydrocarbon solvent. Non-limiting examples of suitable aromatic hydrocarbon solvents that may be used alone or in any combination include benzene, toluene, xylenes (including ortho-xylene, meta-xylene, para-xylene, or mixtures thereof), and ethylbenzene, or combinations thereof; alternatively, benzene; alternatively, toluene; alternatively, xylene; or alternatively, ethylbenzene.

In one aspect, the diluent may comprise (or consist essentially of or consist of) a halogenated aromatic hydrocarbon solvent. Non-limiting examples of suitable halogenated aromatic hydrocarbon solvents that may be used alone or in any combination include chlorobenzene, dichlorobenzene, and combinations thereof; alternatively, chlorobenzene; or alternatively, dichlorobenzene.

In one aspect, the diluent may comprise (or consist essentially of or consist of) an ether solvent. Non-limiting examples of suitable ethereal solvents that can be used alone or in any combination include dimethyl ether, diethyl ether, diisopropyl ether, di-n-propyl ether, di-n-butyl ether, diphenyl ether, methylethyl etherEthers, methyl tert-butyl ether, dihydrofuran, Tetrahydrofuran (THF), 2,5-Me₂THF, 1, 2-dimethoxyethane, 1, 4-dioxane, anisole and combinations thereof; alternatively, diethyl ether, dibutyl ether, THF, 2,5-Me₂THF, 1, 2-dimethoxyethane, 1, 4-dioxane, and combinations thereof; alternatively, THF; or alternatively, diethyl ether.

In another aspect, any of these above-described diluents can be excluded from the diluent or diluent mixture. For example, the diluent may be free of phenol or substituted phenol, alcohol or substituted alcohol, amine or substituted amine, water, ether, aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent, aldehyde or ketone, ester or amide, and/or free of halogenated aromatic hydrocarbon or any substituted analog of halogenated analogs of these diluents, including any of the above diluents. Accordingly, applicants reserve the right to exclude any diluents provided herein.

In all aspects and embodiments disclosed herein, the diluent may comprise or comprise carbon dioxide, an olefin, or a combination thereof. At least a portion of the diluent may comprise an α, β -unsaturated carboxylic acid or salt thereof formed in the process.

In the present disclosure, the terms transition metal precursor, transition metal compound, transition metal catalyst, transition metal precursor compound, carboxylation catalyst, transition metal precursor complex, and the like refer to a compound that is used as a metal lactone precursor before an olefin and carbon dioxide are coupled to the metal center of the transition metal precursor compound. Thus, the metal of the transition metal precursor compound and the metal of the metal lactone are the same. In some aspects, some of the ligand of the transition metal precursor compound is transferred and retained by the metal lactone after the coupling reaction. In other aspects, upon formation of the metal lactone, the transition metal precursor compound loses its existing ligand (referred to herein as the first ligand) in the presence of an additional ligand, such as a chelating ligand (referred to herein as the second ligand). Thus, while in some aspects, the metallolactone may comprise a first ligand incorporated in the transition metal precursor compound, the metallolactone is typically incorporated into a second (added) ligand.

According to one aspect, the transition metal catalyst or compound used in the process may be used without being immobilized on a solid support. That is, the transition metal catalyst may be used in its usual form, which is soluble in most useful solvents, without binding or being supported on any insoluble support, such as an inorganic oxide or mixed oxide material.

A prototype example of a transition metal precursor compound that loses its original ligand in the presence of a second (added) ligand in a coupling reaction, where a metal lactone is incorporated into the second (added) ligand, is the incorporation of Ni (COD)₂(COD is 1, 5-cyclooctadiene) with a diphosphine ligand (e.g. 1, 2-bis (dicyclohexylphosphino) ethane) in a diluent with ethylene and CO₂In the presence of a catalyst to form a nickel lactone having a coordinated 1, 2-bis (dicyclohexylphosphino) ethane bidentate ligand.

Thus, in one aspect, a process for producing an α, β -unsaturated carboxylic acid or a salt thereof can comprise:

(1) in any order

(a) A transition metal precursor compound comprising 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 anionic polyelectrolyte with associated metal cations to provide a reaction mixture; and

(2) conditions suitable to form the α, β -unsaturated carboxylic acid or salt thereof are applied to the reaction mixture.

Generally, the methods disclosed herein use metal lactone or transition metal precursor compounds or complexes. The transition metal of the metal lactone or transition metal precursor compound can be a group 3 to group 8 transition metal, or alternatively, a group 8 to group 11 transition metal. In one aspect, for example, the transition metal can be Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au, while in another aspect, the transition metal can be Fe, Ni, or Rh. Alternatively, the transition metal may be Fe; alternatively, the transition metal may be Co; alternatively, the transition metal may be Ni; alternatively, the transition metal may be Cu; alternatively, the transition metal may be Ru; alternatively, the transition metal may be Rh; alternatively, the transition metal may be Pd; alternatively, the transition metal may be Ag; alternatively, the transition metal may be Ir; alternatively, the transition metal may be Pt; or alternatively, the transition metal may be Au.

In particular aspects contemplated herein, the transition metal can be Ni. Thus, in these aspects, the metal lactone can be a nickel lactone and the transition metal precursor compound can be a Ni-ligand complex.

The ligand of the metalolactone and/or transition metal precursor compound may be any suitable neutral electron donor group and/or lewis base. For example, suitable neutral ligands may include sigma-donor solvents that contain a coordinating atom that can coordinate to a transition metal of a metal lactone (or transition metal precursor compound). Examples of suitable coordinating atoms in the ligand may include, but are not limited to O, N, S and P or combinations of these atoms. In some aspects according to the present disclosure, the ligand can be a bidentate ligand.

In one aspect, the ligand used to form the metal lactone and/or transition metal precursor compound can be an ether, an organic carbonyl, a thioether, an amine, a nitrile, or a phosphine. In another aspect, the ligand used to form the metal lactone or transition metal precursor compound can be an acyclic ether, cyclic ether, acyclic organocarbonyl, cyclic organocarbonyl, acyclic thioether, cyclic thioether, nitrile, acyclic amine, cyclic amine, acyclic phosphine, or cyclic phosphine.

Suitable ethers may include, but are not limited to, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, diphenyl ether, ditolyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 2, 5-dimethyltetrahydrofuran, 2, 3-dihydrofuran, 2, 5-dihydrofuran, furan, benzofuran, isobenzofuran, dibenzofuran, tetrahydropyran, 3, 4-dihydro-2H-pyran, 3, 6-dihydro-2H-pyran, 4H-pyran, 1, 3-dioxane, 1, 4-dioxane, morpholine and the like, including substituted derivatives thereof.

Suitable organic carbonyl groups may include ketones, aldehydes, esters, and amides, alone or in combination, and illustrative examples may include, but are not limited to, acetone, acetophenone, benzophenone, N-dimethylformamide, N-dimethylacetamide, methyl acetate, ethyl acetate, and the like, including substituted derivatives thereof.

Suitable sulfides may include, but are not limited to, dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dibutyl sulfide, methyl ethyl sulfide, methyl propyl sulfide, methyl butyl sulfide, diphenyl sulfide, xylyl sulfide, thiophene, benzothiophene, tetrahydrothiophene, thiacyclohexane, and the like, including substituted derivatives thereof.

Suitable nitriles may include, but are not limited to, acetonitrile, propionitrile, butyronitrile, benzonitrile, 4-methylbenzonitrile, and the like, including substituted derivatives thereof.

Suitable amines may include, but are not limited to, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, aniline, diphenylamine, triphenylamine, toluidine, methylbenzylamine, xylidine, pyridine, quinoline, pyrrole, indole, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 5-dimethylpyrrole, 2, 5-diethylpyrrole, 2, 5-dipropylpyrrole, 2, 5-dibutylpyrrole, 2, 4-dimethylpyrrole, 2, 4-diethylpyrrole, 2, 4-dipropylpyrrole, 2, 4-dibutylpyrrole, 3, 4-dimethylpyrrole, 3, 4-diethylpyrrole, 3, 4-dipropylpyrrole, 3, 4-dibutylpyrrole, 2-methylpyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2-butylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole, 3-ethyl-2, 4-dimethylpyrrole, 2,3,4, 5-tetramethylpyrrole, 2,3,4, 5-tetraethylpyrrole, 2' -bipyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, bis (2-pyridyl) dimethylsilane, N, N, N ', N ' -tetramethylethylenediamine, 1, 10-phenanthroline, 2, 9-dimethyl-1, 10-phenanthroline, glyoxal-bis (mesitylene) -1, 2-diimine, etc., including substituted derivatives thereof. Suitable amines may be primary, secondary or tertiary amines.

Suitable phosphines and other phosphorus compounds may include, but are not limited to, 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' -triisopropyl-1, 1 '-biphenyl, 2-di-t-butylphosphino-2' -methylbiphenyl, tri-ethylphosphino-1, 2-butyl-1, 6 '-isopropylphosphite, tri-butyl-1, 1' -biphenyl, and mixtures thereof, 2- (di-tert-butylphosphinomethyl) pyridine, 2-di-tert-butylphosphino-2 ',4',6' -triisopropyl-1, 1' -biphenyl, 2- (dicyclohexylphosphino) biphenyl, (S) - (+) - (3, 5-dioxa-4-phospha-cyclohepta [2,1 a; 3,4-a ' ] dinaphthylene-4-yl) dimethylamine, 2- (diphenylphosphino) -2' -methoxy-1, 1' -binaphthyl, 1,2,3,4, 5-pentaphenyl-1 ' - (di-tert-butylphosphino) ferrocene, 2' -bis (diphenylphosphino) -1,1' -Binaphthyl (BINAP), 1, 2-bis (dimethylphosphino) ethane, 2-bis (diphenylphosphino) naphthalene, 1' -binaphthyl, and mixtures thereof, 1, 2-bis (diethylphosphino) ethane, 1, 2-bis (dipropylphosphino) -ethane, 1, 2-bis (diisopropylphosphino) ethane, 1, 2-bis (dibutylphosphino) ethane, 1, 2-bis (di-t-butylphosphino) 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' -bis [ bis (3, 5-dimethylphenyl) phosphino ] -4,4',6,6' -tetramethoxybiphenyl, tetramethylbiphenyl, 1, 2-bis (diisopropylphosphino) ethane, 1, 2-bis (dibutylphosphino) ethane, 1, 2-bis (dibutylphosph, 2, 6-bis (di-t-butylphosphinomethyl) pyridine, 2 '-bis (dicyclohexylphosphino) -1,1' -biphenyl, bis (2-dicyclohexylphosphinophenyl) ether, 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, and the like, including substituted derivatives thereof.

In other aspects, the ligand used to form the metallolactone or transition metal precursor compound can be a carbene, such as an N-heterocyclic carbene (NHC) compound. Representative and non-limiting examples of suitable N-heterocyclic carbene (NHC) materials include the following:

illustrative and non-limiting examples of metal lactone complexes (representative nickel lactones) suitable for use as described herein include the following compounds (Cy ═ cyclohexyl, tBu ═ t-butyl):

transition metal precursor compounds corresponding to these illustrative metal lactones are shown below:

can be carried out according to the following general reaction scheme (illustrated with nickel as transition metal; Ni (COD))₂Bis (1, 5-cyclooctadiene) nickel (0)):

and the metal lactones are synthesized according to suitable procedures well known to those skilled in the art.

Suitable ligands, transition metal precursor compounds, and metal lactones are not limited to those ligands, transition metal precursor compounds, and metal lactones disclosed herein. Other suitable ligands, transition metal precursor compounds, and metallolactones are described, for example, in U.S. patent nos. 7,250,510, 8,642,803, and 8,697,909; journal of Organometallic Chemistry, 1983,251, C51-C53; journal of inorganic chemistry and general chemistry (Z.Anorg.Allg.chem.), 1989,577, 111-114; journal of Organometallic Chemistry (Journal of Organometallic Chemistry), 2004,689, 2952-2962; organometallic (Organometallics), 2004, vol 23, 5252-5259; chemical communication (chem. Commun.), 2006, 2510-2512; metals & organics (Organometallics), 2010, 29, 2199-; in the journal of european chemistry (chem. eur.j.), 2012,18, 14017-; organometallic, 2013,32(7), 2152-2159; and in journal of European chemistry (chem. Eur.J.), 2014, vol.20, 11, 3205-3211; the disclosure of which is incorporated herein by reference in its entirety.

In general, features of the methods disclosed herein (e.g., referring to, inter alia, the metallolactone, the diluent, the anionic polyelectrolyte, the α, β -unsaturated carboxylic acid or salt thereof, the transition metal precursor compound, the alkene, and the conditions under which the α, β -unsaturated carboxylic acid or salt thereof is formed) are described individually, and these features can be combined in any combination to further describe the disclosed methods.

In accordance with one aspect of the present disclosure, a process for conducting a metalolactone elimination reaction is disclosed, wherein the process forms an α, β -unsaturated carboxylic acid or salt thereof. The method may comprise (or consist essentially of or consist of):

(1) contact with

(a) A metallolactone comprising at least one ligand;

(b) a diluent; and

(c) an anionic polyelectrolyte with associated metal cations to provide a reaction mixture; and

(2) conditions suitable to initiate the metalolactone elimination reaction are applied to the reaction mixture to produce the α, β -unsaturated carboxylic acid or salt thereof.

Suitable metallolactones, diluents and anionic polyelectrolytes are disclosed above. In the process for conducting the metalolactone elimination reaction, for example, at least a portion of the diluent may comprise the α, β -unsaturated carboxylic acid or salt thereof formed in step (2) of the process.

In accordance with another aspect of the present disclosure, a method for producing an α, β -unsaturated carboxylic acid or a salt thereof is disclosed. The method may comprise (or consist essentially of or consist of):

(1) contact with

(a) A metallolactone comprising at least one ligand;

(b) a diluent; and

(c) an anionic polyelectrolyte having associated metal cations to provide a reaction mixture comprising an adduct of a metallolactone and an anionic polyelectrolyte and its associated metal cations; and

(2) conditions suitable to form the α, β -unsaturated carboxylic acid or salt thereof are applied to the reaction mixture.

In such a process for producing an α, β -unsaturated carboxylic acid or a salt thereof, for example, at least a portion of the diluent of the reaction mixture comprising the adduct of the metal lactone may be removed after step (1) and before step (2). Suitable metallolactones, diluents and anionic polyelectrolytes are disclosed above.

As further discussed in this disclosure, the above-described method may further comprise reacting a transition metal precursor compound comprising at least one first ligand, an olefin, and carbon dioxide (CO)₂) A step of contacting to form a metallolactone comprising at least one ligand. That is, at least one ligand of the transition metal precursor compound may be transferred to the metallolactone. In a further aspect, the above method may further comprise reacting a transition metal precursor compound comprising at least one first ligand with at least one second ligand, an olefin, and carbon dioxide (CO)₂) A step of contacting to form a metallolactone comprising at least one ligand. In this aspect, the ligand set of the metallolactone typically comprises at least one second ligand. That is, the metallolactone ligand can comprise at least one first ligand, at least one second ligand, or a combination thereof.

In some aspects, the contacting step of the above methods, step (1), can comprise contacting the metallolactone, the diluent, and the anionic polyelectrolyte, as well as additional non-recited materials, in any order. In other aspects, the contacting step can consist essentially of or consist of the metallolactone, the diluent, and the anionic polyelectrolyte component. Likewise, additional materials or features may be used to apply the conditional step, step (2), which forms or produces the α, β -unsaturated carboxylic acid or salt thereof. Furthermore, it is contemplated that the methods of preparing an α, β -unsaturated carboxylic acid or salt thereof by a metalolactone elimination reaction may employ more than one metalolactone and/or more than one anionic polyelectrolyte. Additionally, mixtures or combinations of two or more diluents may be used.

Any suitable reactor, vessel or container may be used to contact the metallolactone, diluent, and anionic polyelectrolyte, non-limiting examples of which may include flow reactors, continuous reactors, fixed bed reactors, moving reactor beds, and stirred tank reactors, including more than one reactor in series or parallel, and including any combination of reactor types and arrangements. In certain aspects according to the present disclosure, the metallolactone and diluent may be contacted with a fixed bed of anionic polyelectrolyte, for example, in a suitable vessel, such as in a continuous fixed bed reactor. In a further aspect, a combination of more than one anionic polyelectrolyte may be used, such as a mixed bed of a first anionic polyelectrolyte and a second anionic polyelectrolyte, or a continuous bed of a first anionic polyelectrolyte and a second anionic polyelectrolyte. In these and other aspects, the feed stream may flow upward or downward through the fixed bed. For example, the metallolactone and diluent can be contacted with a first anionic polyelectrolyte in a downward flow orientation and then contacted with a second anionic polyelectrolyte in an upward flow orientation, and vice versa. In various aspects, the metallolactone and the anionic polyelectrolyte can be contacted by, for example, mixing or stirring in a diluent in a suitable vessel (e.g., a stirred tank reactor).

Step (1) of the process for producing an α, β -unsaturated carboxylic acid or salt thereof also recites forming an adduct of a metallolactone and an anionic polyelectrolyte and its associated metal cation. Without being bound by theory, it is believed that there is some interaction between the metallolactone and the anionic polyelectrolyte and its associated metal cations to destabilize the metallolactone and thereby eliminate the metal acrylate. This interaction may be generally referred to as an adduct of the metallolactone and the anionic polyelectrolyte or an adduct of the α, β -unsaturated carboxylic acid and the anionic polyelectrolyte. The adduct may contain all or a portion of the α, β -unsaturated carboxylic acid, and may include salts of the α, β -unsaturated carboxylic acid.

Thus, the application of conditions suitable for the formation of the α, β -unsaturated carboxylic acid or salt thereof to the reaction mixture is intended to reflect any concomitant or subsequent conditions of step (1) of the above-described process that release the α, β -unsaturated carboxylic acid or salt thereof from the adduct, regardless of the specific nature of the adduct.

For example, in step (2) of the method wherein conditions suitable for forming an α, β -unsaturated carboxylic acid or salt thereof are applied to the reaction mixture, the adduct of a metallolactone and an anionic polyelectrolyte and its associated metal cation as defined herein is subjected to some chemical or other conditions or treatments to produce an α, β -unsaturated carboxylic acid or salt thereof. Various methods may be used to release the α, β -unsaturated carboxylic acid or salt thereof from the anionic polyelectrolyte. In one aspect, for example, the treating step can comprise contacting the adduct of the metallolactone and the anionic polyelectrolyte and its associated metal cation with an acid. Representative and non-limiting examples of suitable acids can include HCl, acetic acid, and the like, and combinations thereof. In another aspect, the treating step can include contacting the adduct of the metallolactone and the anionic polyelectrolyte and its associated metal cation with a base. Representative and non-limiting examples of suitable bases can include carbonates (e.g., Na)₂CO₃、CS₂CO₃、MgCO₃) Hydroxides (e.g. Mg (OH))₂Na (OH)), alkoxides (e.g. Al (O)ⁱPr)₃、Na(O^tBu)、Mg(OEt)₂) And the like and combinations thereof (ⁱPr is the isopropyl group,^tbu ═ tert-butyl, Et ═ ethyl). In yet another aspect, the treating step can include contacting the adduct of the metallolactone and the anionic polyelectrolyte and its associated metal cation with a suitable solvent. Representative and non-limiting examples of suitable solvents can include carbonyl-containing solvents such as ketones, esters, amides, and the like (e.g., acetone, ethyl acetate, N-dimethylformamide, and the like, as described above), alcohol solvents, water, and the like, and combinations thereof.

In yet another aspect, the treating step can include heating the adduct of the metallolactone and the anionic polyelectrolyte and its associated metal cation to any suitable temperature. The temperature may be in the range of, for example, 50 to 1000 ℃, 100 to 800 ℃, 150 to 600 ℃,250 to 1000 ℃,250 ℃ to 550 ℃, or 150 ℃ to 500 ℃. The duration of the heating step is not limited to any particular period of time, so long as the period of time is sufficient to release the α, β -unsaturated carboxylic acid from the anionic polyelectrolyte. As will be appreciated by those skilled in the art, the appropriate treatment step depends on several factors, among other considerations, such as the particular diluent used in the process, and the particular anionic polyelectrolyte used in the process. A further processing step may include, for example, a processing step that replaces the olefin-nickel combined acrylate with additional olefin.

In these methods for performing the metalolactone elimination reaction and producing the α, β -unsaturated carboxylic acid (or salt thereof), additional process steps may be performed before, during, and/or after any of the steps described herein. For example, the methods can further include the step of contacting a transition metal precursor compound with an olefin and carbon dioxide to form a metal lactone (e.g., prior to step (1)). The transition metal precursor compounds are described above. Illustrative and non-limiting examples of suitable olefins may include ethylene, propylene, butene (e.g., 1-butene), pentene, hexene (e.g., 1-hexene), heptane, octene (e.g., 1-octene), styrene, and the like, as well as combinations thereof.

However, according to another aspect of the present disclosure, a method for producing an α, β -unsaturated carboxylic acid or a salt thereof is disclosed. The method may comprise (or consist essentially of or consist of):

(1) in any order

(a) A transition metal precursor compound comprising 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 anionic polyelectrolyte with associated metal cations to provide a reaction mixture; and

(2) conditions suitable to form the α, β -unsaturated carboxylic acid or salt thereof are applied to the reaction mixture.

In aspects of the method utilizing a transition metal precursor compound comprising at least one first ligand, the olefin can be ethylene, and the transition metal precursor compound is reacted with the olefin and carbon dioxide (CO)₂) The step of contacting can be performed using any suitable ethylene pressure or any ethylene pressure disclosed herein, for example, from 10psig (70KPa) to 1,000psig (6,895KPa), from 25psig (172KPa) to 500psig (3,447KPa), or from 50psig (345KPa) to 300psig (2,068KPa), and the like. Further, the olefin may be ethylene, and the transition metal precursor compound is reacted with the olefin and carbon dioxide (CO)₂) The step of contacting can be performed using a constant olefin addition, a constant carbon dioxide addition, or a constant olefin and carbon dioxide addition to provide a reaction mixture. For example, ethylene and carbon dioxide (CO) are continuously added thereto₂) In the process of (1), the process may use 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, or about 1:1 of ethylene to CO₂Molar ratio to provide a reaction mixture.

According to another aspect of the above process using a transition metal precursor compound, the process may comprise using any suitable CO₂Pressure or any CO disclosed herein₂Pressure-operated reaction of transition metal precursor compounds with olefins and carbon dioxide (CO)₂) A contacting step, such as 20psig (138KPa) to 2,000psig (13,790KPa), 50psig (345KPa) to 750psig (5,171KPa), or 100psig (689KPa) to 300psig (2,068KPa), and the like. In any of the methods disclosed herein, the method can further comprise the step of monitoring the concentration of at least one reaction mixture component, at least one elimination reaction product, or a combination thereof, for any reason, such as adjusting a process parameter, determining a degree or reaction, or stopping a reaction at a desired point in time.

As shown, the method of utilizing a transition metal precursor compound comprising at least one first ligand includes one aspect in which a second ligand is not used in the contacting step and another aspect in which a second ligand is used in the contacting step. That is, one aspect relates to the contacting step of the method, which comprises contacting a transition metal precursor compound comprising at least one first ligand with at least one second ligand. The order of contacting may vary. For example, the contacting step of the above disclosed method may comprise contacting (a) a transition metal precursor compound comprising at least one first ligand with (b) at least one second ligand to form a precontacted mixture, followed by contacting the precontacted mixture with the remaining components (c) through (f) in any order to provide a reaction mixture.

Further embodiments relate to the order of contacting, for example, the contacting step can comprise or comprise contacting the metallolactone, the diluent, and the anionic polyelectrolyte in any order. The contacting step can also include contacting the metallolactone and a diluent to form a first mixture, followed by contacting the first mixture with an anionic polyelectrolyte to form a reaction mixture. In another aspect, the contacting step can include contacting a diluent and an anionic polyelectrolyte to form a first mixture, followed by contacting the first mixture with a metallolactone to form a reaction mixture. In yet another aspect, the contacting step of the method can further comprise contacting any number of additives, for example, the additives can be selected from acids, bases, or reducing agents.

Suitable transition metal ligands, olefins, diluents, anionic polyelectrolytes having associated metal cations are disclosed above. In some aspects, the contacting step of the method, step (1), can comprise contacting the transition metal ligand, the alkene, the diluent, the anionic polyelectrolyte, and carbon dioxide, and additional non-recited materials, in any order. In other aspects, the contacting step can consist essentially of, or consist of contacting, in any order, a transition metal ligand, an alkene, a diluent, an anionic polyelectrolyte, and carbon dioxide. Also, additional materials or features may be used in the forming step of step (2) of the method. Further, it is contemplated that such methods for producing an α, β -unsaturated carboxylic acid or salt thereof can employ more than one transition metal-ligand complex and/or more than one anionic polyelectrolyte (if desired) and/or more than one olefin. Additionally, mixtures or combinations of two or more diluents may be used.

As noted above, any suitable reactor, vessel, or container may be used to contact the transition metal ligand, olefin, diluent, anionic polyelectrolyte, and carbon dioxide, whether using a fixed bed of anionic polyelectrolyte, a stirred tank for contacting (or mixing), or some other reactor configuration and method. While not wishing to be bound by the following theory, the following provides a proposed illustrative reaction scheme for the process.

Separately, the contacting and forming steps of any of the methods disclosed herein (i.e., for performing a metalolactone elimination reaction, for producing an α, β -unsaturated carboxylic acid or salt thereof) can be performed at various temperatures, pressures, and time periods. For example, the temperature at which the components in step (1) are initially contacted may be the same as or different from the temperature at which the forming step (2) is conducted. As an illustrative example, in the contacting step, the components may be initially contacted at a temperature T1, and after this initial combining, the temperature may be increased to the temperature T2 for the forming step (e.g., to form an α, β -unsaturated carboxylic acid or salt thereof). Also, the pressure in the contacting step and the forming step may be different. In general, the time period in the contacting step may be referred to as a contact time, and the time period in the forming step may be referred to as a reaction time. The contact time and the reaction time may be, and usually are, different.

In one aspect, the contacting step and/or the forming step of the methods disclosed herein can be at 0 ℃ to 250 ℃; alternatively, from 20 ℃ to 200 ℃; alternatively, 0 ℃ to 95 ℃; alternatively, from 10 ℃ to 75 ℃; alternatively, from 10 ℃ to 50 ℃; or alternatively at a temperature in the range of from 15 ℃ to 70 ℃. In these and other aspects, after the initial contacting, the temperature may be changed to another temperature for the forming step, if desired. These temperature ranges are also meant to cover the case where the contacting step and/or the forming step may be performed at a series of different temperatures rather than at a single fixed temperature falling within the respective ranges.

In one aspect, the contacting step and/or the forming step of the methods disclosed herein can be conducted at a pressure in the range of 5(34KPa) to 10,000psig (68,948KPa), such as, for example, 5psig (34KPa) to 2500psig (17,237 KPa). In some aspects, the pressure can be in the range of 5psig (34KPa) to 500psig (3,447 KPa); alternatively, 25psig (172KPa) to 3000psig (20,684 KPa); alternatively, 45psig (310KPa) to 1000psig (6,895 KPa); or alternatively, from 50psig (345KPa) to 250psig (1,724 KPa).

The contacting step of these methods is not limited to any particular duration.

That is, the components may first be brought into contact quickly or over a longer period of time before the formation step is initiated. Thus, the contacting step may be performed, for example, over a period of time ranging as short as 1 to 30 seconds to as long as 1 to 12 hours or more. In a discontinuous or batch operation, the suitable reaction time for the forming step may depend, inter alia, on, for example, the reaction temperature, the reaction pressure, and the proportions of the individual components in the contacting step. In general, however, the forming step may be performed over a period of time in the range of 1 minute to 96 hours, such as, for example, 2 minutes to 96 hours, 5 minutes to 72 hours, 10 minutes to 72 hours, or 15 minutes to 48 hours.

If the process employed is a continuous process, the metallolactone/anionic electrolyte catalyst contact/reaction time (or transition metal ligand/anionic electrolyte catalyst contact/reaction time) can be expressed as a Weight Hourly Space Velocity (WHSV), i.e., the weight ratio (e.g., hr) of the metallolactone (or transition metal-ligand complex) contacted with a given weight of anionic electrolyte per unit time^-1). Although not limited thereto, the WHSV used based on the amount of anionic electrolyte may be in the range of 0.05 to 100hr^-10.05 to 50hr^-10.075 to 50hr^-10.1 to 25hr^-10.5 to 10hr^-11 to 25hr^-1Or 1 to 5hr^-1Within the range of (1).

In the process disclosed herein, the molar yield of the α, β -unsaturated carboxylic acid or salt thereof based on the metal lactone (or transition metal-ligand complex) is at least 2%, and more often may be at least 5%, at least 10%, or at least 15%. In particular aspects of the present disclosure, the molar yield may be at least 18%, at least 20%, at least 25%, at least 35%, at least 50%, at least 60%, at least 75%, or at least 85%, or at least 90%, or at least 95%, or at least 100%. That is, the catalyzed formation of an α, β -unsaturated carboxylic acid or salt thereof can be carried out using the disclosed system. For example, the molar yield of the α, β -unsaturated carboxylic acid or salt thereof based on the metal lactone or based on the transition metal precursor compound can be at least 20%, at least 40%, at least 60%, at least 80%, at least 100%, at least 120%, at least 140%, at least 160%, at least 180%, at least 200%, at least 250%, at least 300%, at least 350%, at least 400%, at least 450%, or at least 500%.

The particular α, β -unsaturated carboxylic acid (or salt thereof) that can be formed or produced using the methods of the present disclosure is not particularly limited. Illustrative and non-limiting examples of α, β -unsaturated carboxylic acids can include acrylic acid, methacrylic acid, 2-ethacrylic acid, cinnamic acid, and the like, as well as combinations thereof.

Illustrative and non-limiting examples of α, β -unsaturated carboxylic acid salts can include sodium acrylate, potassium acrylate, magnesium acrylate, sodium (meth) acrylate, and the like, and combinations thereof.

Once formed, the α, β -unsaturated carboxylic acid (or salt thereof) may be purified and/or isolated and/or separated using suitable techniques, which may include, but are not limited to, evaporation, distillation, chromatography, crystallization, extraction, washing, decantation, filtration, drying, and the like, including combinations of more than one of these techniques. In one aspect, the process for performing a metalolactone elimination reaction (or a process for producing an α, β -unsaturated carboxylic acid or salt thereof) may further comprise separating or isolating the α, β -unsaturated carboxylic acid (or salt thereof) from other components (e.g., diluent, anionic electrolyte, etc.).

Examples of the invention

The present invention is further illustrated by the following examples, which should not be construed as in any way limiting the scope of the invention. Various other aspects, embodiments, modifications, and equivalents thereof will occur to those of ordinary skill in the art upon reading the description herein without departing from the spirit of the invention or the scope of the appended claims.

General considerations

All manipulations were performed under purified nitrogen or under vacuum using standard Schlenk or glove box techniques unless otherwise indicated. Toluene (Honeywell) and tetrahydrofuran (Aldrich) were degassed and activated under nitrogenDrying on a molecular sieve. Sodium tert-butoxide, potassium tert-butoxide, poly (4-vinylphenol) (M)_w11,000g/mol), poly (4-vinylphenol-co- (methyl) acrylate) (M)_w8,000-12,000g/mol) and brominated poly (4-vinylphenol) (M)_wAbout 5,800g/mol) was purchased from Sigma-Aldrich and used as received. Phenol/formaldehyde resins were purchased as hollow beads (-5-127pm) from Polysciences. Bis (1, 5-cyclooctadiene) nickel (0) and 1, 2-bis (dicyclohexylphosphino) ethane were purchased from Strem and used as such. (TMEDA) Ni (CH)₂CH₂CO₂) According to literature procedures (Fischer, R; nestler, B., and Schutz, J.inorganic chemistry and general chemistry (H.Z. and. allg.chem.) 577(1989) 111-.

Preparation of the Compounds

Sodium poly (4-vinylphenol). In a 1L round bottom flask equipped with a stir bar, toluene (600mL) was added to sodium t-butoxide (15g, 125mmol) and poly (4-vinylphenol) (12g, 125 mmol). The mixture was stirred for four days, then filtered through a frit. The filter cake was washed with 30mL of toluene followed by 15mL of toluene and then dried. The dried cake was washed with 3X 20mL of toluene, leaving a solid.

Potassium poly (4-vinylphenol). Analogously to the preparation of sodium poly (4-vinylphenol), potassium tert-butoxide is used instead of sodium tert-butoxide.

Sodium poly (4-vinylphenol-co- (methyl (meth) acrylate). In analogy to the preparation of sodium poly (4-vinylphenol), poly (4-vinylphenol) was replaced by poly (4-vinylphenol-co- (methyl (meth) acrylate).

Sodium poly (4-vinylphenol) bromide. In analogy to the preparation of sodium poly (4-vinylphenol), brominated poly (4-vinylphenol) was used instead of poly (4-vinylphenol).

Sodium phenol/formaldehyde resin. The phenol-formaldehyde resin (phenol/formaldehyde resin) was suspended in a solution of sodium hydroxide in water or methanol and stirred overnight at 55 ℃, then filtered, and subsequently washed with a large amount of solvent, in which it was treated. The solid was then dried under vacuum before storage under nitrogen.

Examples 1 to 10

Experimental procedure for ethylene/carbon dioxide coupling

The ethylene/carbon dioxide reactions of these examples are listed in reaction (1) below, and the specific reagents, reaction conditions and yields are listed in table 1.

To a 1 liter autoclave pressure reactor was added a solvent followed by Ni (COD)₂(0.10mmol), bis (dicyclohexylphosphino) ethane (0.11mmol) and poly (4-vinylphenylphenolate) (1.00g) in 10mL of solvent. The reactor was set at 50 ℃, pressurized with ethylene at the desired level, and equilibrated for 5 to 10 minutes (min), then pressurized and equilibrated with carbon dioxide. The reactor was then set at 100 ℃ and stirred for 6 hours. After this reaction time, and after cooling to ambient temperature, the reactor was slowly emptied and the mixture collected. The solvent is removed in vacuo and the residue is stirred in 10 to 20mL deuterium oxide for 30 minutes, followed by addition of sorbic acid/acetone-d₆And (3) solution. The mixture was filtered and analyzed by NMR (sorbic acid was used as internal standard) to determine the acrylate yield.

TABLE 1 ethylene/carbon dioxide coupling and acrylate yields

^AIn this example 2.00g of poly (4-vinylphenylphenolate) were used.

Examples 11 to 17

Experimental procedure for the conversion of Nickel lactone to acrylate

To investigate the elimination step of the disclosed process, the efficiency of various alkoxides or phenoxides used to convert diphosphine stabilized nickel lactones to acrylic acid was evaluated. Specifically, the following experiment shows the efficiency of sodium and potassium (4-vinylphenol) for the conversion of diphosphine-stabilized nickel lactones prepared in situ, and compares the data with the conversion of similar nickel lactones to acrylates using the molecular sodium tert-butoxide. The reaction of these examples for the conversion of the metal lactone to the acrylate salt is given in the following reaction (2), and the specific reagents, reaction conditions and yields are shown in table 2. In reaction (2), "metal alkoxide" includes the polymeric alkoxides shown in table 2.

In a 10mL vial, (TMEDA) Ni (CH)₂CH₂CO₂) (0.018mmol), bis (dicyclohexylphosphino) ethane (0.018mmol), poly (4-vinylphenylphenolate) and solvent (5mL) were combined and stirred at 60 ℃ for 30 to 60 minutes. After removal of the solvent, the solid residue is dissolved in D₂O (3 to 5mL) for 30 min and filtered. Addition of aliquots of prepared sorbic acid/acetone-d₆The solution was used to determine the acrylic acid yield by NMR.

TABLE 2 Nickel lactone conversion to acrylate and acrylate yields

The study from table 2 reveals, among other things, that increasing the amount of sodium poly (4-vinylphenol) from 100mg to 250mg (examples 11 and 12) provides the same overall yield as sodium acrylate/acrylic acid. The use of the potassium salt (example 14) slightly reduced the sodium acrylate/acrylic acid yield compared to the sodium salt of poly (4-vinylphenolate) (example 11).

Thus, the present disclosure demonstrates at least the following: 1) an easy acid-base reaction which provides metallic polyvinylphenate or a variant thereof in good yield with negligible by-products; 2) nickel lactone destabilization and cracking, which can be performed in a surprisingly short time frame, i.e. shorter than expected (<1 hour); and 3) the increased loading of the metallic polyvinylphenolate does not reduce the acrylate/acrylic acid yield.

Example 18

Polymeric stationary phase for catalyzing formation of acrylate

The present disclosure also provides for the use of a polymeric stationary phase, such as a polyphenolic resin (e.g., poly (4-vinylphenylphenolate) resin) or a polyaromatic resin (e.g., phenol-formaldehyde resin), in a column or other suitable solid state configuration, wherein a metal lactone (e.g., nickel lactone) forms an acrylate in a mobile phase.

Figure 1 illustrates one way in which a polymeric stationary phase catalyst column can be configured in which a coupling reaction can be performed and the metal acrylate can be eluted from the column. As shown, metal (e.g., sodium) poly (4-vinylphenolate) resins were found to be suitable anionic polyelectrolyte promoters or "co-catalysts" in the olefin/carbon dioxide derived nickel lactone intermediate conversion. The process allows for easier separation of the acrylate salt from other materials and for easy regeneration of the polymeric support material into its salt form, such as sodium poly (4-vinylphenol).

Examples 19 to 21

Sodium treated crosslinked polyaromatic resins as stoichiometric cocatalysts in olefin/carbon dioxide conversion to alpha, beta-unsaturated carboxylic acid salts

Since metallic (e.g. sodium) poly (4-vinylphenolate) resins were found to be suitable promoters and cationic sources in the conversion of olefin and carbon dioxide derived nickel lactone intermediates, their crosslinked analogs were evaluated. These crosslinked polyaromatic resins are believed to be insoluble in many commercial diluents to act as polymer promoters and cationic sources in a fixed bed/column reactor setup. The process further allows for the potential regeneration of spent solid promoter in aqueous (e.g., aqueous sodium hydroxide) and/or organic media (e.g., toluene solution of sodium alkoxide).

Reaction (3) below illustrates the conversion reaction of an olefin and a carbon dioxide-derived nickel lactone intermediate for the evaluation of some crosslinked polyelectrolyte analogs. The reaction conditions of the reaction (3) are as follows: 0.10mmol [ Ni ]]0.11mmol of diphosphine ligand, 500mL of toluene, 1.0g of sodium-treated crosslinked polyaromatic resin (solid activator). The reactor was equilibrated to 150psi of ethylene, then to 300psi of carbon dioxide prior to heating. The yields reported in Table 3 are by D relative to the sorbic acid standard₂O/(CD₃)₂In a CO mixture¹H NMR spectroscopy.

The following table describes various examples in which a commercial polyaromatic resin (further treated with sodium base under appropriate conditions or in the commercial sodium form) was found to be effective in nickel-mediated synthesis of ethylene and carbon dioxide to sodium acrylate.

TABLE 3 Nickel-mediated conversion of carbon dioxide and ethylene to sodium acrylate Using sodium-treated polyaromatic^A

^AReaction conditions are as follows: 0.10mmol [ Ni ]]0.11mmol of diphosphine ligand, 500mL of toluene, 1.0g of solid activator (phenol-formaldehyde resin). The reactor was equilibrated to 150psi of ethylene, then to 300psi of carbon dioxide prior to heating. The yield was determined by D2O/(CD) relative to the sorbic acid standard₃)₂1H NMR spectroscopy in CO mixtures.

^BAnd is not detected.

Even though the yield of acrylate may be modest when using these sodium treated crosslinked resins, the data indicate that nickel-mediated conversion of carbon dioxide and ethylene to sodium acrylate can be performed using sodium treated crosslinked polyaromatic resins. Further, the insolubility of these resins in many commercial solvents would allow their use in fixed bed/column configurations.

The phenol/formaldehyde resin can be treated with sodium hydroxide to produce sodium phenolate sites believed to have activity promoting cleavage of nickel lactones, and more so when NaOH is dissolved in water to provide higher solubility relative to methanol (example 19) (example 20).

Example 21

CROSS-LINKED POLYAROMATIC RESIN CO-CATALYSTS IN OLEFIN/CARBON DIOXIDE CONVERSION TO ALPHA, BETA-UNSATURATED CARBOXYLATES USING CO-MONOMERS

In this example, a co-monomer phenol compound was used with formaldehyde to prepare a crosslinked polyaromatic resin for use according to the present disclosure. The resin is prepared using resorcinol (m-dihydroxybenzene) and 2-fluorophenol monomers in combination with formaldehyde comonomers, and the resulting resin is subjected to sodium treatment (NaOH, dissolved in water or alcohol) according to formula (4) to produce an anionic polyelectrolyte.

Polyaromatic resins are believed to act as a promoter when treated with sodium hydroxide, as are believed to be the sodium phenolate sites that promote nickel lactone cleavage. Notably, increased crosslink density can be achieved using longer drying times to remove excess water trapped.

Examples 22 to 25

Additional stationary phase for catalyzing acrylate formation

The present disclosure also provides for the use of other polymeric stationary phases and modifications thereof, for example in columns or other suitable solid state configurations. Further variations of this technique include, but are not limited to, the following examples.

Example 22 polymer modification including acid-base reactions is carried out using a wide range of metal bases including alkali metal and alkaline hydroxides, alkoxides, phenoxides, amides, alkyl or aryl amides, and the like, such that various electrophiles can be used for nickel lactone destabilization as demonstrated herein for polyvinylphenols.

Example 23 polymer modification may also include the use of a variant of polyvinylphenol, which may be prepared by polymerization of hydroxy-substituted styrenes with a variety of organic and inorganic substituents, such as alkyl, halogen, and heteroatom substituents.

Example 24 polymer modification may also include the use of copolymers based on, for example, copolymerization of protected hydroxyl-substituted styrene (e.g., acetoxystyrene) with other styrene and (meth) acrylate salts (typically followed by hydrolysis to produce polyvinyl phenol copolymers) to produce a library of polymeric electrophiles.

Example 25. variations of polymeric carriers are also contemplated, including, for example, polymers that can be loaded onto beads or other surfaces. One class of polymer support variations contemplated is cast polymers that can be used as ion exchange membranes.

The invention has been described above with reference to various aspects and embodiments and specific examples. Many variations will occur to those of skill in the art in view of the above detailed description. All such obvious variations are within the full intended scope of the appended claims. Other embodiments of the invention may include, but are not limited to, the following embodiments. Unless specifically stated otherwise, many embodiments are described as "comprising" certain components or steps, but alternatively may "consist essentially of" or "consist of" those components or steps.

Embodiment 1. a process for forming an α, β -unsaturated carboxylic acid or salt thereof, the process comprising:

(1) contact with

(a) A metallolactone comprising at least one ligand;

(b) a diluent; and

(c) an anionic polyelectrolyte with associated metal cations to provide a reaction mixture; and

(2) conditions suitable to initiate the metalolactone elimination reaction are applied to the reaction mixture to produce the α, β -unsaturated carboxylic acid or salt thereof.

Embodiment 2. a process for producing an α, β -unsaturated carboxylic acid or salt thereof, the process comprising:

(1) contact with

(a) A metallolactone comprising at least one ligand;

(b) a diluent; and

(c) an anionic polyelectrolyte with associated metal cations to provide a reaction mixture comprising an adduct of a metallolactone and the anionic polyelectrolyte and its associated metal cations; and

(2) conditions suitable to form the α, β -unsaturated carboxylic acid or salt thereof are applied to the reaction mixture.

Embodiment 3. a process for producing an α, β -unsaturated carboxylic acid or salt thereof, the process comprising:

(1) in any order

(a) A transition metal precursor compound comprising 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 anionic polyelectrolyte with associated metal cations to provide a reaction mixture; and

(2) conditions suitable to form the α, β -unsaturated carboxylic acid or salt thereof are applied to the reaction mixture.

Embodiment 4. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte is insoluble in a diluent or reaction mixture.

Embodiment 5. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte is soluble in a diluent or reaction mixture.

Embodiment 6. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte comprises alkoxide, phenoxide, acrylate, (meth) acrylate, sulfonate, alkyl thiolate, aryl thiolate, alkyl amide, or aryl amine groups.

Embodiment 7. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte comprises poly (vinyl phenolate), poly (vinyl alkoxide), poly (acrylate), poly ((meth) acrylate), poly (styrene sulfonate), phenol-formaldehyde resins, polyhydroxyarene-formaldehyde resins (e.g., resorcinol-formaldehyde resins), polyhydroxyarene-and fluorophenol-formaldehyde resins (e.g., resorcinol-and 2-fluorophenol-formaldehyde resins), poly (vinyl arylamides), poly (vinyl alkylamides), or combinations thereof.

Embodiment 8. the method of any one of embodiments 1 to 5, wherein the anionic polyelectrolyte comprises any suitable lewis acidic metal cation or any lewis acidic metal cation disclosed herein.

Embodiment 9. the method of any of embodiments 1 to 5, wherein the associated metal cation is an alkali metal, an alkaline earth metal, or a combination thereof.

Embodiment 10. the method of any of embodiments 1 to 5, wherein the associated metal cation is lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, or zinc.

Embodiment 11 the method of any one of embodiments 1 to 5, wherein the associated metal cation is sodium or potassium.

Embodiment 12. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte comprises poly (vinylphenoxide), poly (vinylalkoxide), substituted analogs thereof, or combinations thereof.

Embodiment 13. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte comprises sodium (poly-4-vinylphenol).

Example 14: the method of any one of embodiments 1 to 3, wherein the anionic polyelectrolyte comprises phenol-formaldehyde resins, polyhydroxyarene-formaldehyde resins (e.g., resorcinol-formaldehyde resins), polyhydroxyarene-and fluorophenol-formaldehyde resins (e.g., resorcinol-and 2-fluorophenol-formaldehyde resins), or combinations thereof.

Embodiment 15. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte comprises a phenol-formaldehyde resin, a resorcinol-and fluorophenol-formaldehyde resin, or a combination thereof.

Embodiment 16. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte comprises a phenol-formaldehyde resin or a resorcinol-and 2-fluorophenol-formaldehyde resin.

Embodiment 17. the method of any of embodiments 1 to 3, wherein the anionic polyelectrolyte comprises a phenol-formaldehyde resin.

Embodiment 18. the method of any one of embodiments 1 to 17, wherein the diluent comprises any suitable aprotic solvent or any aprotic solvent disclosed herein.

Embodiment 19. the method of any one of embodiments 1 to 17, wherein the diluent comprises any suitable weakly coordinating or non-coordinating solvent, or any weakly coordinating or non-coordinating solvent disclosed herein.

Embodiment 20. the method of any of embodiments 1 to 17, wherein the diluent comprises any suitable aromatic hydrocarbon solvent or any aromatic hydrocarbon solvent disclosed herein, e.g., benzene, xylene, toluene, and the like

Embodiment 21. the method of any one of embodiments 1 to 17, wherein the diluent comprises any suitable ether solvent or any ether solvent disclosed herein, e.g., THF, dimethyl ether, diethyl ether, dibutyl ether, and the like.

Embodiment 22. the method of any one of embodiments 1 to 17, wherein the diluent comprises any suitable carbonyl-containing solvent or any carbonyl-containing solvent disclosed herein, such as a ketone, ester, amide, and the like (e.g., acetone, ethyl acetate, N-dimethylformamide, and the like).

Embodiment 23. the method of any of embodiments 1 to 17, wherein the diluent comprises any suitable halogenated aromatic hydrocarbon solvent or any halogenated aromatic hydrocarbon solvent disclosed herein, e.g., chlorobenzene, dichlorobenzene, and the like.

Embodiment 24. the method of any one of embodiments 1 to 17, wherein the diluent comprises THF, 2,5-Me₂THF, methanol, acetone, toluene, chlorobenzene, pyridine, or combinations thereof.

Embodiment 25 the method of any of the preceding embodiments, wherein the diluent comprises carbon dioxide.

Embodiment 26. the method of any of the preceding embodiments, wherein at least a portion of the diluent comprises an α, β -unsaturated carboxylic acid or salt thereof formed in the method.

Embodiment 27. the method of any of embodiments 3 to 26, wherein the contacting step further comprises contacting an additive selected from an acid, a base, or a reducing agent.

Embodiment 28. the method of any of embodiments 3 to 26, wherein the contacting step comprises contacting a transition metal precursor compound comprising at least one first ligand with at least one second ligand.

Embodiment 29. the method of any one of embodiments 3 to 26, wherein the contacting step comprises contacting (a) a transition metal precursor compound comprising at least one first ligand with (b) at least one second ligand to form a precontacted mixture, followed by contacting the precontacted mixture with the remaining components (c) to (f) in any order to provide a reaction mixture.

Embodiment 30. the method of any of embodiments 1-2 and 4-26, wherein the contacting step comprises contacting the metallolactone, the diluent, and the anionic polyelectrolyte in any order.

Embodiment 31. the method of any of embodiments 1-2 and 4-26, wherein the contacting step comprises contacting a metallolactone and a diluent to form a first mixture, followed by contacting the first mixture with an anionic polyelectrolyte to form a reaction mixture.

Embodiment 32. the method of any of embodiments 1-2 and 4-26, wherein the contacting step comprises contacting a diluent and an anionic polyelectrolyte to form a first mixture, followed by contacting the first mixture with a metallolactone to form a reaction mixture.

Embodiment 33. the method of any one of embodiments 1 to 26, wherein the conditions suitable for forming the α, β -unsaturated carboxylic acid or salt thereof comprise contacting the reaction mixture with any suitable acid or any acid disclosed herein, e.g., HCl, acetic acid, and the like.

Embodiment 34. the method of any one of embodiments 1 to 26, wherein the conditions suitable for forming the α, β -unsaturated carboxylic acid or salt thereof comprise contacting the reaction mixture with any suitable solvent or any solvent disclosed herein, e.g., a carbonyl-containing solvent such as a ketone, ester, amide, etc. (e.g., acetone, ethyl acetate, N-dimethylformamide), alcohol, water, and the like.

Embodiment 35 the method of any one of the preceding embodiments, wherein the conditions suitable for forming the α, β -unsaturated carboxylic acid or salt thereof comprise heating the reaction mixture to any suitable temperature or temperature within any range disclosed herein, e.g., 50 to 1000 ℃, 100 to 800 ℃, 150 to 600 ℃,250 to 550 ℃, and the like.

Embodiment 36. the method of any of the preceding embodiments, wherein the molar yield of the α, β -unsaturated carboxylic acid or salt thereof based on the metal lactone (in those preceding embodiments comprising the metal lactone) or based on the transition metal precursor compound (in those preceding embodiments comprising the transition metal precursor compound) is within any range disclosed herein, e.g., at least 20%, at least 40%, at least 60%, at least 80%, at least 100%, at least 120%, at least 140%, at least 160%, at least 180%, at least 200%, at least 250%, at least 300%, at least 350%, at least 400%, at least 450%, or at least 500%, etc.

Embodiment 37. the method of any of the preceding embodiments, wherein the contacting step and/or the forming step is performed at any suitable pressure or at any pressure disclosed herein, e.g., 5psig (34KPa) to 10,000psig (68,948KPa), 45psig (310KPa) to 1000psig (6,895KPa), and the like.

Embodiment 38. the method of any one of the preceding embodiments, wherein the contacting step and/or the applying step is performed at any suitable temperature or at any temperature disclosed herein, e.g., 0 ℃ to 250 ℃,0 ℃ to 95 ℃, 15 ℃ to 70 ℃, etc.

Embodiment 39. the method of any of the preceding embodiments, wherein the contacting step is performed at any suitable Weight Hourly Space Velocity (WHSV) based on the amount of anionic polyelectrolyte or any WHSV disclosed herein, e.g., 0.05 to 50hr^-11 to 25hr^-1、1-5hr^-1And the like.

Embodiment 40 the method of any one of the preceding embodiments, wherein the method further comprises a step of isolating the α, β -unsaturated carboxylic acid or salt thereof, e.g., using any suitable separation/purification step or any separation/purification step disclosed herein, e.g., evaporation, distillation, chromatography, and the like.

Embodiment 41. the method of any one of embodiments 1 to 40, wherein the anionic polyelectrolyte of contacting step (1) comprises a fixed bed.

Embodiment 42. the method of any one of embodiments 1 to 40, wherein the anionic polyelectrolyte of contacting step (1) is supported on beads or used in the absence of a carrier.

Embodiment 43. the method of any one of embodiments 1 to 40, wherein the contacting step (1) is performed by mixing/stirring the anionic polyelectrolyte in a diluent.

Embodiment 44. the method of any of the preceding embodiments, wherein the α, β -unsaturated carboxylic acid or salt thereof comprises any suitable α, β -unsaturated carboxylic acid or any α, β -unsaturated carboxylic acid or salt thereof disclosed herein, e.g., acrylic acid, methacrylic acid, 2-ethacrylic acid, cinnamic acid, sodium acrylate, potassium acrylate, magnesium acrylate, sodium (meth) acrylate, and the like.

Embodiment 45. the method of any of embodiments 1-2 or 4-44, further comprising reacting a transition metal precursor compound comprising at least one first ligand, an olefin, and carbon dioxide (CO)₂) A step of contacting to form a metallolactone comprising at least one ligand.

Embodiment 46. the method of any of embodiments 1-2 or 4-44, further comprising reacting a transition metal precursor compound comprising at least one first ligand, at least one second ligand, an olefin, and carbon dioxide (CO)₂) A step of contacting to form a metallolactone comprising at least one ligand.

Embodiment 47 the method of embodiment 46, wherein the metallolactone ligand comprises at least one first ligand, at least one second ligand, or a combination thereof.

Embodiment 48 the method of embodiment 46, wherein the metallolactone ligand comprises at least one second ligand.

Embodiment 49 the method of any one of embodiments 3 or 45, wherein the olefin comprises any suitable olefin or any olefin disclosed herein, such as ethylene, propylene, butene (e.g., 1-butene), pentene, hexene (e.g., 1-hexene), heptane, octene (e.g., 1-octene), styrene, and the like.

Embodiment 50 the method of any one of embodiments 3 or 45 to 49, wherein the olefin is ethylene and the reacting the transition metal precursor compound with the olefin and carbon dioxide (CO) is performed using any suitable ethylene pressure or any ethylene pressure disclosed herein₂) A step of contacting, for example, from 10psig (69KPa) to 1,000psig (6895KPa), from 25psig (172KPa) to 500psig (3,447KPa), or from 50psig (345KPa) to 300psig (2,068KPa), and the like.

Embodiment 51. the method of any of embodiments 3 or 45 to 49, wherein the olefin is ethylene and the continuously adding olefin and carbon dioxide is performed to react the transition metal precursor compound with the olefin and carbon dioxide (CO)₂) The step of contacting to provide a reaction mixture.

Embodiment 52. the method of embodiment 51, wherein ethylene and carbon dioxide (CO)₂) With 3:1 to 1:3 of ethylene CO₂The molar ratio is continuously added to provide a reaction mixture.

Embodiment 53. the method of any of embodiments 3 or 45 to 49, wherein any suitable CO is used₂Pressure or any CO disclosed herein₂Pressure is carried out to react the transition metal precursor compound with the olefin and carbon dioxide (CO)₂) A contacting step, such as 20psig (138KPa) to 2,000psig (13,790KPa), 50psig (345KPa) to 750psig (5,171KPa), or 100psig (689KPa) to 300psig (2,068KPa), and the like.

Embodiment 54 the method of any of the preceding embodiments, further comprising the step of monitoring the concentration of at least one reaction mixture component, at least one elimination reaction product, or a combination thereof.

Embodiment 55. the method of any of embodiments 1 to 54, wherein the metal of the metal lactone or the metal of the transition metal precursor compound is a group 8 to 11 transition metal.

Embodiment 56. the method of any of embodiments 1 to 54, wherein the metal of the metal lactone or the metal of the transition metal precursor compound is Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au.

Embodiment 57 the method of any one of embodiments 1 to 54, wherein the metal of the metal lactone or the metal of the transition metal precursor compound is Ni, Fe, or Rh.

Embodiment 58. the method of any of embodiments 1 to 54, wherein the metal of the metal lactone or the metal of the transition metal precursor compound is Ni.

Embodiment 59. the method of any one of embodiments 1 to 2 or 4 to 44, wherein the metal lactone is a nickel lactone, e.g., any suitable nickel lactone or any nickel lactone disclosed herein.

Embodiment 60 the method of any one of embodiments 1 to 54, wherein any of the nickel lactone ligand, the first ligand, or the second ligand is any suitable neutral electron donor group and/or lewis base, or any neutral electron donor group and/or lewis base disclosed herein.

Embodiment 61 the method of any one of embodiments 1 to 54, wherein any of the metallolactone ligand, the first ligand, or the second ligand is a bidentate ligand.

Embodiment 62 the method of any one of embodiments 1 to 54, wherein any one of the metallolactone ligand, the first ligand, or the second ligand comprises at least one of nitrogen, phosphorus, sulfur, or an oxygen heteroatom.

Embodiment 63 the method of any one of embodiments 1 to 54, wherein any one of the metallolactone ligand, the first ligand, or the second ligand comprises or is selected from a diphosphine ligand, a diamine ligand, a diene ligand, a diether ligand, or a disulfide ligand.

Embodiment 64. the method of any of embodiments 1 to 63, further comprising the step of regenerating the anionic polyelectrolyte after forming the α, β -unsaturated carboxylic acid or salt thereof by contacting the anionic polyelectrolyte with a base comprising a metal cation.

Embodiment 65. the method of embodiment 64, further comprising the step of washing the anionic polyelectrolyte with a solvent or diluent.

Embodiment 66. the method of embodiment 64, wherein the base comprising a metal cation is any suitable base or any base disclosed herein, such as a carbonate (e.g., Na)₂CO₃、CS₂CO₃、MgCO₃) Hydroxides (e.g. Mg (OH))₂Na (OH)), alkoxides (e.g. Al (O)ⁱPr)₃、Na(O^tBu)、Mg(OEt)₂) And the like.

Embodiment 67. the method of embodiment 64, wherein the step of regenerating the anionic polyelectrolyte is performed in the absence of alkoxide, phenoxide, amide, alkylamide, arylamide, amine, hydride, phosphazene, and/or substituted analog thereof.

Embodiment 68. the method of embodiment 64, wherein the step of regenerating the anionic polyelectrolyte is performed in the absence of alkoxide, phenoxide, hydride, and/or phosphazene.

Embodiment 69. the method of embodiment 64, wherein the step of regenerating the anionic polyelectrolyte is carried out in the absence of phenolate or metal hydride.

Embodiment 70. the method of embodiment 64, wherein the step of regenerating the anionic polyelectrolyte is performed in the absence of a non-nucleophilic base.

Embodiment 71 the method of embodiment 64, wherein the anionic polyelectrolyte is not supported.

Embodiment 72 the method of any one of embodiments 1 to 3, wherein the metallolactone, metallolactone ligand, transition metal precursor compound, first ligand, second ligand, anionic polyelectrolyte, or metal cation is any suitable metallolactone, metallolactone ligand, transition metal precursor compound, first ligand, second ligand, anionic polyelectrolyte, or metal cation, or is any metallolactone, metallolactone ligand, transition metal precursor compound, first ligand, second ligand, anionic polyelectrolyte, or metal cation disclosed herein.

Embodiment 73. a method for forming an α, β -unsaturated carboxylic acid or salt thereof, the method comprising:

(1) contact with

(a) A metallolactone comprising a group 8 to 10 metal and at least one ligand;

(b) a diluent; and

(c) a polyaromatic resin having associated metal cations to provide a reaction mixture; and

(2) conditions suitable to initiate the metalolactone elimination reaction are applied to the reaction mixture to form the α, β -unsaturated carboxylic acid or salt thereof.

Embodiment 74. a method for producing an α, β -unsaturated carboxylic acid or salt thereof, the method comprising:

(1) in any order

(a) A group 8 to 11 transition metal precursor;

(b) an olefin;

(c) carbon dioxide (CO)₂)；

(d) A diluent; and

(e) a polyaromatic resin having associated metal cations to provide a reaction mixture; and

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

Embodiment 75. a process for producing an α, β -unsaturated carboxylic acid or salt thereof, the process comprising:

(1) in any order

(a) A group 8 to 11 transition metal catalyst;

(b) an olefin;

(c) carbon dioxide (CO)₂)；

(d) A diluent; and

(e) an anionic polyelectrolyte with associated metal cations to provide a reaction mixture; and

(2) contacting the reaction mixture with a metal-containing base selected from an alkali or alkaline earth metal oxide, hydroxide, alkoxide, phenoxide, amide, alkylamide, arylamide or carbonate to produce an α, β -unsaturated carboxylate;

wherein the contacting step is carried out in the absence of a non-nucleophilic base.