A CATALYST COMPOSITION FOR A PRODUCING PROCESS OF AN UNSATURATED CARBOXYLIC ACID SALT AND ITS DERIVATIVES FROM CARBON DIOXIDE AND OLEFIN

Abstract

This invention relates to a catalyst composition for a producing process of an unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin, wherein the catalyst composition in the present invention has been proved to be effective in catalyzing the carboxylation of carbon dioxide and olefin, wherein said catalyst composition comprises: a) a palladium metal complex as shown in structure (I);

##STR00001## wherein, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently represents a group selected from hydrogen atom, halogen atom, alkyl group, alkyl halide group, alkoxy group, amine group, optionally from alkenyl group, alkynyl group, phenyl group, benzyl group, or cylic hydrocarbon group comprising hetero atom; R.sup.5 represents group selected from alkyl group or phenyl group; b) a ligand selected from organophosphorus compound; c) a base selected from sodium tert-butoxide, sodium isopropoxide, sodium 2,6-dimethylphenolate, sodium 2,6-difluorophenolate, sodium 2-methylphenolate, or sodium 2-fluorophenol); and d) a reducing agent.

Claims

1. A catalyst composition for a producing process of an unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin, wherein said catalyst composition comprises: a) a palladium metal complex as shown in structure (I); ##STR00011## wherein, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently represents a group selected from hydrogen atom, halogen atom, alkyl group, alkyl halide group, alkoxy group, amine group, optionally from alkenyl group, alkynyl group, phenyl group, benzyl group, or cylic hydrocarbon group comprising hetero atom; R.sup.5 represents group selected from as alkyl group or phenyl group; b) a ligand selected from organophosphorus compound; c) a base selected from sodium tert-butoxide, sodium isopropoxide, sodium 2,6-dimethylphenolate, sodium 2,6-difluorophenolate, sodium 2-methylphenolate, or sodium 2-fluorophenolate); and d) a reducing agent.

2. The catalyst composition according to claim 1, wherein the palladium metal complex in a) comprising R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently selected from hydrogen atom, halogen atom, alkyl halide group, alkyl group having 1-4 carbon atoms, alkoxy group having 1-4 carbon atoms or secondary amine with general formula NR.sub.2.sup.6 wherein R.sup.6 represents alkyl group having 1-4 carbon atoms.

3. The catalyst composition according to claim 2, wherein the palladium metal complex in a) comprising R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently represents a group selected from hydrogen atom, chlorine atom, tert-butyl group, methoxy group, trifluoromethyl group, or diethylamine group.

4. The catalyst composition according to claim 1, wherein the palladium metal complex in a) comprising R.sup.5 represents alkyl group selected from ethylene, 1,2-phenylene, binaphthyl, or 1,2-cyclohexyl.

5. The catalyst composition according to claim 1, wherein the palladium metal complex in a) is selected from the palladium metal complex as shown in structure (II), (III), (IV), (V), (VI), or (VIII); ##STR00012##

6. The catalyst composition according to claim 1, wherein the organophosphorus compound in b) is selected from diphosphine group with a general formula PR.sup.7.sub.3CH.sub.2CH.sub.2PR.sup.7.sub.3, wherein R.sup.7 is selected from alkyl group, phenyl group, or cycloalkyl group.

7. The catalyst composition according to claim 6, wherein the organophosphorus compound in diphosphine group is selected from bis(dicyclohexylphosphino)ethane, (S,S,R,R)-TangPhos, (R,R)-()-2,3-bis(tert-butylmethylphosphino)quinoxaline, (1R,1R,2S, 2S)-DuanPhos, and ()-1,2-bis[2R,5R)-2,5-dimethylphospholano]benzene.

8. The catalyst composition according to claim 1, wherein the organophosphorus compound is bis(dicyclohexylphosphino)ethane.

9. The catalyst composition according to claim 1, wherein the base in c) is sodium tert-butoxide or sodium 2-fluorophenolate.

10. The catalyst composition according to claim 1, wherein the reducing agent in d) is selected from zinc, L-ascorbic acid, or sodium citrate.

11. The catalyst composition according to claim 1, wherein the reducing agent in d) is zinc.

12. The catalyst composition according to claim 1, wherein said catalyst further comprises an additive selected from phosphorus compound with a general formula PR.sub.3.sup.8 wherein R.sup.8 is selected from alkoxy group, cycloalkyl group, aryl group, or alkoxy aryl group.

13. The catalyst composition according to claim 12, wherein the additive is selected from triphenylphosphine, tricyclohexylphosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine,tris(2,6-dimethoxyphenyl)phosphine), tristearyl phosphite, triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tri-p-tolyl phosphite, or the mixture thereof.

14. The catalyst composition according to claim 13, wherein the additive is triphenylphosphine or tristearyl phosphite.

15. The catalyst composition according to claim 1, wherein the mole ratio of the catalyst composition comprising: a) 1 part of the palladium metal complex; b) from 0.5 to 2 parts of ligand; c) from 50 to 400 parts of base; and d) from 50 to 500 parts of reducing agent.

16. The catalyst composition according to claim 12, wherein said catalyst composition further comprises 0 to 8 parts of additive.

17. A producing process of an unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin, wherein said process comprises: a) adding of the catalyst composition according to claim 1 in the solvent into the reactor; and b) condensing olefin and carbon dioxide with the mixture obtained from step a) in the reactor, then rising the temperature from 100 to 180 C. and heated for 10-25 hours.

18. The process according to claim 17, wherein the mole ratio of olefin to carbon dioxide is from 1 to 2 to 1 to 4.

19. The process according to claim 17, wherein olefin is selected from ethylene, 1,3-butadiene, or 1-hexene.

20. The process according to claim 17, wherein the solvent in a) is selected from tetrahydrofuran, anisole, N-cyclohexyl-2-pyrrolidone, phenyl butyl ether, dibutyl glycol ether, dibutyl ether, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dibutylformamide, or the mixture thereof.

21. The process according to claim 20, wherein the solvent is tetrahydrofuran or N-cyclohexyl-2-pyrrolidone.

22. The process according to claim 17, wherein the temperature in step b) is from 130 to 150 C. and heated for 15-25 hours.

Description

DESCRIPTION OF THE INVENTION

[0027] The present invention relates to the catalyst composition for a producing process of the unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin, wherein the catalyst composition according to this invention is efficiently catalyze the production process of unsaturated carboxylic acid salt and its derivatives. Moreover, the catalyst composition according to the invention is easily synthesized from cheap precursors, stable to air and humid, wherein the catalyst composition according to the invention will be described according to the following description of the invention.

[0028] Any aspect showed herein is meant to include its application to other aspects of this invention unless stated otherwise.

[0029] Technical terms or scientific terms used herein have definitions as by an ordinary person skilled in the art unless stated otherwise.

[0030] Any tools, equipment, methods, or chemicals named here mean tools, equipment, methods, or chemicals being used commonly by an ordinary person skilled in the art unless stated otherwise that they are tools, equipment, methods, or chemicals specific only in this invention.

[0031] Use of singular noun or singular pronoun with comprising in claims or specification means one and including one or more, at least one, and one or more than one.

[0032] All compositions and/or methods disclosed and claims in this application aim to cover embodiments from any action, performance, modification, or adjustment without any experiment that significantly different from this invention, and obtain with the objection to utility and resulted as same as the present embodiment according to an ordinary person ordinary skilled in the art although without specifically stated in claims. Therefore, substitutable or similar object to the present embodiment, including any little modification or adjustment that clearly seen by an ordinary person skilled in the art should be construed as remains in spirit, scope, and concept of invention as appeared in appended claims.

[0033] Throughout this application, term about means any number that appeared or showed here that could be varied or deviated from any error of equipment, method, or personal using said equipment or method.

[0034] Hereafter, invention embodiments are shown without any purpose to limit any scope of the invention.

[0035] This invention relates to the catalyst composition for a producing process of the unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin, wherein the said catalyst composition comprises:

[0036] a) a palladium metal complex as shown in structure (I);

##STR00003##

[0037] wherein,

[0038] R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently represents a group selected from hydrogen atom, halogen atom, alkyl group, alkyl halide group, alkoxy group, amine group, optionally from alkenyl group, alkynyl group, phenyl group, benzyl group, or cylic hydrocarbon group comprising hetero atom;

[0039] R.sup.5 represents group selected from as alkyl group or phenyl group;

[0040] b) a ligand selected from organophosphorus compound;

[0041] c) a base selected from sodium tert-butoxide, sodium isopropoxide, sodium 2,6-dimethylphenolate, sodium 2,6-difluorophenolate, sodium 2-methylphenolate, or sodium 2-fluorophenolate); and

[0042] d) a reducing agent, selected from zinc, L-ascorbic acid, or sodium citrate.

[0043] In one embodiment, the palladium metal complex in a) comprises R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently represents group selected from hydrogen atom, halogen atom, alkyl halide group, alkyl group having 1-4 carbon atoms, alkoxy group having 1-4 carbon atoms, or secondary amine with a general formula NRZ wherein R.sup.6 represents alkyl group having 1-4 carbon atoms.

[0044] In one embodiment, the palladium metal complex in a) comprises R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently represents group selected from, but not limited to hydrogen atom, chlorine atom, tert-butyl group, methoxy group, trifluoromethyl group, or diethylamine group.

[0045] In one embodiment, the palladium metal complex in a) comprising R.sup.5 is selected from, but not limited to alkyl group or phenyl group, wherein R.sup.5 represents alkyl group selected from, but not limited to ethylene, 1,2-phenylene, binaphthyl, or 1,2-cyclohexyl.

[0046] In one embodiment, the palladium metal complex in a) is selected from the palladium metal complex as shown in structure (II), (III), (IV), (V), (VI), or (VIII);

##STR00004##

[0047] In one embodiment, the palladium metal precursor is selected from, but not limited to palladium chloride (PdCl.sub.2), palladium bromide (PdBr.sub.2), palladium trifluoroacetate (Pd(TFA).sub.2), or palladium acetate (Pd(OAc).sub.2), preferably palladium acetate.

[0048] In one embodiment, the organophosphorus compound in b) is selected from diphosphine group with a general formula PR.sup.7.sub.3CH.sub.2CH.sub.2PR.sup.7.sub.3, wherein R.sup.7 is selected from alkyl group, phenyl group, or cycloalkyl group.

[0049] In one embodiment, the organophosphorus compound in diphosphine group is selected from, but not limited to bis(dicyclohexylphosphino)ethane, (S, S,R,R)-TangPhos, (R,R)-()-2,3-bis(tert-butylmethylphosphino)quinoxaline, (1R,1R,2S,2S)-DuanPhos, and ()-1,2-bis [(2R,5R)-2,5-dimethylphospholano]benzene, preferably bis(dicyclohexylphosphino)ethane.

[0050] In one embodiment, the base in c) is selected from, but not limited to sodium tert-butoxide, sodium isopropoxide, sodium 2,6-dimethylphenolate, sodium 2,6-difluorophenolate, sodium 2-methylphenolate, or sodium 2-fluorophenolate, preferable is sodium tert-butoxide or sodium 2-fluorophenolate, most preferable is sodium tert-butoxide.

[0051] In one embodiment, the reducing agent in d) is selected from, but not limited to zinc, L-ascorbic acid, or sodium citrate, preferably zinc and sodium citrate, most preferably zinc.

[0052] In one embodiment, said catalyst further comprises additive selected from phosphorus compound with a general formula PR.sub.3.sup.8 wherein R.sup.8 is selected from alkoxy group, cycloalkyl group, aryl group, or alkoxy aryl group.

[0053] In one embodiment, the additive is selected from, but not limited to triphenylphosphine, tricyclohexylphosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine), tristearyl phosphite, triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tri-p-tolyl phosphite, or the mixture thereof, preferably triphenylphosphine or tristearyl phosphite.

[0054] In one embodiment, the mole ratio of the catalyst composition comprising:

[0055] a) 1 part of the palladium metal complex;

[0056] b) from 0.5 to 2 parts of ligand;

[0057] c) from 50 to 400 parts of base; and

[0058] d) from 50 to 500 parts of reducing agent.

[0059] In one embodiment, this invention relates to the producing process of the unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin comprises:

[0060] a) adding of the catalyst composition according to any one of claims 1 to 16 in the solvent into the reactor; and

[0061] b) condensing olefin and carbon dioxide with mixture obtained from step a) in the reactor;

[0062] then, rising the temperature from 100 to 180 C., and heated for 10-25 hours, wherein the mole ratio of olefin to carbon dioxide is from 1 to 2 to 1 to 4.

[0063] Preferably, the producing process of the unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin comprises:

[0064] a) adding of the catalyst composition according to any one of claims 1 to 16 in the solvent into the reactor; and

[0065] b) condensing olefin and carbon dioxide with mixture obtained from step a) in the reactor. Then, rising the temperature from 130 to 150 C. and heated for 50-25 hours, wherein the mole ratio of olefin to carbon dioxide is from 1 to 4.

[0066] In one embodiment, olefin is selected from, but not limited to ethylene, 1,3-butadiene, or 1-hexene.

[0067] In each step of the producing process of the unsaturated carboxylic acid salt and its derivatives according to the invention, unless being stated otherwise, the organic solvent may be selected from, but not limited to tetrahydrofuran, anisole, N-cyclohexyl-2-pyrrolidone, phenyl butyl ether, dibutyl glycol ether, dibutyl ether, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dibutylformamide, or the mixture thereof.

[0068] The producing process of the unsaturated carboxylic acid salt and its derivatives according to this invention further comprises the step of drying if needed. Said step is selected from, but not limited to stirring evaporation, vacuum drying, etc.

[0069] In one embodiment, the producing process of the unsaturated carboxylic acid salt and its derivatives according to this invention may be operated in the reactor, but not limited to fixed-bed reactor, batch reactor or continuous reactor.

[0070] The following examples are for demonstrating of the embodiments of this invention only, not for limitation of the scope of this invention in any way.

[0071] Synthesis of Palladium Complex Catalyst

[0072] Synthesis of Complex Compound (II)

##STR00005##

[0073] Palladium acetate (0.89 mmol) was dissolved in hot methanol solvent. Then, N,N-bis(salicylidene)ethylenediamine (0.89 mmol) in acetone solvent was added and stirred overnight. The obtained suspension was filtered and washed with acetone solvent. The dried yellow powder complex compound was obtained.

[0074] Synthesis of Complex Compound (III)

##STR00006##

[0075] Palladium acetate (0.89 mmol) was dissolved in hot methanol solvent. Then, (S,S)-(+)-N,N-bis(salicylidene)-1,2-cyclohexanediamine (0.89 mmol) in acetone solvent was added and stirred overnight. The obtained suspension was filtered and washed with acetone solvent. The dried green powder complex compound was obtained.

[0076] Synthesis of Complex Compound (IV)

##STR00007##

[0077] Palladium acetate (1.34 mmol) was dissolved in hot methanol solvent. Then, (S,S)-(+)-N,N-bis(5-methoxylsalicylidene)-1,2-cyclohexanediamine (1.34 mmol) in acetone solvent was added and stirred overnight. The obtained suspension was filtered and washed with acetone solvent. The dried green powder complex compound was obtained.

[0078] Synthesis of Complex Compound (V)

##STR00008##

[0079] Palladium acetate (1.34 mmol) was dissolved in hot methanol solvent. Then, (S,S)-(+)-N,N-bis(3,5-dichlorosalicylidene)-1,2-cyclohexanedi-amine (1.34 mmol) in acetone solvent was added and stirred overnight. The obtained suspension was filtered and washed with acetone solvent. The dried green powder complex compound was obtained.

[0080] Synthesis of Complex Compound (VI)

##STR00009##

[0081] Palladium acetate (1.34 mmol) was dissolved in hot methanol solvent. Then, (S,S)-(+)-N,N-bis(3-trifluoromethylsalicylidene)-1,2-cyclohexanediamine (1.34 mmol) in acetone solvent was added and stirred overnight. The obtained suspension was filtered and washed with acetone solvent. The dried green powder complex compound was obtained.

[0082] Synthesis of Complex Compound (VII)

##STR00010##

[0083] Palladium acetate (0.65 mmol) was dissolved in hot methanol solvent. Then, (S,S)-(+)-N,N-bis(4-diethylaminosalicylidene)-1,2-cyclohexanedi-amine (1.34 mmol) in acetone solvent was added and stirred overnight. The obtained suspension was filtered and washed with acetone solvent. The dried green powder complex compound was obtained.

[0084] Production of Unsaturated Carboxylic Acid Salt and its Derivatives from Reaction of Carbon Dioxide and Olefins

[0085] The complex compounds (II) to (VII) were tested for their catalytic performance in the production of unsaturated carboxylic acid salt and its derivatives for the reaction of carbon dioxide and olefins, wherein dichloro(1,5-cyclooctadiene)palladium(II) (COD)PdCl.sub.2) (Sigma Aldrich) is used as the reference catalyst (REF CAT).

[0086] The palladium complex compound (0.1 mmol), ligand (0.11 mmol), base (30 mmol), reducing agent (1-10 mmol), and solvent (30 mL) were added into reactor. Then, olefins (10 bars) and carbon dioxide (20-40 bars) were condensed into reactor. Then, reactor was heated at the temperature of 100-180 C. for 20-25 hours. Then, the temperature was reduced to the room temperature. The obtained mixture was subjected to removal of olefins and carbon dioxide under vacuum. The obtained mixture was used to identify product by NMR spectroscopy, wherein the turn over number (TON) was calculated by the following equation:

The turn over number(TON)=mole of obtained product/mole of catalyst

[0087] wherein sodium 3-(trimethylsilyl)-2,2,3,3-d4-propionate is used as the internal standard calculated from H.sub.2O suppression by NMR spectroscopy.

[0088] The following is the testing examples for properties of palladium catalysts produced according to this invention. The methods and instruments used for testing of properties are methods and instruments being used generally and not intended to limit the scope of the invention.

TABLE-US-00001 TABLE 1 Catalytic efficiency of 1,3-butadiene and carbon dioxide catalysts of the catalyst compositions according to this invention Catalyst compositions Phosphorous Reducing Catalyst compound Base agent Additive Solvent TON.sup.a (COD)PdCl.sub.2 dcpe Sodium Zinc Tetrahydrofuran 4 2-fluorophenolate (COD)PdCl.sub.2 dcpe Sodium Zinc Tetrahydrofuran 21 tert-butoxide III dcpe Sodium Zinc Tetrahydrofuran 2 2-fluorophenolate III dcpe Sodium Zinc Triphenylphosphine N-cyclohexyl- 32 tert-butoxide 2-pyrrolidone III dcpe Sodium Trisodium Triphenylphosphine N-cyclohexyl- 7 tert-butoxide citrate 2-pyrrolidone II dcpe Sodium Zinc Tetrahydrofuran 34 tert-butoxide III dcpe Sodium Zinc Tetrahydrofuran 35 tert-butoxide IV dcpe Sodium Zinc Tetrahydrofuran 29 tert-butoxide V dcpe Sodium Zinc Tetrahydrofuran 35 tert-butoxide VI dcpe Sodium Zinc Tetrahydrofuran 18 tert-butoxide VII dcpe Sodium Zinc Tetrahydrofuran 20 tert-butoxide .sup.aThe turn over number (TON) was recorded as (mole of product)/(mole of palladium catalyst), wherein sodium 3-(trimethylsilyl)-2,2,3,3-d4-propionate is used as the internal standard calculated from H.sub.2O suppression by NMR spectroscopy; (COD)PdCl.sub.2 was the reference catalyst (REF CAT); and dcpe represented bis(dicyclohexylphosphino)ethane).

TABLE-US-00002 TABLE 2 Catalytic efficiency of ethylene and carbon dioxide of the catalyst compositions according to this invention Catalyst compositions Phosphorous Reducing Catalyst compound Base agent Additive Solvent TON.sup.a III dcpe Sodium Zinc tris(2-methoxyphenyl) N-cyclohexyl- 16 tert-butoxide phosphine 2-pyrrolidone III dcpe Sodium Zinc tri-p-tolyl phosphite N-cyclohexyl- 14 tert-butoxide 2-pyrrolidone III dcpe Sodium Zinc tris(2,4-di-tert-butylphenyl) N-cyclohexyl- 11 tert-butoxide phosphite 2-pyrrolidone III dcpe Sodium Zinc Triphenylphosphine N-cyclohexyl- 24 tert-butoxide 2-pyrrolidone III dcpe Sodium Trisodium Triphenylphosphine N-cyclohexyl- 23 tert-butoxide citrate 2-pyrrolidone III dcpe Sodium L-ascorbic Triphenylphosphine N-cyclohexyl- 22 tert-butoxide acid 2-pyrrolidone III dcpe Sodium Trisodium tristearyl phosphite N-cyclohexyl- 29 tert-butoxide citrate 2-pyrrolidone III dcpe Sodium Trisodium tri-p-tolyl phosphite N-cyclohexyl- 16 tert-butoxide citrate 2-pyrrolidone II dcpe Sodium Zinc N-cyclohexyl- 14 2-fluorophenolate 2-pyrrolidone III dcpe Sodium Zinc N-cyclohexyl 16 2-fluorophenolate -2-pyrrolidone IV dcpe Sodium Zinc N-cyclohexyl- 20 2-fluorophenolate 2-pyrrolidone V dcpe Sodium Zinc N-cyclohexyl 21 2-fluorophenolate -2-pyrrolidone II dcpe Sodium Zinc Triphenylphosphine N-cyclohexyl- 21 2-fluorophenolate 2-pyrrolidone III dcpe Sodium Zinc Triphenylphosphine N-cyclohexyl- 19 2-fluorophenolate 2-pyrrolidone IV dcpe Sodium Zinc Triphenylphosphine N-cyclohexyl- 23 2-fluorophenolate 2-pyrrolidone V dcpe Sodium Zinc Triphenylphosphine N-cyclohexyl- 23 2-fluorophenolate 2-pyrrolidone .sup.aThe turn over number (TON) was recorded as (mole of product)/(mole of palladium catalyst), wherein sodium 3-(trimethylsilyl)-2,2,3,3-d4-propionate is used as the internal standard calculated from H.sub.2O suppression by NMR spectroscopy; (COD)PdCl.sub.2 was the reference catalyst (REF CAT); and dcpe represented bis(dicyclohexylphosphino)ethane).

[0089] Table 1 shows the catalytic efficiency of 1,3-butadiene and carbon dioxide of the catalyst compositions according to this invention. It was found that the palladium catalyst II, III, IV, or V had higher turn over number (TON) than the reference catalyst (REF CAT), which showed that the catalyst compositions according to the invention has high catalytic efficiency in the production process of unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefins.

[0090] Table 2 shows the catalytic efficiency of ethylene and carbon dioxide. Samples in the table aimed to show the application of the catalyst compositions according to the invention, but not intended to limit the scope of the invention by the sample being shown. From the table, the catalyst compositions according to the invention had high turn over number (TON) for catalyzing the production process of the unsaturated carboxylic acid salt and its derivatives from carbon dioxide and ethylene especially when additives were added into the catalyst compositions.

[0091] From all above results, it can be said that the catalyst compositions according to the invention has high efficiency in catalyzing the producing process of an unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin as aimed in the objective of the invention.

Preferred Embodiment of the Invention

[0092] Preferred embodiment of the invention is as provided in the description of the invention.