阅读说明：本技术 一种用于得自二氧化碳和烯烃的不饱和羧酸盐及其衍生物的生产方法的催化剂组合物 (Catalyst composition for use in a process for the production of unsaturated carboxylic acid salts and derivatives thereof from carbon dioxide and olefins ) 是由 彭皮莫·旺格玛哈斯里坤 苏奇温·乔奇卡塔万科 哈姆佩·福姆帕莱 梭蓬·凯奥提 于 2018-11-23 设计创作，主要内容包括：本发明涉及一种催化剂组合物,所述催化剂组合物用于得自二氧化碳和烯烃的不饱和羧酸盐及其衍生物的生产方法,其中已证明本发明的催化剂组合物有效地催化二氧化碳和烯烃的羧化,其中所述催化剂组合物包括：a)如结构式(I)所示的钯金属配合物；{式I}<Image he="292" wi="700" file="DDA0002525595540000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,R<Sup>1</Sup>、R<Sup>2</Sup>、R<Sup>3</Sup>和R<Sup>4</Sup>独立地代表选自氢原子、卤素原子、烷基、卤代烷基、烷氧基、胺基的基团,可选地,选自烯基、炔基、苯基、苄基或包含杂原子的环状烃基；R<Sup>5</Sup>代表选自烷基或苯基的基团；b)选自有机磷化合物的配体；c)选自叔丁醇钠、异丙醇钠、2,6-二甲基苯酚钠、2,6-二氟苯酚钠、2-甲基苯酚钠或2-氟苯酚钠的碱；和d)还原剂。(The present invention relates to a catalyst composition for use in a process for the production of unsaturated carboxylic acid salts derived from carbon dioxide and olefins and derivatives thereof, wherein the catalyst composition of the invention has proven effective in catalyzing the carboxylation of carbon dioxide and olefins, wherein the catalyst composition comprises: a) a palladium metal complex represented by the structural formula (I); { formula I } Wherein R is 1 、R 2 、R 3 And R 4 Independently represent a hydrogen atomA halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an amine group, optionally selected from an alkenyl group, an alkynyl group, a phenyl group, a benzyl group or a cyclic hydrocarbon group containing heteroatoms; r 5 Represents a group selected from alkyl or phenyl; b) a ligand selected from organophosphorus compounds; 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.)

1. A catalyst composition for use in a process for the production of unsaturated carboxylic acid salts derived from carbon dioxide and olefins and derivatives thereof, wherein the catalyst composition comprises:

a) a palladium metal complex represented by the structural formula (I);

wherein the content of the first and second substances,

R¹、R²、R³and R⁴Independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an amine group, optionally an alkenyl group, an alkynyl group, a phenyl group, a benzyl group or a cyclic hydrocarbon group containing a heteroatom;

R⁵represents a group selected from alkyl or phenyl;

b) a ligand selected from organophosphorus compounds;

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 of claim 1, wherein the palladium metal complex in a) comprises R¹、R²、R³And R⁴Independently selected from the group consisting of a hydrogen atom, a halogen atom, a haloalkyl group, an alkyl group having 1 to 4 carbon atoms, an alkane having 1 to 4 carbon atomsOxy or of the general formulaOf (a) wherein R is⁶Represents an alkyl group having 1 to 4 carbon atoms.

3. The catalyst composition of claim 1 or 2, wherein the palladium metal complex in a) comprises R¹、R²、R³And R⁴Independently represents a group selected from a hydrogen atom, a chlorine atom, a tert-butyl group, a methoxy group, a trifluoromethyl group or a diethylamino group.

4. The catalyst composition of any of claims 1-3, wherein the palladium metal complex in a) comprises R⁵Represents an alkyl group selected from ethylene, 1, 2-phenylene, binaphthyl or 1, 2-cyclohexyl.

5. The catalyst composition of any one of claims 1 to 4, wherein the palladium metal complex in a) is selected from palladium metal complexes represented by structural formula (II), (III), (IV), (V), (VI) or (VIII);

6. the catalyst composition of claim 1, wherein the organophosphorus compound in b) is selected from compounds having the general formula PR⁷ ₃CH₂CH₂PR⁷ ₃A diphosphine group of (a), wherein R⁷Selected from alkyl, phenyl or cycloalkyl.

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

8. The catalyst composition of any of claims 1, 6 or 7, wherein the organophosphorus compound is bis (dicyclohexylphosphine) ethane.

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

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

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

12. The catalyst composition of claim 1, wherein the catalyst further comprises an additive selected from the group consisting of those having the general formulaWherein R is⁸Selected from alkoxy, cycloalkyl, aryl or alkoxyaryl.

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

14. The catalyst composition of claim 12 or 13, wherein the additive is triphenylphosphine or trioctadecyl phosphite.

15. The catalyst composition of claim 1, wherein the molar ratio of the catalyst composition comprises:

a)1 part of a palladium metal complex;

b)0.5 to 2 parts of ligand;

c)50 to 400 parts of a base; and

d)50 to 500 parts of a reducing agent.

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

17. A process for the production of unsaturated carboxylic acid salts derived from carbon dioxide and an olefin and derivatives thereof, wherein the process comprises:

a) adding a catalyst composition according to any one of claims 1 to 16 in a solvent to a reactor; and

b) condensing olefins and carbon dioxide with the mixture obtained in step a) in a reactor, then raising the temperature to 100 ℃ to 180 ℃ and heating for 10-25 hours.

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

19. The process according to claim 17 or 18, wherein the olefin is selected from ethylene, 1, 3-butadiene or 1-hexene.

20. The process of claim 17, wherein the solvent in a) is selected from tetrahydrofuran, anisole, N-cyclohexyl-2-pyrrolidone, phenylbutyl ether, dibutyl glycol ether, dibutyl ether, N-dimethylacetamide, N-dimethylformamide, N-dibutylformamide, or mixtures thereof.

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

22. The method according to claim 17, wherein the temperature in step b) is 130 ℃ to 150 ℃ and is heated for 10-25 hours.

Technical Field

Chemistry relates to a catalyst composition for use in a process for the production of unsaturated carboxylic acid salts derived from carbon dioxide and olefins and derivatives thereof.

Background

Carbon dioxide gas is one of greenhouse gases, and is a major factor causing global warming, resulting in environmental problems that considerably affect humans. Atmospheric carbon dioxide is produced by natural and man-made means. According to the analysis result of the carbon dioxide information analysis center, about 91.7 million tons of carbon dioxide (in terms of carbon quantity) generated from petroleum energy and cement production was discharged into the atmosphere in 2010. 4.9% higher than 2009. Such a large amount of carbon dioxide has at least a 2-fold higher effect on global surface temperature than the sum of the other gases.

It is well known that carbon dioxide is an important natural resource because it can be used as a raw material in the production of fuels and chemicals. The used carbon dioxide is a renewable resource. However, the main problem faced with the use of carbon dioxide is its inertness to chemical reactions, and therefore a highly reactive substance or catalyst is required to convert the carbon dioxide to the desired product.

Carbon dioxide has been used as a precursor in the production of desirable chemicals, such as unsaturated carboxylates, particularly in the production of acrylates and derivatives thereof, which are further used as precursors for the synthesis of acrylate polymers. The acrylate polymers can be used in a wide variety of applications.

Typically, unsaturated carboxylates and their derivatives can result from the carboxylation of carbon dioxide and small olefins. The product obtained in the production process is low in price and can be produced in large quantities in petrochemical industry. Although carbon dioxide has long been an option for the preparation of sodium acrylate and its derivatives for the production of acrylate polymers, the use of olefins in this process has been in use for less than 10 years.

European Chemistry (Chemistry-A European Journal, 2012) discloses the synthesis of a bis (cyclooctadiene) nickel (Ni (COD))₂) And a strong base via a catalytic reaction of nickel lactone (nickelalactone) deprotonation, sodium acrylate is produced from carbon dioxide and ethylene, yielding a stable acrylate pi-complex (conversion number (TON) of 10.2).

WO2013098772 and US20130172616 disclose the synthesis of sodium acrylate by reaction of a transition metal-olefin complex with carbon dioxide and then with a base and an olefin, wherein the catalyst composition comprises bis (cyclooctadiene) nickel, (ni (cod)₂) A reducing agent, a phosphorus-based ligand and a carbene (carbene), a base and a solvent. The TON obtained was 10.

European chemistry (2014) and patent document WO2015173276 disclose the use of bis (cyclooctadiene) nickel in the synthesis of unsaturated carboxylic acid salts from ethylene or butadiene by varying the precursors. The results show that the base and the solvent play an important role in the production of the yield. Sodium 2-fluorophenol is the most preferred base (TON less than 116), but (R, R) - (+) -1,2-bis (di-t-butylmethylphosphino) benzene must be used as the ligand for this reaction.

Chemical Communications 2015 discloses the use of (1, 5-cyclooctadiene) palladium (II) dichloride ((COD) PdCl) in the synthesis of sodium acrylate and its derivatives (TON below 29)₂) As catalyst, Pd was catalytically cycled in bis (dicyclohexylphosphine) ethane using Zn (0) as reducing agent(II) reaction of carbon dioxide converted to Pd (0) with an olefin.

European Journal of Organic Chemistry 2015 and WO2015173277 disclose catalyst compositions based on tetrakis (triphenylphosphine) palladium (0) (tetrachlorokis (triphenylphosphine) palladium (0)) and bis (dicyclohexylphosphine) ethane. The results show that the catalytic system produces sodium acrylate at a TON of 106.

Catalytic chemistry (ChemCatChem, 2017) discloses the synthesis of sodium acrylate in high boiling solvents such as N-cyclohexylpyrrolidone while increasing the pressure of carbon dioxide. The results show that the efficiency of sodium acrylate production increases with TON of 514.

WO2015173295 discloses the synthesis of sodium acrylate using co-components (co-components) of ethylene and carbon dioxide at different temperatures, times and pressures using transition metal complexes immobilized on solid supports such as silica or cross-linked polystyrene including bases and solvents.

WO2015173296 discloses the use of a base and bis (cyclooctadiene) nickel (Ni (COD))₂) Bis (dicyclohexylphosphine) ethane, a base and a solvent. The results showed a TON of 1.1.

WO2015173307A1 discloses the use of ethylene and carbon dioxide as co-components, at different temperatures, times and pressures, of a tertiary amine and phosphazene as bases and of bis (cyclooctadiene) nickel (Ni (COD)₂) Bis (dicyclohexylphosphine) ethane and Tetrahydrofuran (THF) were used as solvents to synthesize sodium acrylate. The results showed a TON of 18.8.

US20160229782 discloses the synthesis of acrylic acid and its derivatives by scavenging acrylates from nickel lactones (nickelactones) at different temperatures, times and pressures using treated solid oxides as co-components. The results showed a TON of 1.81.

However, the presently disclosed methods for the synthesis of olefins from carbon dioxideThe catalysts used in the production of unsaturated carboxylic acid salts and their derivatives are limited to palladium complexes and ligands in the group of cyclooctadienyl or triphenylphosphino. These materials have not been improved in their structure to increase their catalytic ability. In addition, palladium compounds and triphenylphosphine ligands are very expensive and air-sensitive and require storage of (bis (cyclooctadiene) nickel (ni) (cod) under cryogenic conditions₂) 2-8 ℃; and tetrakis (triphenylphosphine) palladium (0) (Pd (PPh)₃)₄) -20 ℃), which results in limited use under normal conditions. Furthermore, compounds such as (1, 5-cyclooctadiene) palladium (II) dichloride ((COD) PdCl)₂) And tetrakis (triphenylphosphine) palladium (Pd (PPh)₃)₄) The palladium compounds and ligands in the triphenylphosphine or cyclooctadiene ligand groups of (a) are very expensive, resulting in limitations for large scale applications on an industrial scale.

In view of the foregoing, the present invention is directed to a catalyst composition for use in the production of unsaturated carboxylic acid salts and derivatives thereof, which is stable in operation under conventional conditions (normal conditions), low in air sensitivity, inexpensive, and efficient.

Disclosure of Invention

The present invention relates to a catalyst composition for use in a process for the production of unsaturated carboxylic acid salts derived from carbon dioxide and olefins and derivatives thereof, wherein the catalyst composition is effective in catalyzing carboxylation, wherein the catalyst composition comprises:

a) a palladium metal complex (palladium metal complex) shown as a structural formula (I);

wherein the content of the first and second substances,

R¹、R²、R³and R⁴Independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an amine group, optionally an alkenyl group, an alkynyl group, a phenyl group, a benzyl group or a cyclic hydrocarbon group containing a heteroatom;

R⁵represents a group selected from alkyl or phenyl;

b) a ligand selected from organophosphorus compounds;

c) a base selected from sodium tert-butoxide, sodium isopropoxide, sodium 2,6-dimethylphenolate (sodium 2,6-dimethylphenolate), sodium 2, 6-difluorophenoxide (sodium 2,6-difluorophenolate), sodium 2-methylphenolate (sodium 2-methylphenolate) or sodium 2-fluorophenol (sodium 2-fluorophenol); and

d) a reducing agent.

Detailed Description

The present invention relates to a catalyst composition for use in a process for the production of unsaturated carboxylic acid salts and derivatives thereof derived from carbon dioxide and olefins, wherein the catalyst composition according to the present invention is effective in catalyzing the production process of unsaturated carboxylic acid salts and derivatives thereof. Furthermore, the catalyst composition according to the present invention, which is easily synthesized from inexpensive precursors and is stable to air and humidity, will be described according to the following description of the present invention.

Unless otherwise indicated, any aspect shown in this document is intended to include its use in other aspects of the invention.

Unless otherwise defined, technical or scientific terms used herein have the definitions understood by one of ordinary skill in the art.

Any reference herein to a tool, apparatus, method, or chemical means that a person skilled in the art would normally operate or use unless otherwise stated to be a tool, apparatus, method, or chemical specifically for use with the present invention.

The use of a singular noun or singular referent in the claims or the specification with the singular "comprising" means "a" and "one or more", "at least one" and "one or more".

All compositions and/or methods disclosed and claimed herein are intended to encompass embodiments from any act, property, modification or adjustment, without undue experimentation in light of the present disclosure, to achieve the same results as the present embodiments, even if not specifically recited in the claims. Therefore, alternatives or similar objects to the present embodiments, including minor modifications or adaptations apparent to those skilled in the art, will be construed as being within the spirit, scope and concept of the present invention as set forth in the appended claims.

Throughout this application, the term "about" means that any numerical value appearing or displayed herein may vary or deviate. Such variations or deviations may result from any errors in the apparatus, method, or individual using the apparatus or method.

The embodiments of the invention shown below do not limit the scope of the invention in any way.

The present invention relates to a catalyst composition for use in a process for the production of unsaturated carboxylic acid salts derived from carbon dioxide and olefins and derivatives thereof, wherein the catalyst composition comprises:

a) a palladium metal complex represented by the structural formula (I);

wherein the content of the first and second substances,

R¹、R²、R³and R⁴Independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an amine group, optionally an alkenyl group, an alkynyl group, a phenyl group, a benzyl group or a cyclic hydrocarbon group containing a heteroatom;

R⁵represents a group selected from alkyl or phenyl;

b) a ligand selected from organophosphorus compounds;

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 selected from zinc, L-ascorbic acid or sodium citrate.

In one embodiment, the palladium metal complex in a) includes R¹、R²、R³And R⁴Independently represent a group selected from a hydrogen atom, a halogen atom, a haloalkyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a group of the formulaOf a secondary amine of (a), wherein R⁶Represents an alkyl group having 1 to 4 carbon atoms.

In one embodiment, the palladium metal complex in a) includes R¹、R²、R³And R⁴Independently represents a group selected from, but not limited to, a hydrogen atom, a chlorine atom, a tert-butyl group, a methoxy group, a trifluoromethyl group or a diethylamino group.

In one embodiment, the palladium metal complex in a) includes R⁵Selected from, but not limited to, alkyl or phenyl, wherein R⁵Represents an alkyl group selected from, but not limited to, ethylene, 1, 2-phenylene, binaphthyl, or 1, 2-cyclohexyl.

In one embodiment, the palladium metal complex in a) is selected from palladium metal complexes shown in structural formula (II), (III), (IV), (V), (VI) or (VIII);

in one embodiment, the palladium metal precursor (palladium metal precursor) is selected from, but not limited to, palladium chloride (PdCl)₂) Palladium bromide (PdBr)₂) Palladium trifluoroacetate (Pd (TFA))₂) Or palladium acetate (Pd (OAc)₂) Palladium acetate is preferred.

In one embodiment, the organophosphorus compounds in b) are selected from compounds having the general formula PR⁷ ₃CH₂CH₂PR⁷ ₃Diphosphine group(s) of (a), wherein R is⁷Selected from alkyl, phenyl or cycloalkyl.

In one embodiment, the organophosphorus compound in the diphosphine group is selected from, but is not limited to, bis (dicyclohexylphosphine) ethane (bis (dicyclohexylphosphine) ethane), (S, S ', R, R') -Tangphos ((1S,1S ',2R,2R') -1,1'-di-tert-butyl- (2,2') -diphosphane (1S,1S ',2R,2R') -1,1'-di-tert-butyl- (2,2') -diphosphorane), (R, R) - (-) -2,3-bis (tert-butylmethylphosphino) quinoxaline ((R, R) - (-) -2,3-bis (tert-butylmethylphosphino) quinoxaline), (1R,1'R,2S,2' S) -Duanphos ((1R, 1'R,2S,2' S) -2,2' -Di-tert-butyl-2, 3,2',3' -tetrahydro-1H, 1' H- (1,1 ') diisophosphine indole, (1R,1' R,2S,2' S) - (+) -2,2' -Di-t-butyl-2,3,2',3' -tetrahydrogen-1, 1' -bi-1H-isophosphandole) and (-) -1,2-bis [ (2R,5R) -2, 5-dimethylphosphino ] benzene ((-) -1,2-bis [ (2R,5R) -2, 5-dimethylphosphino ] benzene), preferably bis (dicyclohexylphosphine) ethane.

In one embodiment, the base in c) is selected from, but not limited to, sodium tert-butoxide, sodium isopropoxide, sodium 2,6-dimethylphenol, sodium 2,6-difluorophenolate, sodium 2-methylphenol or sodium 2-fluorophenol, preferably sodium tert-butoxide or sodium 2-fluorophenol, most preferably sodium tert-butoxide.

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.

In one embodiment, the catalyst further comprises an additive selected from the group consisting of those having the general formulaWherein R is⁸Selected from alkoxy, cycloalkyl, aryl or alkoxyaryl groups.

In one embodiment, the additive is selected from, but not limited to, triphenylphosphine (triphenylphosphine), tricyclohexylphosphine (tricyclohexylphosphine), tris (2-methoxyphenyl) phosphine (tris (2-methoxyphenyl) phosphine), tris (4-methoxyphenyl) phosphine (tris (4-methoxyphenyl) phosphine), tris (2,6-dimethoxyphenyl) phosphine (tris (2,6-dimethoxyphenyl) phosphine), trioctadecyl phosphite (tristearylphosphite), triphenyl phosphite (triphenylphosphate), tris (2,4-di-tert-butylphenyl) phosphite (tris (2,4-di-tert-butylphenyl) phosphite), tri-p-tolylphosphite, or a mixture thereof, preferably triphenyl phosphine or trioctadecyl phosphite.

In one embodiment, the molar ratio of the catalyst composition comprises:

a)1 part of a palladium metal complex;

b)0.5 to 2 parts of ligand;

c)50 to 400 parts of a base; and

d)50 to 500 parts of a reducing agent.

In one embodiment, the present invention relates to a process for the production of unsaturated carboxylic acid salts derived from carbon dioxide and an olefin, and derivatives thereof, said process comprising:

a) adding a catalyst composition according to any one of claims 1 to 16 in a solvent to a reactor; and

b) condensing olefins and carbon dioxide with the mixture obtained in step a) in a reactor;

the temperature is then raised to 100 ℃ to 180 ℃ and heated for 10-25 hours with a molar ratio of olefin to carbon dioxide of 1 to 2 to 1 to 4.

Preferably, the method for producing unsaturated carboxylic acid salts derived from carbon dioxide and olefins and derivatives thereof comprises:

a) adding a catalyst composition according to any one of claims 1 to 16 in a solvent to a reactor; and

b) condensing olefins and carbon dioxide with the mixture obtained in step a) in a reactor. The temperature is then raised to 130 ℃ to 150 ℃ and heated for 50-25 hours with a molar ratio of olefin to carbon dioxide of 1 to 4.

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

In each step of the process for producing unsaturated carboxylic acid salts and derivatives thereof according to the present invention, unless otherwise specified, 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-dimethylacetamide, N-dimethylformamide, N-dibutylformamide, or a mixture thereof.

The process for the production of the unsaturated carboxylic acid salt and the derivative thereof according to the present invention further comprises a drying step if necessary. The step is selected from, but not limited to, stirring evaporation, vacuum drying, and the like.

In one embodiment, the process for the production of unsaturated carboxylic acid salts and derivatives thereof according to the present invention may be carried out in a reactor, but is not limited to a fixed bed reactor, a batch reactor, or a continuous reactor.

The following examples are intended only to illustrate embodiments of the present invention and do not limit the scope of the invention in any way.

Synthesis of palladium complex catalyst

Synthesis of Complex Compound (II)

Palladium acetate (0.89mmol) was dissolved in hot methanol solvent. N, N' -bis (salicylidene) ethylenediamine (0.89mmol) in acetone solvent was then added and stirred overnight. The resulting suspension was filtered and washed with acetone solvent. The complex was obtained as a dry yellow powder.

Synthesis of Complex Compound (III)

Palladium acetate (0.89mmol) was dissolved in hot methanol solvent. (S, S) - (+) -N, N '-bis (salicylidene) -1,2-cyclohexanediamine ((S, S) - (+) -N, N' -bis (salicylidene) -1, 2-cyclohexenediamine) (0.89mmol) in acetone solvent was then added and stirred overnight. The resulting suspension was filtered and washed with acetone solvent. A dry, green powder of the complex was obtained.

Synthesis of Complex Compound (IV)

Palladium acetate (1.34mmol) was dissolved in hot methanol solvent. Then (S, S) - (+) -N, N '-bis (5-methoxysalicylidene) -1,2-cyclohexanediamine ((S, S) - (+) -N, N' -bis (5-methoxysalicylidene) -1, 2-cyclohexenediamine) (1.34mmol) in acetone solvent was added and stirred overnight. The resulting suspension was filtered and washed with acetone solvent. A dry, green powder of the complex was obtained.

Synthesis of Complex Compound (V)

Palladium acetate (1.34mmol) was dissolved in hot methanol solvent. Then (S, S) - (+) -N, N '-bis (3,5-dichlorosalicylidene) -1,2-cyclohexanediamine ((S, S) - (+) -N, N' -bis (3,5-dichlorosalicylidene) -1, 2-cyclohexadio-amine) (1.34mmol) in acetone solvent was added and stirred overnight. The resulting suspension was filtered and washed with acetone solvent. A dry, green powder of the complex was obtained.

Synthesis of Complex Compound (VI)

Palladium acetate (1.34mmol) was dissolved in hot methanol solvent. Then (S, S) - (+) -N, N '-bis (3-trifluoromethylsalicylidene) -1,2-cyclohexanediamine ((S, S) - (+) -N, N' -bis (3-trifluoromethylsalicylidene) -1, 2-cyclohexadiomine) (1.34mmol) in acetone solvent was added and stirred overnight. The resulting suspension was filtered and washed with acetone solvent. A dry, green powder of the complex was obtained.

Synthesis of Complex Compound (VII)

Palladium acetate (0.65mmol) was dissolved in hot methanol solvent. Then (S, S) - (+) -N, N '-bis (4-diethylaminosalicylidene) -1,2-cyclohexanediamine ((S, S) - (+) -N, N' -bis (4-diaminosalicylidene) -1, 2-cyclohexadio-amine) (1.34mmol) in acetone solvent was added and stirred overnight. The resulting suspension was filtered and washed with acetone solvent. A dry, green powder of the complex was obtained.

Unsaturated carboxylate and its derivatives by reaction of carbon dioxide and olefin

The catalytic performance of the complexes (II) to (VII) in the reaction of carbon dioxide and an olefin used in the production of an unsaturated carboxylic acid salt and its derivatives was tested with (1, 5-cyclooctadiene) palladium (II) dichloride ((COD) PdCl₂) (Sigma Aldrich) as reference catalyst (REF CAT).

A palladium complex (0.1mmol), a ligand (0.11mmol), a base (30mmol), a reducing agent (1-10mmol) and a solvent (30mL) were charged into a reactor. The olefin (10 bar) and carbon dioxide (20-40 bar) were then compressed into the reactor. The reactor was then heated at a temperature of 100 ℃ and 180 ℃ for 20-25 hours. Then, the temperature was decreased to room temperature. The resulting mixture was subjected to olefin and carbon dioxide removal under vacuum. The resulting mixture was used to identify the product by nuclear magnetic resonance spectroscopy (NMR spectroscopy), in which the turnover number (TON) was calculated by the following formula:

conversion number (TON) ═ molar value of product/molar value of catalyst obtained

Wherein sodium 3- (trimethylsilyl) -2,2,3,3-d4-propionate (sodium 3- (trimethylsilyl) -2,2,3,3-d4-propionate) was used as an internal standard and inhibited by the water peak of the NMR spectrum (H₂Osuppression) is calculated.

The following are examples of performance tests on palladium catalysts produced according to the present invention. The method and apparatus for performance testing are commonly used methods and apparatus and do not limit the scope of the present invention.

Table 1: catalytic efficiency of 1, 3-butadiene and carbon dioxide catalyst of the catalyst composition according to the invention

^aThe number of Transitions (TON) was recorded as (product moles)/(moles palladium catalyst) using sodium 3- (trimethylsilyl) -2,2,3,3-d4-propionate as internal standard and water peak suppression (H) by NMR spectroscopy₂Osuppression) is calculated.

-(COD)PdCl₂Reference catalyst (REF CAT); and

-dcpe represents bis (dicyclohexylphosphine) ethane (bis (dicyclohexylphosphino)) or a salt thereof.

Table 2: catalytic efficiency of ethylene and carbon dioxide of the catalyst composition according to the invention

^aThe number of Transitions (TON) was recorded as (product moles)/(moles palladium catalyst) using sodium 3- (trimethylsilyl) -2,2,3,3-d4-propionate as internal standard and water peak suppression (H) by NMR spectroscopy₂Osuppression) is calculated.

-(COD)PdCl₂Is reference catalyst (REF CAT); and

-dcpe represents bis (dicyclohexylphosphine) ethane.

Table 1 shows the catalytic efficiency of 1, 3-butadiene and carbon dioxide of the catalyst composition according to the invention. The palladium catalysts II, III, IV or V were found to have higher turnover numbers (TON) than the reference catalyst (REF-CAT), indicating that the catalyst composition according to the invention has a high catalytic efficiency in the production process of unsaturated carboxylates and derivatives thereof derived from carbon dioxide and olefins.

Table 2 shows the catalytic efficiency of ethylene and carbon dioxide. The purpose of the samples in the table is to show the use of the catalyst composition according to the invention, but it is not intended to limit the scope of protection of the invention by the samples shown. As can be seen from the table, the catalyst composition according to the invention has a high turnover number (TON) when used in a process for the catalysis of the production of unsaturated carboxylic acid salts and derivatives thereof derived from carbon dioxide and olefins, in particular with the addition of additives to the catalyst composition.

From all the above results, it can be said that the catalyst composition according to the present invention has high catalytic efficiency in the production process of catalyzing unsaturated carboxylic acid salts derived from carbon dioxide and olefins and derivatives thereof, as pursued with the object of the present invention.

Preferred embodiments of the invention

Preferred embodiments of the invention are as provided in the description of the invention.