Organic phosphine ligand and preparation method thereof, catalyst composition and preparation method of polyketone

Abstract

The invention relates to the field of fine chemical engineering and polymeric material synthesis, in particular to an organic phosphine ligand and a preparation method thereof, a catalyst composition and a preparation method of polyketone, and particularly provides the organic phosphine ligand with the structure shown in the formula (I). The obtained catalyst is stable in chemical property and high in catalytic activity, can be used for production and preparation of polyketone, and has relatively high polymerization reaction rate and relatively high polymer yield.

Description

Technical Field

[0001] The present invention relates to the fields of fine chemicals and polymer material synthesis, and in particular to an organic phosphine ligand and a preparation method thereof, a catalyst composition and a preparation method of a polyketone. Background Art

[0002] Polyketones are a new type of polymer material obtained by the polymerization of olefins and carbon monoxide. Depending on the olefin monomers used (ethylene, propylene, 1-butene, styrene, etc.), polyketones can be divided into aliphatic polyketones and aromatic polyketones. Based on the degree of structural regularity, polyketones can be divided into regular polyketones and irregular polyketones. Polyketones have excellent toughness, chemical resistance, and wear resistance, and their overall performance is comparable to that of various engineering plastics such as polyoxymethylene, nylon 6, and polybutylene terephthalate (PBT), showing excellent application prospects and development potential. Currently, the regular polyketone PK-E obtained by the polymerization of ethylene and carbon monoxide has been well developed and applied. However, due to its high regularity, its melting point is high, making it inconvenient for downstream processing and application. Therefore, a small amount of propylene is added to the polymerization of ethylene and carbon monoxide to form a random terpolymer PK-EP, which lowers the melting point of the polyketone and promotes its commercial production and application.

[0003] Palladium and nickel are commonly used as metal catalysts in polyketone synthesis. Palladium, with its relatively higher catalytic activity, is currently a focus of academic and applied research. Shell has played a key role in the development of polyketones, having discovered that ligands are crucial in the preparation of polyketones, not only determining catalyst activity but also influencing key polyketone properties such as molecular weight, molecular weight distribution, and propylene insertion rate. Based on 1,3-bisphenylphosphinopropane (dppp), Shell has developed a variety of highly effective polyketone ligands, such as 1,3-bis(bis(2-methoxyphenyl)phosphino)propane (bdompp) (EP257663) and 1,3-bis(bis(2-methoxyphenyl)phosphino)-2,2-diethyl-propane (diEt-XPhos) (EP300583, EP454270, EP743336, WO0008030). The discovery and application of these ligands have significantly improved the efficiency of polyketone preparation and reduced its production cost. In recent years, some other polyketone efficient ligands have also been reported. For example, Hyosung Patent CN105518056 reported ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine), Patent CN101134812A reported 1,3-bis(bis(2-methoxy-5-methylphenyl)phosphino)propane, and Patent CN108290913B reported ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine).

[0004] Based on the results reported in the aforementioned literature and patents, the ligands described above generally have high catalytic activity in polyketone synthesis, generally around 10 kg / (g Pd h), which is already quite economical. However, the preparation process of these ligands is relatively cumbersome, generally requiring multiple steps and resulting in high costs.

[0005] Therefore, developing a new type of polyketone catalyst ligand and its preparation method to achieve a simple synthesis route, low cost and high catalytic activity has become a technical problem that needs to be solved urgently by those skilled in the art. Summary of the Invention

[0006] In view of this, the object of the present invention is to provide an organophosphine ligand and a preparation method thereof, a catalyst composition and a preparation method of a polyketone. The ligand has a novel structure and can be well complexed with an active metal. The resulting catalyst has stable chemical properties and high catalytic activity. The preparation method of the ligand has a simple process route. No hazardous chemicals such as Grignard reagents and alkyl lithium are required during the preparation process. The ligand is obtained in a single step reaction. The overall yield of the route is high and the operation is convenient, which is conducive to the industrialization of polyketone.

[0007] To this end, the present invention provides an organic phosphine ligand having a structure shown in formula (I):

[0008]

[0009] wherein R is selected from a C1-C10 alkyl group, a C6-C20 aryl group, a C3-C8 heterocyclic compound, a C1-C5 acyl group, a C1-C5 sulfonyl group, or a halogen-substituted C1-C10 alkyl group;

[0010] k(X) represents that k hydrogen atoms on the benzene ring are replaced by X, k is an integer from 0 to 4, and k Xs are independently selected from a C1-C10 alkyl group, a C1-C10 alkoxy group, a halogen atom, an amino group, a nitro group, a sulfonic acid group, a C1-C10 alkoxycarbonyl group, a halogen-substituted C1-C10 alkyl group, or a C1-C10 acylamino group.

[0011] In the present application, the halogen or halogen atom is selected from F, Cl, Br or I.

[0012] Furthermore, R is selected from C1-C4 alkyl; preferably, R is methyl, ethyl or propyl.

[0013] Furthermore, k is 0, 1 or 2. When k is 1 or 2, k Xs are independently selected from C1-C4 alkyl, halogen or C1-C4 acylamino groups. Preferably, when k is 1 or 2, k Xs are independently selected from methyl, propyl, chlorine or CH3CONH-.

[0014] Furthermore, the structural formula of the organophosphine ligand is as follows:

[0015]

[0016]

[0017] Among them, Me is methyl, Et is ethyl, OMe is methoxy, and Ac-NH or AcNH is acetylamino.

[0018] The present invention also provides a method for preparing the organic phosphine ligand described in any one of the above, comprising: subjecting compound a to a substitution reaction with compound b in the presence of a basic catalyst to obtain the organic phosphine ligand;

[0019]

[0020] R and k(X) in the above compounds are defined as in any one of the above items, and L is a halogen atom.

[0021] Furthermore, the preparation method satisfies one or more of the following A and F:

[0022] A. The alkaline catalyst is selected from one or more of organic bases and inorganic bases;

[0023] Optionally, the organic base is selected from one or more of tetramethylguanidine, N-(3-methoxyphenyl)guanidine, diphenylguanidine, 1,5,7-triazabicyclo[4,4,0]decene-5-ene, 1,8-diazabicyclo(5.4.0)undec-7-ene (also known as DBU), and 1,5-diazabicyclo[4.3.0]non-5-ene (also known as DBN);

[0024] Optionally, the amount of the organic base is 4.5-10 mol% of the molar amount of compound a;

[0025] Optionally, the inorganic base is selected from one or more of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, lithium phosphate, sodium phosphate, calcium phosphate, and cesium phosphate;

[0026] Optionally, the amount of the inorganic base is 210-350 mol% of the molar amount of compound a;

[0027] B. The amount of compound b is 200.0 to 350.0 mol%, preferably 220.0 to 300.0 mol%, of the molar amount of compound a;

[0028] C. The reaction system of the substitution reaction further comprises an iodine salt;

[0029] Optionally, the iodine salt is selected from one or more of lithium iodide, sodium iodide, and potassium iodide;

[0030] Optionally, the amount of the iodine salt is 4.5-10 mol% of the molar amount of compound a;

[0031] D. The reaction solvent of the substitution reaction is selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, N,N-dimethylformamide (DMF), dimethyl sulfoxide, dichloromethane, dichloroethane, and chloroform; preferably tetrahydrofuran and / or acetonitrile;

[0032] E. The reaction temperature of the substitution reaction is 0 to 25° C., the reaction pressure is normal pressure, and the reaction time is 8 to 12 hours;

[0033] F. The compound a is selected from o-catechol, 3,6-dimethyl-1,2-benzenediol, 4-isopropyl-1,2-benzenediol, 4-chloro-1,2-benzenediol or 4-acetylamino-1,2-benzenediol; and / or, the compound b is selected from di(2-methoxyphenyl)phosphine chloride or di(2-ethoxyphenyl)phosphine chloride.

[0034] Furthermore, the preparation method specifically comprises the following steps: mixing a reaction solvent with compound a, a basic catalyst and an iodine salt to obtain a mixed solution, dropwise adding a solution containing compound b to the mixed solution, and reacting to obtain an organic phosphine ligand;

[0035] Optionally, after the reaction, the step of filtering the filtrate, evaporating the solvent, collecting the crude product and purifying the crude product is further included;

[0036] Optionally, the concentration of the solution containing compound b is 0.1-0.5 g / mL;

[0037] Optionally, the ratio of the volume of the reaction solvent to the molar amount of compound a is 30-50 mL: 4-15 mmol;

[0038] Optionally, the ratio of the volume of the solution containing compound b to the molar amount of compound a is 15-20 mL:4-15 mmol.

[0039] The present invention also provides a catalyst composition comprising any of the above-mentioned organophosphine ligands or an organophosphine ligand prepared by any of the above-mentioned preparation methods, and an active metal;

[0040] Optionally, the active metal is selected from one or more of palladium, nickel, and platinum;

[0041] Optionally, the molar ratio of the active metal to the organophosphine ligand is 1:1-1.2.

[0042] Furthermore, the catalyst composition further comprises a monodentate phosphine ligand and / or an acid;

[0043] Preferably, the acid is selected from one or more of trifluoroacetic acid, trichloroacetic acid, methanesulfonic acid, toluenesulfonic acid, sulfuric acid, and trifluoromethanesulfonic acid;

[0044] Preferably, the molar ratio of the acid to the active metal is 4-7:1;

[0045] Preferably, the monodentate phosphine ligand is selected from one or more of triphenylphosphine, tri(2-methylphenyl)phosphine, tri(3-methylphenyl)phosphine, tri(4-methylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, and tri(1-naphthyl)phosphine;

[0046] Preferably, the molar ratio of the monodentate phosphine ligand to the active metal is 2.5-7:1;

[0047] More preferably, the catalyst composition comprises the active metal, the organic phosphine ligand, methanesulfonic acid and tris(2-methoxyphenyl)phosphine in a molar ratio of 1:1-1.2:4-7:2.5-7.

[0048] The present invention also provides an application of the catalyst composition in catalyzing the polymerization of olefins and carbon monoxide to prepare polyketones.

[0049] The present invention also provides a method for preparing polyketone, comprising: in the presence of any one of the above-mentioned catalyst compositions, polymerizing olefins and carbon monoxide to obtain polyketone;

[0050] Preferably, one or more of the following A and F are met:

[0051] A. The olefin is selected from one or more of ethylene, propylene, and 1-butene; and / or the molar ratio of the olefin to carbon monoxide is 0.5-2:1;

[0052] B. The reaction pressure of the polymerization reaction is 3.0 to 6.0 MPaG;

[0053] C. The reaction temperature of the polymerization reaction is 60 to 80° C.

[0054] D. The reaction time of the polymerization reaction is 1 to 3 hours;

[0055] E. The reaction solvent of the polymerization reaction is selected from one or more of methanol and water, preferably a methanol solution containing 2000 to 6000 ppm of water;

[0056] F. The mass ratio of the organic phosphine ligand in the catalyst composition to the reaction solvent in the polymerization reaction is 1:20,000-50,000.

[0057] The technical solution of the present invention has the following advantages:

[0058] 1. The organophosphine ligand having the structure shown in formula (I) provided by the present invention has a novel ligand structure and can be well complexed with active metals. The resulting catalyst has stable chemical properties and high catalytic activity and can be used for the production and preparation of polyketones, with a faster polymerization reaction rate and a higher polymer yield.

[0059] 2. The present invention provides a method for preparing an organophosphine ligand, wherein compound a undergoes a substitution reaction with compound b in the presence of a basic catalyst to produce the organophosphine ligand. This method provides a one-step preparation of the organophosphine ligand. The preparation utilizes readily available, inexpensive raw materials, a novel and concise synthetic route, high yields, and ease of scale-up and preparation.

[0060] The reaction system of the substitution reaction also includes iodine salt. By adding iodine during the ligand preparation and synthesis process, the yield is improved and the cost of ligand synthesis is further reduced.

[0061] 3. The preparation method of the organophosphine ligand provided by the present invention, wherein the alkaline catalyst is selected from one or more organic bases and inorganic bases, especially the synergistic catalysis of organic bases and inorganic bases in the ligand synthesis, not only accelerates the reaction rate, but also further improves the selectivity and yield of the reaction.

[0062] 4. The catalyst composition provided by the present invention comprises an organic phosphine ligand and an active metal, and also comprises a monodentate phosphine ligand and / or an acid. In the preparation of polyketone, the present invention has found that the use of a monodentate phosphine ligand and / or an acid together with a complex formed by the organic phosphine ligand and the active metal can effectively improve the stability of the catalyst, further improving the catalytic activity and product yield of the catalyst.

[0063] 5. The present invention provides a catalyst composition comprising an active metal, an organophosphine ligand, methanesulfonic acid, and tris(2-methoxyphenyl)phosphine in a molar ratio of 1:1-1.2:4-7:2.5-7. The catalytic activity of the catalyst can be further enhanced by combining the active metal, organophosphine ligand, methanesulfonic acid, and tris(2-methoxyphenyl)phosphine in a specific ratio.

[0064] 6. The method for preparing polyketone provided by the present invention is simple and easy to operate. The catalytic activity of the catalyst can be further enhanced by limiting the polymerization reaction solvent to one or more of methanol and water, preferably a methanol solution containing 2000-6000 ppm of water. The catalytic activity of the catalyst can be further enhanced by limiting the olefin to one or more of ethylene, propylene, and 1-butene; and / or limiting the molar ratio of olefin to carbon monoxide to 0.5-2:1. DETAILED DESCRIPTION

[0065] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0066] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0067] The main raw material information is as follows:

[0068] Catechol, 3,6-dimethyl-1,2-benzenediol, and 4-isopropyl-1,2-benzenediol (also known as 4-isopropylcatechol) were all purchased from Anaiji Chemical with a purity of ≥99%. Bis(2-methoxyphenyl)phosphine chloride (CAS No. 263369-88-6) was purchased from Aladdin Reagent with a purity of ≥99%. Bis(2-ethoxyphenyl)phosphine chloride was purchased from Inokane with a purity of ≥98%. DBU, tetramethylguanidine, and 1,5,7-triazabicyclo[4,4,0]decene-5-ene were all purchased from Aladdin Reagent with a purity of ≥99%. Diphenylguanidine (purity ≥99%) was purchased from Anaiji Chemical. Potassium carbonate, cesium carbonate, and potassium phosphate were purchased from Sinopharm Reagent and were of analytical grade (AR). Potassium iodide, sodium iodide, and lithium iodide were purchased from Aladdin Reagent and were of analytical grade (AR). Tri(2-methoxyphenyl)phosphine was purchased from Xi'ans Biochemical, with a purity of ≥99%. Anhydrous tetrahydrofuran and acetonitrile were purchased from Sinopharm Reagents, AR; triethylamine and diisopropylethylamine were purchased from TCI, with a purity of ≥98%; palladium acetate was purchased from Sinochem, with a purity of ≥99%; trifluoroacetic acid was purchased from J&K, with a purity of ≥99%; p-toluenesulfonic acid and methanesulfonic acid were purchased from Aladdin Reagents, with a purity of ≥99%; triphenylphosphine, tri(2-methylphenyl)phosphine, and tri(3-methylphenyl)phosphine were purchased from Sinochem, with a purity of ≥99%; tri(1-naphthyl)phosphine was purchased from Xiaochi Reagents, with a purity of ≥99%. Anhydrous methanol and acetone were purchased from Strem Reagents, chromatographic grade. The ethylene and CO mixture (molar ratio of 1:1) and the ethylene, CO and propylene mixture (molar ratio of 4.5:4.5:1.0) were purchased from Dalian Special Gas Co., Ltd., with a purity of ≥99%.

[0069] The compounds in the following examples were characterized by hydrogen spectroscopy using a Bruker Avance Neo 400M nuclear magnetic resonance spectrometer at a temperature of 25°C.

[0070] Example A1

[0071] This embodiment provides a method for preparing an organic phosphine ligand, and its reaction route and preparation method are as follows:

[0072]

[0073] Under nitrogen, a 250 mL three-necked flask equipped with a magnetic rod was placed in an ice-water bath at room temperature. After nitrogen replacement three times, anhydrous tetrahydrofuran (35 mL), tetramethylguanidine (46 mg, 0.4 mmol), potassium carbonate (2.43 g, 17.6 mmol), sodium iodide (60 mg, 0.4 mmol) and catechol (0.88 g, 8.0 mmol, compound a-1) were added in sequence and stirred for 10 minutes to obtain a clear solution; finally, a tetrahydrofuran solution (15 mL) of di(2-methoxyphenyl)phosphine chloride (4.72 g, 16.8 mmol, compound b-1) was slowly added dropwise to the reaction solution through a constant pressure dropping funnel. The addition was completed over 15 minutes, the ice-water bath was removed, and the reaction solution was stirred at room temperature. The reaction was stopped for 12 hours.

[0074] For post-treatment, the reaction solution was first quickly filtered to remove the insoluble salts in the reaction solution, and then the reaction solvent tetrahydrofuran was removed by rotary evaporation to obtain a light yellow oily crude product. Finally, the product was separated and purified by rapid silica gel column chromatography (200-300 mesh silica gel powder, eluent n-hexane: ethyl acetate = 10:1 (V / V)). After rotary evaporation of the eluent, the target product 1,2-bis(bis(2-methoxyphenyl)phosphino)oxy)benzene (1,2-bis((bis(2-methoxyphenyl)phosphino)oxy)benzene, recorded as product II) 4.36g was obtained with a yield of 91%. Product II 1 H NMR (400MHz, Chloroform-d): δ7.36-7.25(m,8H),7.06-6.92(m,8H),6.86-6.76(m,4H),3.83(s,12H); 13 CNMR(101MHz,Chloroform-d):δ159.3,148.5,132.1,129.7,122.6,121.1,116.7,111.7,111.1,56.2.HRMS(ESI):calcd for C 34 H 33 O6P2[M+H] + :599.1752,found 599.1751.

[0075] Example A2

[0076] This embodiment provides a method for preparing an organic phosphine ligand. The reaction route is the same as that of Example 1. The specific preparation method is as follows:

[0077] Under nitrogen, a 250 mL three-necked flask containing a magnetic rod was placed in an ice-water bath at room temperature. After nitrogen replacement three times, anhydrous tetrahydrofuran (30 mL), tetramethylguanidine (58 mg, 0.5 mmol), potassium carbonate (2.42 g, 17.5 mmol), sodium iodide (75 mg, 0.5 mmol), and catechol (0.55 g, 5.0 mmol) were added in sequence. After stirring for 10 minutes, a clear solution was obtained. Finally, a tetrahydrofuran solution (15 mL) of di(2-methoxyphenyl)phosphine chloride (4.21 g, 15.0 mmol) was slowly added dropwise to the reaction solution through a constant pressure dropping funnel. The addition was completed over 15 minutes. The ice-water bath was removed and the reaction solution was stirred at room temperature for 8 hours to stop the reaction. After post-treatment, the reaction solution was first rapidly filtered to remove undissolved salts in the reaction solution, and then the reaction solvent tetrahydrofuran was removed by rotary evaporation to obtain a light yellow oily crude product. Finally, the product was separated and purified by rapid silica gel column chromatography (200-300 mesh silica gel powder, eluent n-hexane:ethyl acetate = 10:1 (V / V)). After rotary evaporation of the eluent, 2.84 g of the target product 1,2-bis(bis(2-methoxyphenyl)phosphinooxy)benzene was obtained in a yield of 95%.

[0078] Example A3

[0079] This embodiment provides a method for preparing an organic phosphine ligand, and its reaction route and preparation method are as follows:

[0080]

[0081] Under nitrogen, a 250 mL three-necked flask containing a magnetic rod was placed in an ice-water bath at room temperature. After nitrogen replacement three times, anhydrous tetrahydrofuran (35 mL), diphenylguanidine (56 mg, 0.3 mmol), potassium phosphate (2.81 g, 13.3 mmol), lithium iodide (35 mg, 0.3 mmol), and catechol (0.58 g, 5.3 mmol) were added in sequence. Stirring for 10 minutes yielded a clear solution. Finally, a tetrahydrofuran solution (15 mL) of di(2-ethoxyphenyl)phosphine chloride (3.60 g, 11.7 mmol, compound b-2) was slowly added dropwise to the reaction solution via a constant pressure dropping funnel. The addition was complete over 15 minutes. The ice-water bath was removed, and the reaction solution was stirred at room temperature for 10 hours to terminate the reaction. Post-treatment: First, the reaction solution was rapidly filtered to remove undissolved salts, and then the tetrahydrofuran solvent was removed by rotary evaporation to yield a pale yellow oily crude product. Finally, the product was separated and purified by rapid silica gel column chromatography (200-300 mesh silica gel powder, eluent n-hexane:ethyl acetate = 10:1 (V / V)). After rotary evaporation of the eluent, 3.37 g of the target product 1,2-bis(bis(2-ethoxyphenyl)phosphino)oxy)benzene (referred to as Product III) was obtained with a yield of 97%. 1 H NMR (400MHz, Chloroform-d): δ7.35-7.26(m,8H),7.04-6.94(m,8H),6.85-6.78(m,4H),4.09(q,8H),1.33(t,12H); 13 CNMR(101MHz,Chloroform-d):δ155.9,148.5,131.6,129.3,122.7,120.3,116.9,111.9,111.2,64.9,14.7.HRMS(ESI):calcd for C 38 H 41 O6P2[M+H] + :655.2378,found 655.2379.

[0082] Example A4

[0083] This embodiment provides a method for preparing an organic phosphine ligand, and the reaction equation and preparation method are as follows:

[0084]

[0085] Under nitrogen, a 250 mL three-necked flask equipped with a magnetic rod was placed in an ice-water bath at room temperature. After nitrogen replacement three times, anhydrous tetrahydrofuran (50 mL), 1,5,7-triazabicyclo[4,4,0]decene-5-ene (72 mg, 0.5 mmol), cesium carbonate (7.46 g, 22.9 mmol), lithium iodide (70 mg, 0.5 mmol) and 3,6-dimethyl-1,2-benzenediol (1.44 g, 10.4 mmol, compound a-2) were added in sequence and stirred for 10 minutes to obtain a clear solution. Finally, a tetrahydrofuran solution (20 mL) of di(2-methoxyphenyl)phosphine chloride (6.71 g, 23.9 mmol) was slowly added dropwise to the reaction solution through a constant pressure dropping funnel. The addition was completed over 15 minutes, the ice-water bath was removed, and the reaction solution was stirred at room temperature. The reaction was stopped for 12 hours. For post-treatment, the reaction solution was first quickly filtered to remove the insoluble salts in the reaction solution, and then the reaction solvent tetrahydrofuran was removed by rotary evaporation to obtain a light yellow oily crude product. Finally, the product was separated and purified by rapid silica gel column chromatography (200-300 mesh silica gel powder, eluent n-hexane: ethyl acetate = 8:1 (V / V)). After rotary evaporation of the eluent, the target product 1,2-bis(bis(2-methoxyphenyl)phosphinoyl)-3,6-dimethylbenzene (((3,6-dimethyl-1,2-phenylene)bis(oxy))bis(bis(2-methoxyphenyl)phosphine), denoted as product IV) 6.0 g, with a yield of 92%. Product IV 1 H NMR (400MHz, Chloroform-d): δ7.36-7.26(m,8H),7.06-6.93(m,8H),6.50(d,2H),3.83(s,12H),2.15(s,6H); 13 C NMR(101MHz,Chloroform-d): δ159.2,145.1,132.0,129.7,124.5,122.9,121.0,116.8,111.1,56.1,15.7.HRMS(ESI):calcd for C 36 H 37 O6P2[M+H] + :627.6229,found627.6230.

[0086] Example A5

[0087] This embodiment provides a method for preparing an organic phosphine ligand, and the reaction equation and preparation method are as follows:

[0088]

[0089] Under nitrogen, a 250 mL three-necked flask containing a magnetic rod was placed in an ice-water bath at room temperature. After nitrogen replacement three times, anhydrous acetonitrile (30 mL), DBU (31 mg, 0.2 mmol), potassium carbonate (1.25 g, 9.0 mmol), potassium iodide (34 mg, 0.2 mmol), and 4-isopropyl-1,2-benzenediol (0.62 g, 4.1 mmol, compound a-3) were added sequentially. Stirring for 10 minutes yielded a suspension. Finally, a solution of di(2-methoxyphenyl)phosphine chloride (2.53 g, 9.0 mmol) in acetonitrile (15 mL) was slowly added dropwise to the reaction solution via a constant pressure dropping funnel over 15 minutes. The ice-water bath was removed, and the reaction solution was stirred at room temperature for 12 hours to terminate the reaction. For post-processing, the reaction solution was first rapidly filtered to remove undissolved salts, and then the acetonitrile solvent was removed by rotary evaporation to yield a crude, pale yellow oily product. Finally, the product was separated and purified by rapid silica gel column chromatography (200-300 mesh silica gel powder, eluent n-hexane:ethyl acetate = 10:1 (V / V)). After rotary evaporation of the eluent, the target product 1,2-bis(bis(2-methoxyphenyl)phosphinoyl)-4-isopropylbenzene (((4-isopropyl-1,2-phenylene)bis(oxy))bis(bis(2-methoxyphenyl)phosphine), referred to as product V) 2.55 g was obtained with a yield of 97%. 1 H NMR (400MHz, Chloroform-d): δ7.34-7.27(m,8H),7.05-6.93(m,8H),6.91-6.60(m,3H),3.83(s,12H),3.05(m,1H),1.20(d,6H); 13 C NMR (101MHz, Chloroform-d): δ159.1,148.2,142.3,139.4,132.0,129.7,122.4,121.2,120.1,116.8,111.1,109.1,56.1,27.6,23.6; HRMS (ESI): calcd for C 37 H 39 O6P2[M+H] + :641.2222,found 641.2220.

[0090] Example A6

[0091] This embodiment provides a method for preparing an organic phosphine ligand, and the reaction equation and preparation method are as follows:

[0092]

[0093] Under nitrogen, a 250 mL three-necked flask containing a magnetic rod was placed in an ice-water bath at room temperature. After nitrogen replacement three times, anhydrous acetonitrile (30 mL), DBU (40 mg, 0.3 mmol), potassium carbonate (1.46 g, 11.7 mmol), sodium iodide (40 mg, 0.3 mmol), and 4-chloro-1,2-benzenediol (0.77 g, 5.3 mmol, compound a-4) were added sequentially. Stirring for 10 minutes yielded a suspension. Finally, a solution of di(2-methoxyphenyl)phosphine chloride (3.27 g, 11.7 mmol) in acetonitrile (15 mL) was slowly added dropwise to the reaction solution via a constant pressure dropping funnel over 15 minutes. The ice-water bath was removed, and the reaction solution was stirred at room temperature for 12 hours to terminate the reaction. For post-processing, the reaction solution was first rapidly filtered to remove undissolved salts, and then the acetonitrile solvent was removed by rotary evaporation to yield a crude, pale yellow oily product. Finally, the product was separated and purified by rapid silica gel column chromatography (200-300 mesh silica gel powder, eluent n-hexane:ethyl acetate = 10:1 (V / V)). After rotary evaporation of the eluent, the target product 1,2-bis(bis(2-methoxyphenyl)phosphinoyl)-4-chlorobenzene (((4-chloro-1,2-phenylene)bis(oxy))bis(bis(2-methoxyphenyl)phosphine), referred to as product VI) 3.22 g was obtained with a yield of 96%. 1 HNMR (400MHz, Chloroform-d): δ7.35-7.27(m,8H),7.04-6.99(m,8H),6.97-6.88(m,3H),3.84(s,12H); 13 C NMR (101MHz, Chloroform-d): δ159.3,149.9,146.6,132.0,129.7,129.5,123.9,121.0,118.7,118.1,116.8,111.1,56.1; HRMS (ESI):calcd for C 34 H 32 ClO6P2[M+H] + :633.1363,found 633.0148.

[0094] Example A7

[0095] This embodiment provides a method for preparing an organic phosphine ligand, and the reaction equation and preparation method are as follows:

[0096]

[0097] Under nitrogen, a 250 mL three-necked flask containing a magnetic rod was placed in an ice-water bath at room temperature. After nitrogen replacement three times, anhydrous DMF (30 mL), DBN (34 mg, 0.3 mmol), potassium carbonate (1.67 g, 12.1 mmol), sodium iodide (41 mg, 0.3 mmol), and 4-acetamido-1,2-benzenediol (0.92 g, 5.5 mmol, compound a-5) were added sequentially. Stirring for 10 minutes yielded a suspension. Finally, a DMF solution (15 mL) of di(2-methoxyphenyl)phosphine chloride (3.4 g, 12.1 mmol) was slowly added dropwise to the reaction solution via a constant pressure dropping funnel over 15 minutes. The ice-water bath was removed, and the reaction solution was stirred at room temperature for 12 hours to terminate the reaction. For post-processing, the reaction solution was first rapidly filtered to remove undissolved salts, and then the acetonitrile solvent was removed by rotary evaporation to yield a crude, pale yellow oily product. Finally, the product was separated and purified by rapid silica gel column chromatography (200-300 mesh silica gel powder, eluent n-hexane:ethyl acetate = 5:1 (V / V)). After rotary evaporation of the eluent, 3.35 g of the target product 1,2-bis(bis(2-methoxyphenyl)phosphino)oxy)phenyl)acetamide (denoted as product VII) was obtained with a yield of 93%. 1 H NMR (400MHz, Chloroform-d): δ7.55(b,1H),7.33-7.26(m,8H),7.15(s,1H),7.04-6.98(m,9H),6.76(d,1H),3.83(s,12H),2.25(s,1H); 13 C NMR (101MHz, Chloroform-d): δ168.9,159.2,148.7,144.1,132.5,132.1,129.6,121.0,117.5,116.8,115.6,111.2,107.7,56.1,24.0; HRMS (ESI): calcd for C 36 H 36 NO7P2[M+H] + :656.1967,found 656.6211.

[0098] Example B1

[0099] This embodiment provides a method for preparing a catalyst composition, comprising the following steps: in a glove box, first, adding acetone (2 mL) to an ampoule equipped with a magnetic stirrer, placing the single-necked flask on a magnetic stirrer, and starting stirring. Then, palladium acetate (1.0 mg, 0.0044 mmol), the organophosphine ligand 1,2-bis(bis(2-methoxyphenyl)phosphinooxy)benzene (2.9 mg, 0.0048 mmol) prepared in Example A1, and trifluoroacetic acid (2.0 mg, 0.018 mmol) are added to the single-necked flask in sequence. The mixture is stirred at room temperature for 10 minutes to obtain a clear catalyst solution. Finally, triphenylphosphine (3.5 mg, 0.013 mmol) is added to the solution. After the triphenylphosphine is completely dissolved, the catalyst composition is obtained.

[0100] This embodiment also provides a method for synthesizing a binary polyketone from ethylene and carbon monoxide, comprising the following steps: transferring the above-obtained catalyst composition to a single-necked bottle, followed by sequentially adding anhydrous methanol (98.0 g) and deionized water (0.49 g), sealing the single-necked bottle with a rubber stopper, removing it from the glove box, and protecting it with a nitrogen balloon. The obtained catalyst solution is pumped into an autoclave using a horizontal flow pump. The autoclave used has been replaced with nitrogen three times in advance. After the above-mentioned materials are added, the nitrogen is replaced three times with a mixture of ethylene and carbon monoxide in a molar ratio of 1:1, each time at 0.3 MPaG, and finally filled with 4.0 MPaG of the above-mentioned mixture. Turn on the stirring and heating of the autoclave, and when the temperature in the reactor rises rapidly to 70°C, the reaction begins, the temperature and the pressure of the mixture are kept constant, and the reaction is stirred for 2 hours. For post-treatment, the heating of the autoclave jacket was turned off, and the inner coil was turned on to remove heat. After the temperature of the reaction liquid dropped to room temperature, the high-pressure mixed gas in the autoclave was vented, the reactor was opened, the polymerization reaction liquid was taken out and filtered, and the filter cake was washed with methanol 2 to 3 times to obtain a white polyketone product. After drying under reduced pressure at 50°C, it was weighed to obtain 21.6 g of binary polyketone product with a catalyst activity of 23.1 kg / (g-Pd.h).

[0101] Example B2

[0102] This example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene, propylene, and carbon monoxide. The method is substantially the same as Example B1, differing only in that an equal molar amount of 1,2-bis(bis(2-ethoxyphenyl)phosphinoxy)benzene prepared in Example A3 is used in place of the 1,2-bis(bis(2-methoxyphenyl)phosphinoxy)benzene in Example B1. All other process conditions are the same as those in Example B1. The polymerization reaction liquid is filtered, and the filter cake is washed two to three times with methanol to obtain a white polyketone product. The product is dried under reduced pressure at 50°C and weighed to yield 16.4 g of the binary polyketone product, with a catalyst activity of 17.5 kg / (g-Pd.h).

[0103] Example B3

[0104] This example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene, propylene, and carbon monoxide. The method is substantially the same as Example B1, differing only in that an equal molar amount of 1,2-bis(bis(2-methoxyphenyl)phosphinooxy)-3,6-dimethylbenzene prepared in Example A4 is used in place of the 1,2-bis(bis(2-methoxyphenyl)phosphinooxy)benzene in Example B1. All other process conditions are the same as those in Example B1. The polymerization reaction liquid is filtered, and the filter cake is washed two to three times with methanol to obtain a white polyketone product. The product is dried under reduced pressure at 50°C and weighed to yield 19.2 g of the binary polyketone product, with a catalyst activity of 20.5 kg / (g-Pd.h).

[0105] Example B4

[0106] This Example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene, propylene, and carbon monoxide. The method is substantially the same as Example B1, differing only in that an equal molar amount of 1,2-bis(bis(2-methoxyphenyl)phosphinooxy)-4-isopropylbenzene prepared in Example A5 is used in place of the 1,2-bis(bis(2-methoxyphenyl)phosphinooxy)benzene in Example B1. All other process conditions are the same as those in Example B1. The polymerization reaction liquid is filtered, and the filter cake is washed two to three times with methanol to obtain a white polyketone product. The product is dried under reduced pressure at 50°C and weighed to yield 16.3 g of the binary polyketone product, with a catalyst activity of 17.5 kg / (g-Pd.h).

[0107] Example B5

[0108] This embodiment provides a method for preparing a catalyst composition, comprising the following steps: in a glove box, first, adding acetone (2 mL) to an ampoule equipped with a magnetic stirrer, placing the single-necked flask on a magnetic stirrer, and starting stirring. Then, palladium acetate (1.1 mg, 0.0047 mmol), the organophosphine ligand 1,2-bis(bis(2-methoxyphenyl)phosphinoyl)-3,6-dimethylbenzene (3.5 mg, 0.0056 mmol) prepared in Example A1, and methanesulfonic acid (1.8 mg, 0.019 mmol) are added to the single-necked flask in sequence. The mixture is stirred at room temperature for 10 minutes to obtain a clear catalyst solution. Finally, tri(2-methoxyphenyl)phosphine (11.6 mg, 0.033 mmol) is added to the solution. After the triphenylphosphine is completely dissolved, the catalyst composition is obtained.

[0109] This embodiment also provides a method for synthesizing a binary polyketone from ethylene and carbon monoxide, comprising the following steps: transferring the above-obtained catalyst composition to a single-necked bottle, followed by sequentially adding anhydrous methanol (105.0 g) and deionized water (0.53 g), sealing the single-necked bottle with a rubber stopper, removing it from the glove box, and protecting it with a nitrogen balloon. The obtained catalyst solution is pumped into an autoclave using a horizontal flow pump. The autoclave used has been replaced with nitrogen three times in advance. After the above-mentioned materials are added, the nitrogen is replaced three times with a mixture of ethylene and carbon monoxide in a molar ratio of 1:1, each time at 0.3 MPaG, and finally filled with 4.0 MPaG of the above-mentioned mixed gas. Turn on the stirring and heating of the autoclave, and when the temperature in the reactor rises rapidly to 70°C, the reaction begins, the temperature and the mixed gas pressure are kept constant, and the reaction is stirred continuously for 2 hours. For post-treatment, the heating of the autoclave jacket was turned off, and the inner coil was turned on to remove heat. After the temperature of the reaction liquid dropped to room temperature, the high-pressure mixed gas in the autoclave was vented, the reactor was opened, the polymerization reaction liquid was taken out and filtered, and the filter cake was washed with methanol 2 to 3 times to obtain a white polyketone product. After drying under reduced pressure at 50°C, it was weighed to obtain 27.1g of binary polyketone product with a catalyst activity of 27.1kg / (g-Pd.h).

[0110] Example B6

[0111] This embodiment provides a method for preparing a catalyst composition, comprising the following steps: in a glove box, first, acetone (2 mL) is added to an ampoule equipped with a magnetic stirrer, the single-necked flask is placed on a magnetic stirrer, and stirring is started. Then, palladium acetate (1.5 mg, 0.0064 mmol), the organophosphine ligand 1,2-bis(bis(2-methoxyphenyl)phosphinooxy)-3,6-dimethylbenzene (4.4 mg, 0.0071 mmol) prepared in Example A1, and trifluoroacetic acid (3.0 mg, 0.026 mmol) are added to the single-necked flask in sequence, and stirred at room temperature for 10 minutes to obtain a clear catalyst solution. Finally, tri(2-methylphenyl)phosphine (5.9 mg, 0.019 mmol) is added to the solution, and after the tri(2-methylphenyl)phosphine is completely dissolved, a catalyst composition is obtained.

[0112] This embodiment also provides a method for synthesizing a binary polyketone from ethylene, propylene and carbon monoxide, comprising the following steps: transferring the obtained catalyst solution to a single-necked bottle, then adding anhydrous methanol (120.0 g) and deionized water (0.60 g) in sequence, sealing the single-necked bottle with a rubber stopper, removing it from the glove box, and protecting it with a nitrogen balloon. The obtained catalyst solution is pumped into an autoclave using a horizontal flow pump. The autoclave used has been replaced with nitrogen three times in advance. After the above materials are added, the nitrogen is replaced three times with a mixture of ethylene, carbon monoxide and propylene in a molar ratio of 4.5:4.5:1.0, each time at 0.3 MPaG, and finally filled with 6.0 MPaG of the above mixture. Turn on the stirring and heating of the autoclave, and when the temperature in the reactor is rapidly raised to 80°C, the reaction begins, the temperature and the pressure of the mixture are kept constant, and the reaction is stirred for 2 hours. For post-treatment, the heating of the autoclave jacket was turned off, and the inner coil was turned on to remove heat. After the temperature of the reaction liquid dropped to room temperature, the high-pressure mixed gas in the autoclave was vented, the reactor was opened, the polymerization reaction liquid was taken out and filtered, and the filter cake was washed with methanol 2 to 3 times to obtain a white polyketone product. After drying under reduced pressure at 50°C, it was weighed to obtain 28.3g of ternary polyketone product with a catalyst activity of 20.8kg / (g-Pd.h).

[0113] Example B7

[0114] This example provides a method for preparing a catalyst composition and synthesizing a binary polyketone from ethylene, propylene, and carbon monoxide. The method is essentially the same as Example B6, differing only in that an equal molar amount of p-toluenesulfonic acid is used instead of trifluoroacetic acid. All other process conditions remain the same as those in Example B6. The polymerization reaction liquid is filtered, and the filter cake is washed two to three times with methanol to obtain a white polyketone product. This product is dried under reduced pressure at 50°C and weighed to yield 30.1 g of the ternary polyketone product, with a catalyst activity of 22.1 kg / (g-Pd.h).

[0115] Example B8

[0116] This example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene and carbon monoxide, which is basically the same as Example B5, except that the same molar amount of p-toluenesulfonic acid is used instead of methanesulfonic acid.

[0117] Example B9

[0118] This example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene and carbon monoxide, which is basically the same as Example B5, except that the same molar amount of tri(1-naphthyl)phosphine is used instead of tri(2-methoxyphenyl)phosphine.

[0119] Example B10

[0120] This embodiment provides a method for preparing a catalyst composition using ethylene and carbon monoxide to synthesize a binary polyketone, which is basically the same as that of Example B5, except that tris(2-methoxyphenyl)phosphine is not added during the preparation of the catalyst composition.

[0121] Example B11

[0122] This embodiment provides a method for synthesizing a binary polyketone from ethylene and carbon monoxide, which is basically the same as that of Example B5. The catalyst composition adopts the catalyst composition of Example B5, with the only difference being that “adding anhydrous methanol (105.0 g)” is used instead of “adding anhydrous methanol (105.0 g) and deionized water (0.53 g)”.

[0123] Example B12

[0124] This example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene, propylene, and carbon monoxide. This method is essentially the same as Example B1, differing only in that an equal molar amount of 1,2-bis(bis(2-methoxyphenyl)phosphinoxy)-4-chlorobenzene prepared in Example A6 is used in place of the 1,2-bis(bis(2-methoxyphenyl)phosphinoxy)benzene in Example B1. The polymerization reaction liquid is filtered, and the filter cake is washed two to three times with methanol to obtain a white polyketone product. The product is dried under reduced pressure at 50°C and weighed to yield 19.7 g of the binary polyketone product, with a catalyst activity of 21.1 kg / (g-Pd.h).

[0125] Example B13

[0126] This example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene, propylene, and carbon monoxide. This method is essentially the same as Example B1, differing only in that an equal molar amount of 1,2-bis(bis(2-methoxyphenyl)phosphinoxy)-4-acetamidobenzene prepared in Example A7 is used in place of the 1,2-bis(bis(2-methoxyphenyl)phosphinoxy)benzene in Example B1. The polymerization reaction liquid is filtered, and the filter cake is washed two to three times with methanol to obtain a white polyketone product. The product is dried under reduced pressure at 50°C and weighed to yield 22.3 g of the binary polyketone product, with a catalyst activity of 23.8 kg / (g-Pd.h).

[0127] Comparative Example 1

[0128] This comparative example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene and carbon monoxide, which are basically the same as Example B1, except that the same molar amount of dppp ligand (1,3-bis(diphenylphosphino)propane) is used instead of 1,2-bis(bis(2-methoxyphenyl)phosphinooxy)benzene in Example B1.

[0129] Comparative Example 2

[0130] This comparative example provides a method for preparing a catalyst composition and a method for synthesizing a binary polyketone using ethylene and carbon monoxide, which are basically the same as Example B1, except that the same molar amount of 1,2-bis(di(2-methylphenyl)phosphinoxy)benzene (referred to as "ligand C") is used instead of 1,2-bis(di(2-methoxyphenyl)phosphinoxy)benzene in Example B1.

[0131] The preparation method of ligand C is basically the same as that of Example A1, except that the same molar amount of di(o-tolyl)phosphine chloride is used instead of compound b-1. The structural formula of ligand C is:

[0132] Ligand C 1 H NMR (400MHz, Chloroform-d): δ7.35-7.26(m,16H),6.76-6.86(m,4H),2.38(s,12H); 13 C NMR(101MHz,Chloroform-d):δ148.5,137.1,132.3,131.9,131.7,130.9,125.7,122.6,111.9,22.3.HRMS(ESI):calcd for C 34 H 33 O2P2[M+H] + :535.1956,found 535.1954.

[0133] Table 1 Experimental results

[0134]

[0135]

[0136] As shown in the table above, the use of the organophosphine ligand with a specific structure according to the present invention significantly improved catalyst activity compared to Comparative Examples 1-2. Compared to Examples B1-B4 and Example B12 and Example B13, the organophosphine ligands used in Examples B1 and B13 exhibited higher catalyst activity. Compared to Examples B5 and Examples B8-B10, Example B5 exhibited higher catalyst activity by optimizing the material composition of the catalyst composition. Compared to Example B5 and Example B11, Example B5 exhibited higher catalyst activity by optimizing the composition of the reaction solvent used in the polymerization reaction.

[0137] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. An organic phosphine ligand, characterized in that The organic phosphine ligand has a structure shown in formula (I): wherein R is selected from a C1-C10 alkyl group, a C6-C20 aryl group, a C3-C8 heterocyclic compound, a C1-C5 acyl group, a C1-C5 sulfonyl group, or a halogen-substituted C1-C10 alkyl group; k(X) represents that k hydrogen atoms on the benzene ring are replaced by X, k is an integer from 0 to 4, and k Xs are independently selected from a C1-C10 alkyl group, a C1-C10 alkoxy group, a halogen atom, an amino group, a nitro group, a sulfonic acid group, a C1-C10 alkoxycarbonyl group, a halogen-substituted C1-C10 alkyl group, or a C1-C10 acylamino group.

2. The organic phosphine ligand according to claim 1, characterized in that The organic phosphine ligand satisfies one or more of the following AB: A and R are selected from C1-C4 alkyl groups; preferably, R is methyl, ethyl or propyl; B. k is 0, 1 or 2. When k is 1 or 2, k Xs are independently selected from C1-C4 alkyl, halogen or C1-C4 acylamino groups; preferably, when k is 1 or 2, k Xs are independently selected from methyl, propyl, chlorine or CH3CONH-.

3. The organic phosphine ligand according to claim 1, characterized in that The structural formula of the organophosphine ligand is as follows:

4. A method for preparing the organophosphine ligand according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: subjecting compound a to a substitution reaction with compound b under the action of a basic catalyst to prepare an organic phosphine ligand; R and k(X) in the above compounds are defined as described in any one of claims 1 to 3, and L is a halogen atom.

5. The preparation method according to claim 4, characterized in that The preparation method satisfies one or more of the following A to F: A. The alkaline catalyst is selected from one or more of organic bases and inorganic bases; Optionally, the organic base is selected from one or more of tetramethylguanidine, N-(3-methoxyphenyl)guanidine, diphenylguanidine, 1,5,7-triazabicyclo[4,4,0]decene-5-ene, 1,8-diazabicyclo(5.4.0)undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene; Optionally, the amount of the organic base is 4.5-10.0 mol% of the molar amount of compound a; Optionally, the inorganic base is selected from one or more of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, lithium phosphate, sodium phosphate, calcium phosphate, and cesium phosphate; Optionally, the amount of the inorganic base is 210.0-350.0 mol% of the molar amount of compound a; B. The amount of compound b is 200.0 to 350.0 mol%, preferably 220.0 to 300.0 mol%, of the molar amount of compound a; C. The reaction system of the substitution reaction further comprises an iodine salt; Optionally, the iodine salt is selected from one or more of lithium iodide, sodium iodide, and potassium iodide; Optionally, the amount of the iodine salt is 4.5-10.0 mol% of the molar amount of compound a; D. The reaction solvent of the substitution reaction is selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, dichloroethane, and chloroform; preferably tetrahydrofuran and / or acetonitrile; E. The reaction temperature of the substitution reaction is 0 to 25° C., the reaction pressure is normal pressure, and the reaction time is 8 to 12 hours; F. The compound a is selected from o-catechol, 3,6-dimethyl-1,2-benzenediol, 4-isopropyl-1,2-benzenediol, 4-chloro-1,2-benzenediol or 4-acetylamino-1,2-benzenediol; and / or, the compound b is selected from di(2-methoxyphenyl)phosphine chloride or di(2-ethoxyphenyl)phosphine chloride.

6. The preparation method according to claim 4 or 5, characterized in that The preparation method specifically comprises the following steps: mixing a reaction solvent with compound a, a basic catalyst and an iodine salt to obtain a mixed solution, dropwise adding a solution containing compound b into the mixed solution, and reacting to obtain an organic phosphine ligand; Optionally, after the reaction, the step of filtering the filtrate, evaporating the solvent, collecting the crude product and purifying the crude product is further included; Optionally, the concentration of the solution containing compound b is 0.1-0.5 g / mL; Optionally, the ratio of the volume of the reaction solvent to the molar amount of compound a is 30-50 mL: 4-15 mmol; Optionally, the ratio of the volume of the solution containing compound b to the molar amount of compound a is 15-20 mL:4-15 mmol.

7. A catalyst composition, characterized in that The organic phosphine ligand comprises the organic phosphine ligand according to any one of claims 1 to 3 or the organic phosphine ligand prepared by the preparation method according to any one of claims 4 to 6, and further comprises an active metal; Optionally, the active metal is selected from one or more of palladium, nickel, and platinum; Optionally, the molar ratio of the active metal to the organophosphine ligand is 1:1-1.

2.

8. The catalyst composition according to claim 7, characterized in that The catalyst composition further comprises a monodentate phosphine ligand and / or an acid; Preferably, the acid is selected from one or more of trifluoroacetic acid, trichloroacetic acid, methanesulfonic acid, toluenesulfonic acid, sulfuric acid, and trifluoromethanesulfonic acid; Preferably, the molar ratio of the acid to the active metal is 4-7:1; Preferably, the monodentate phosphine ligand is selected from one or more of triphenylphosphine, tri(2-methylphenyl)phosphine, tri(3-methylphenyl)phosphine, tri(4-methylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, and tri(1-naphthyl)phosphine; Preferably, the molar ratio of the monodentate phosphine ligand to the active metal is 2.5-7:1; More preferably, the catalyst composition comprises the active metal, the organic phosphine ligand, methanesulfonic acid and tris(2-methoxyphenyl)phosphine in a molar ratio of 1:1-1.2:4-7:2.5-7.

9. Use of the catalyst composition according to claim 7 or 8 in catalyzing the polymerization of olefins and carbon monoxide to prepare polyketones.

10. A method for preparing a polyketone, characterized in that: The method comprises the following steps: in the presence of the catalyst composition according to claim 7 or 8, polymerizing olefins with carbon monoxide to obtain polyketone; Preferably, one or more of the following A and F are met: A. The olefin is selected from one or more of ethylene, propylene, and 1-butene; and / or the molar ratio of the olefin to carbon monoxide is 0.5-2:1; B. The reaction pressure of the polymerization reaction is 3.0 to 6.0 MPaG; C. The reaction temperature of the polymerization reaction is 60 to 80° C. D. The reaction time of the polymerization reaction is 1 to 3 hours; E. The reaction solvent of the polymerization reaction is selected from one or more of methanol and water, preferably a methanol solution containing 2000 to 6000 ppm of water; F. The mass ratio of the organic phosphine ligand in the catalyst composition to the reaction solvent in the polymerization reaction is 1:20,000-50,000.

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