Bidentate phosphite polymers, methods for their preparation and use, and methods for olefin carbonylation

Abstract

The application provides a bidentate phosphite polymer, a preparation method and application thereof, and a method for olefin carbonyl synthesis reaction. The bidentate phosphite polymer provided by the application is shown in formula (I) and is copolymerized by a specific bidentate phosphite ligand and 2-vinyl naphthalene. The bidentate phosphite polymer can be used in catalyzing the olefin carbonyl synthesis reaction, can not only ensure the catalytic performance of the olefin carbonyl synthesis reaction, but also can improve the solvent swelling resistance of the polymer, thereby being beneficial to ensuring the catalyst form stability and being beneficial to the stable production of aldehydes synthesized by the olefin carbonyl synthesis.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of material synthesis, in particular to a bidentate phosphite polymer, a preparation method and application thereof, and a method of olefin carbonylation synthesis. BACKGROUND

[0002] In 1938, Otto Roelen of the Ruhr Chemical Plant in Germany accidentally discovered that, in the presence of a catalyst composed of cobalt, rhodium and magnesium oxide, ethylene, carbon monoxide and hydrogen reacted to generate not only alkanes, but also diethyl ketone and propionaldehyde, which was the earliest discovery of carbonylation synthesis. Carbonylation synthesis technology is widely used, and the annual production of olefin carbonylation synthesis products worldwide has exceeded 12 million tons, and the generated aldehyde, alcohol, acid, ester, amine and other products are widely used in the synthesis of plasticizers, surfactants, solvents, drugs and fragrances, etc.

[0003] The transition metals commonly used in carbonylation synthesis are cobalt, rhodium, ruthenium, palladium, platinum, iridium, iron, etc., and the ligands are triphenylphosphine, phosphite, phosphoramidite, etc. Organic ligands play an important role in changing the inherent catalytic properties of the metal in carbonylation synthesis, and have a great influence on the reaction activity, chemical, regional and spatial selectivity of the catalyst. After more than 80 years of development, carbonylation synthesis technology has become increasingly sophisticated, but there are still some deficiencies. Low-carbon olefins use homogeneous rhodium process, after the reaction is completed, the generated aldehyde needs to be distilled out by high-temperature distillation process, which has high energy consumption. High-carbon olefin carbonylation synthesis uses high-pressure cobalt process, after the reaction is completed, acetic acid is added to dissolve the cobalt catalyst into an aqueous solution, realizing the separation of the catalyst and the reaction product, and the catalyst treatment process is complex.

[0004] In recent years, a heterogeneous carbonylation synthesis method has been developed, as disclosed in patent applications CN108067307, CN104710289, CN104707663 and CN110343209, etc. An ethylene group is introduced into the phosphine ligand, and then polymerized to form a high molecular polymer. The high molecular polymer is not only a carrier for transition metals, but also an organic ligand, which can catalyze the carbonylation synthesis reaction of olefins, and after the reaction is completed, the catalyst and the reaction product can be easily separated. Compared with the existing homogeneous rhodium process, the energy consumption for separation of the catalyst and the reaction product is greatly reduced; compared with the high-pressure cobalt process, the complex catalyst and reaction product separation process is avoided.

[0005] However, in the current patent technology, the high molecular polymer formed by polymerization of small molecule phosphine ligands or copolymerization with styrene usually has low strength and poor stability. The pores are easy to collapse during the drying process, and the catalyst form changes during use due to swelling when in contact with organic solvents, which is not conducive to stable production. SUMMARY

[0006] Therefore, the application provides a bidentate phosphite polymer, a preparation method and application thereof, and a method for olefin carbonyl synthesis.

[0007] The application provides a bidentate phosphite polymer having a structure shown in formula (I).

[0008]

[0009]

[0010] m and n are polymerization degrees, and a copolymerization ratio of m:n is (0.1-10):(0.1-10).

[0011] Preferably, the weight average molecular weight is 70000-110000 g / mol.

[0012] Preferably, the copolymerization ratio of m:n is (0.5-5):(0.5-5).

[0013] Preferably, the copolymerization ratio of m:n is (0.8-2):(0.8-2).

[0014] The application further provides a preparation method of the bidentate phosphite polymer.

[0015] a) reacting compound A with phosphorus trichloride to obtain compound B;

[0016] b) under alkaline conditions, compound C is subjected to oxidative coupling to obtain compound D;

[0017] c) reacting the compound B with the compound D to obtain compound E;

[0018] d) copolymerizing the compound E with 2-vinyl naphthalene to obtain the bidentate phosphite polymer shown in formula (I);

[0019] The steps a) and b) are not limited in sequence.

[0020] The structures of the compounds A-E are as follows.

[0021]

[0022] Preferably, in the step a), the reaction temperature is 40-100 DEG C, and the reaction time is 2-8 h.

[0023] In the step b), the oxidative coupling reaction temperature is 50-100 DEG C, and the reaction time is 1-5 h.​

[0024] Preferably, in step c), the temperature of the reaction is -20-20℃, and the time is 1-20h.

[0025] In step d), the temperature of the reaction is 60-120℃, and the time is 10-30h.

[0026] The application further provides the use of the bidentate phosphite polymer in the technical solution in the above in olefin carbonyl synthesis reaction.

[0027] The application further provides a method for olefin carbonyl synthesis reaction, comprising the following steps: mixing bidentate phosphite polymer, acetylacetone dicarbonyl rhodium, olefin and solvent to react.

[0028] The bidentate phosphite polymer is the bidentate phosphite polymer in any one of claims 1-4.

[0029] Preferably, the olefin is at least one of α-olefin, linear internal olefin, branched internal olefin, branched terminal olefin, cyclic olefin, vinyl aromatic hydrocarbon, diene and polyene.

[0030] The bidentate phosphite polymer provided by the application is shown in formula (I), which is copolymerized by a specific bidentate phosphite ligand and 2-vinyl naphthalene, and can be used in catalyzing olefin carbonyl synthesis reaction, which not only ensures the catalytic performance of olefin carbonyl synthesis reaction, but also improves the solvent swelling resistance of the polymer, thereby being beneficial to ensuring the stability of the catalyst form and the stable production of aldehydes in olefin carbonyl synthesis.

[0031] The experimental results show that the bidentate phosphite polymer shown in formula (I) obtained by the application can make the conversion rate of olefin raw materials reach more than 83% and the selectivity of aldehyde main product reach more than 96% in catalyzing olefin carbonyl synthesis reaction, thereby ensuring good catalytic performance. Meanwhile, the bidentate phosphite polymer shown in formula (I) obtained by the application has good particle morphology after being soaked in solvent, and shows excellent solvent swelling resistance, that is, the bidentate phosphite polymer catalyst shown in formula (I) provided by the application improves the solvent swelling resistance of the material on the basis of ensuring the catalytic performance, thereby being beneficial to the stable production of aldehydes in olefin carbonyl synthesis. BRIEF DESCRIPTION OF DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only the embodiments of the application, and other drawings can be obtained by those skilled in the art without any creative effort on the basis of the provided drawings.

[0033] Figure 1 NMR spectrum of the bidentate phosphite polymer obtained in Example 1;

[0034] Figure 2 NMR spectrum of the bidentate phosphite polymer obtained in Example 1;

[0035] Figure 3 Adsorption-desorption curve of the bidentate phosphite polymer obtained in Example 1;

[0036] Figure 4 Thermogravimetric analysis curve of the bidentate phosphite polymer obtained in Example 1;

[0037] Figure 5 SEM image of the bidentate phosphite polymer obtained in Example 1;

[0038] Figure 6 Anti-swelling test effect diagram of the test sample of Example 1;

[0039] Figure 7 Anti-swelling test effect diagram of the comparative sample. DETAILED DESCRIPTION

[0040] The present application provides a bidentate phosphite polymer, having a structure shown in formula (I):

[0041]

[0042] wherein,

[0043] m and n are polymerization degrees, and the copolymerization ratio of m:n is (0.1-10):(0.1-10), preferably (0.5-5):(0.5-5), and more preferably (0.8-2):(0.8-2).

[0044] In the present application, the polymerization degree m is preferably 70-120, and specifically can be 70, 80, 90, 100, 110 or 120. The polymerization degree n is preferably 70-120, and specifically can be 70, 80, 90, 100, 110 or 120.

[0045] In the present application, the weight average molecular weight of the bidentate phosphite polymer shown in formula (I) is preferably 70000-110000 g / mol, and specifically can be 70000 g / mol, 80000 g / mol, 90000 g / mol, 100000 g / mol or 110000 g / mol.

[0046] The present application also provides a preparation method of the bidentate phosphite polymer described in the above technical solution, comprising the following steps:

[0047] a) the compound A reacts with phosphorus trichloride to obtain compound B;

[0048] b) the compound C is subjected to oxidative coupling reaction under alkaline condition to obtain compound D;

[0049] c) the compound B reacts with the compound D to obtain compound E;

[0050] d) the compound E is subjected to copolymerization reaction with 2-vinyl naphthalene to obtain the bidentate phosphite polymer shown in formula (I);

[0051] wherein, the step a) and the step b) are not limited in sequence;

[0052] the structures of the compound A to the compound E are as follows:

[0053]

[0054]

[0055] Regarding step a) : the compound A reacts with phosphorus trichloride to obtain compound B.

[0056] in the present application, the reaction route of the above step a) is as follows:

[0057]

[0058] in the present application, the compound A (i.e. the compound shown in the above formula A) is 2,2'-diphenylol, which is not limited in source, and can be a commercial product or prepared according to the conventional preparation method in the art.

[0059] in the present application, the source of the phosphorus trichloride (PCl3) is not limited, and can be a commercial product.

[0060] in the present application, the use amount ratio of the compound A to the phosphorus trichloride is preferably (10-30) g:(5-25) mL, and can be 10 g:5 mL, 13.9 g:13.1 mL or 30 g:25 mL.

[0061] in the present application, the reaction is preferably carried out under a protective atmosphere. The present application is not limited in the type of the protective gas for providing the protective atmosphere, and can be a conventional protective gas in the art, such as nitrogen or argon.

[0062] In the present application, the reaction is preferably carried out in an organic solvent medium. In the present application, the organic solvent is preferably at least one of toluene, xylene, ethylbenzene, tetrahydrofuran and acetonitrile. In the present application, the ratio of the amount of organic solvent to compound A is preferably (20-100) mL : (10-30) g, and can be specifically 20 mL : 10 g, 60 mL : 13.9 g, 100 mL : 30 g.

[0063] In the present application, the temperature of the reaction is preferably 40-100°C, and can be specifically 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C. The reaction time is preferably 2-8 h, and can be specifically 2 h, 3 h, 4 h, 5 h, 6 h, 7 h or 8 h.

[0064] In the present application, step a) preferably specifically comprises the following steps: under a protective atmosphere, mixing compound A with an organic solvent, starting stirring, adding phosphorus trichloride dropwise to the system, raising the reaction temperature to carry out the reaction, and obtaining compound B. The stirring rate is preferably 100-500 rpm. The dropwise addition is preferably carried out slowly using a constant-pressure dropping funnel.

[0065] In the present application, after the above reaction, the following post-treatment is preferably carried out: distillation under reduced pressure, and distilling off excess phosphorus trichloride and organic solvent, thereby obtaining compound B (6-chloro-dibenzo[d,f][1,3,2]-dioxaphosphepin), which is an oily liquid.

[0066] Regarding step b) Under alkaline conditions, compound C undergoes oxidative coupling to obtain compound D.

[0067] In the present application, the reaction route of step b) is as follows:

[0068]

[0069] In the present application, the alkaline conditions are using an alkaline substance solution as the medium of the reaction system, and the alkaline substance solution is preferably at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution and potassium carbonate aqueous solution. In the present application, the mass percentage concentration of the alkaline substance solution is preferably 2%-20%, and can be specifically 2%, 5%, 10%, 15% or 20%.

[0070] In the present application, compound C (i.e. the compound represented by the above formula C) is 2-vinyl-4-tert-butyl-phenol, and its source is not particularly limited, and can be a commercially available product or prepared according to conventional methods in the art. In the present application, the ratio of the amount of compound C to the alkaline substance solution is preferably (5-50) g : 100 g, and can be specifically 5 g : 100 g, 26.4 g : 100 g or 100 g : 100 g.

[0071] In the present application, an oxidizing agent is preferably added in step b) to allow the oxidative coupling reaction of compound C. In the present application, the oxidizing agent is preferably hydrogen peroxide. In the present application, the ratio of the amount of the oxidizing agent to the amount of compound C is preferably (10-50) mL : (10-50) g, and more specifically 10 mL : 10 g, 30 mL : 26.4 g, or 40 mL : 45 g.

[0072] In the present application, the oxidative coupling reaction is preferably carried out at a temperature of 50-100°C, and more specifically at 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C. The reaction time is preferably 1-5 h, and more specifically 1 h, 2 h, 3 h, 4 h, or 5 h.

[0073] In the present application, step b) preferably specifically comprises adding a solution of an alkaline substance, compound C, and an oxidizing agent into a reactor, and then carrying out the oxidative coupling reaction at an elevated temperature to obtain compound D (2,2'-divinyl-4,4'-di-tert-butyl-biphenol).

[0074] In the present application, after the above reaction, the following post-treatment is preferably carried out: filtration, washing, and drying. The washing is preferably carried out with water. The drying is preferably carried out at a temperature of 50-110°C. After the above post-treatment, compound D is obtained as a white solid.

[0075] In the present application, the order of steps a) and b) is not particularly limited.

[0076] Regarding step c) The compound B is reacted with compound D to obtain compound E.

[0077] In the present application, the reaction route of step c) is as follows:

[0078]

[0079] In the present application, the mass ratio of compound D to compound B is preferably (10-20) : 12.5, and more specifically 10 : 12.5, 17.5 : 12.5, or 20 : 12.5.

[0080] In the present application, the reaction is preferably carried out in a protective atmosphere. The type of protective gas for providing the protective atmosphere is not particularly limited, and any conventional protective gas in the art can be used, such as nitrogen or argon.

[0081] In the present application, the reaction is preferably carried out in an organic solvent medium. In the present application, the organic solvent is preferably at least one of tetrahydrofuran, toluene, acetonitrile, and N,N-dimethylformamide.

[0082] In the present application, the reaction is preferably carried out under the action of an acid-binding agent. In the present application, the acid-binding agent is preferably at least one of triethylamine, pyridine and imidazole. In the present application, the mass ratio of the acid-binding agent to compound D is preferably (5-20):17.5, and can be specifically 5:17.5, 15:17.5 or 20:17.5.

[0083] In the present application, the temperature of the reaction is preferably -20-30℃, and can be specifically -20℃, -10℃, 0℃, 10℃, 20℃ or 30℃. The time of the reaction is preferably 1-20h, and can be specifically 1h, 5h, 10h, 15h or 20h.

[0084] In the present application, step a) preferably specifically comprises: under a protective atmosphere, adding an organic solvent, compound D and an acid-binding agent into a reaction container, starting stirring, and cooling; then, adding a solution of compound B dropwise into the reaction container, after the dropwise addition is completed, carrying out a reaction to obtain compound E (6,6'-[(3,3'-divinyl-5,5'-di-tert-butyl-[1,1'-biphenyl]-2,2'-diyl)bis(oxy)]bisdibenzo[d,f][1,3,2]-dioxaphosphepin).

[0085] In the present application, step a) preferably specifically comprises: under a protective atmosphere, adding an organic solvent, compound D and an acid-binding agent into a reaction container, starting stirring, and cooling; then, adding a solution of compound B dropwise into the reaction container, after the dropwise addition is completed, carrying out a reaction to obtain compound E (6,6'-[(3,3'-divinyl-5,5'-di-tert-butyl-[1,1'-biphenyl]-2,2'-diyl)bis(oxy)]bisdibenzo[d,f][1,3,2]-dioxaphosphepin).

[0086] The type and amount of the acid-binding agent are as described above and will not be repeated here.

[0087] The type and amount of the acid-binding agent are as described above and will not be repeated here.

[0088] The stirring rate is preferably 100-500rpm.

[0089] The cooling method is preferably cold-bath cooling. The cooling is preferably to 5℃.

[0090] The solution of compound B is preferably a solution formed by dissolving compound B in an organic solvent. The organic solvent is preferably at least one of tetrahydrofuran, toluene and acetonitrile. The amount ratio of compound B to the organic solvent is preferably 12.5g:(10-30)mL, and can be specifically 12.5g:10mL, 12.5g:20mL or 12.5g:30mL.

[0091] The dropwise addition is preferably slow dropwise addition by using a constant-pressure dropping funnel.

[0092] The temperature and time of the reaction are as described above and will not be repeated here. After the above reaction, compound E is obtained.

[0093] In the present application, after the above reaction, the following post-treatment is preferably performed: extraction with an extraction agent, collection of the organic phase, rotary evaporation and column chromatography separation. The extraction agent is preferably ethyl acetate. After the above post-treatment, compound E is obtained as a solid.

[0094] Regarding step d) :

[0095] d) copolymerization of compound E with 2-vinyl naphthalene to obtain the bidentate phosphite polymer shown in formula (I).

[0096] In the present application, the reaction route of step d) is as follows:

[0097]

[0098] In the present application, the molar ratio of compound E to 2-vinyl naphthalene is m:n, and the ratio m:n is as described above and will not be repeated here. In the present application, compound E is used as a ligand and 2-vinyl naphthalene is used as an ethenylating raw material to prepare a bidentate phosphite polymer. Compared with other organic phosphine ligands and other vinyl compounds, not only the catalytic performance of the polymer catalyst is ensured, but also the strength and solvent swelling resistance of the polymer are improved.

[0099] In the present application, the reaction is preferably performed under a protective atmosphere. The type of protective gas for providing the protective atmosphere is not particularly limited in the present application, and any conventional protective gas in the art can be used, such as nitrogen or argon.

[0100] In the present application, the reaction is preferably performed in an organic solvent medium. In the present application, the organic solvent is preferably at least one of tetrahydrofuran, toluene and acetonitrile. In the present application, the ratio of the amount of the organic solvent to the amount of compound E is preferably (50-100) mL:(5-20) g, and specifically can be 100 mL:10 g.

[0101] In the present application, the reaction is preferably performed in the presence of an initiator. In the present application, the initiator is preferably at least one of azobisisoheptane nitrile, azobisisobutane nitrile and benzoyl peroxide. In the present application, the amount of the initiator is preferably 0.1%-5% of the mass of compound E, and specifically can be 0.1%, 0.5%, 1%, 2%, 2.8%, 4%, 5%.

[0102] In the present application, the temperature of the reaction is preferably 60-120°C, and specifically can be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C. The time of the reaction is preferably 10-30 h, and specifically can be 10 h, 15 h, 20 h, 25 h, 30 h.

[0103] In the present application, the step d) preferably specifically comprises: adding compound E, 2-vinyl naphthalene, initiator and organic solvent into the reaction container under a protective atmosphere, starting stirring, heating and reacting to obtain the bidentate phosphite polymer shown in formula (I). The stirring rate is preferably 100-500 rpm.

[0104] In the present application, after the above reaction, the post-treatment of cooling and drying is preferably further performed. The cooling is preferably to room temperature. The drying is preferably vacuum drying. The drying temperature is preferably 40-80℃. After the above post-treatment, the bidentate phosphite polymer shown in formula (I) is obtained, which is a white solid.

[0105] The present application also provides the use of the bidentate phosphite polymer described in the above technical solution in olefin carbonyl synthesis reaction. The bidentate phosphite polymer acts as a catalyst, specifically as an auxiliary catalyst in olefin carbonyl synthesis reaction.

[0106] The present application also provides a method for olefin carbonyl synthesis reaction, comprising the following steps: mixing bidentate phosphite polymer, acetylacetone dicarbonyl rhodium, olefin and solvent for reaction.

[0107] In the present application, the step d) preferably specifically comprises: adding compound E, 2-vinyl naphthalene, initiator and organic solvent into the reaction container under a protective atmosphere, starting stirring, heating and reacting to obtain the bidentate phosphite polymer shown in formula (I). The stirring rate is preferably 100-500 rpm.

[0108] The bidentate phosphite polymer is the bidentate phosphite polymer shown in formula (I) described in the above technical solution. The mass ratio of the bidentate phosphite polymer to acetylacetone dicarbonyl rhodium is preferably 1.2g:(5-50)mg, specifically 1.2g:5mg, 1.2g:12.5mg, 1.2g:50mg. The amount of acetylacetone dicarbonyl rhodium is preferably 0.005%-0.05% of the mass of olefin, specifically 0.01%, 0.02%, 0.03%, 0.04%.

[0109] The bidentate phosphite polymer of formula (I) is particularly suitable as a catalyst ligand for the hydroformylation reaction of an olefin feedstock containing one or more olefinically unsaturated double bonds. The olefin is a reaction feedstock, and the kind thereof is preferably at least one of α-olefin, linear internal olefin, branched internal olefin, branched terminal olefin, cyclic olefin, vinyl aromatic hydrocarbon, diene and polyene. Among them, the α-olefin is preferably at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. The branched internal olefin is preferably at least one of 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, 2,4,4-trimethyl-1-pentene, branched internal heptene mixture, branched internal octene mixture, branched internal nonene mixture, branched internal decene mixture, branched internal undecene mixture and branched internal dodecene mixture. The cyclic olefin is preferably at least one of cyclopentene, cyclohexene, cycloheptene, cyclooctene and cyclooctene derivative. The vinyl aromatic hydrocarbon is preferably at least one of styrene, α-methylstyrene and 4-isobutylstyrene. The diene and polyene are preferably at least one of 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene and vinyl cyclohexene. In the present application, the olefin is most preferably at least one of 1-butene, 2-methyl-2-butene, 2,4,4-trimethyl-1-pentene and styrene.

[0110] The solvent is preferably at least one of toluene, tetrahydrofuran and n-hexane. The ratio of the solvent to the olefin is preferably 50 mL:(0.5-2) mol.

[0111] The temperature of the reaction is preferably 50-150°C, and specifically can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C. The time of the reaction is preferably 1-24 h, and specifically can be 1 h, 4 h, 8 h, 12 h, 16 h, 20 h or 24 h.

[0112] In the present application, the above reaction process preferably specifically comprises: adding the bidentate phosphite polymer, acetylacetone dicarbonyl rhodium, olefin and solvent into a reaction kettle, performing gas replacement on the reactor with inert gas, stirring at room temperature, performing gas replacement on the reactor with synthesis gas, charging the synthesis gas to a pressure of 0.2-8 MPa, and stirring at 50-150°C.

[0113] wherein:

[0114] The inert gas is not particularly limited, and can be a conventional protective gas known to those skilled in the art, such as nitrogen or argon. The number of times of replacement with the inert gas is preferably 3. The stirring rate at room temperature is preferably 100-500 rpm, and the time is preferably 24 h. The synthesis gas is a mixed gas of hydrogen and carbon monoxide; the volume ratio of hydrogen to carbon monoxide is preferably 1:1. The number of times of replacement with the synthesis gas is preferably 3. The pressure of the synthesis gas can be 0.2 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, or 8 MPa. The stirring rate of the stirring reaction is preferably 100-500 rpm. The temperature and time of the stirring reaction are as described above, and are not described here again. After the above reaction, the following steps are further performed: cooling, depressurization of the reaction kettle, replacement with an inert gas, opening of the reaction kettle, sampling, and obtaining of the reaction product.

[0115] The present application adopts bidentate phosphite polymer as a cocatalyst and acetylacetone dicarbonyl rhodium as a main catalyst to catalyze the carbonyl synthesis reaction of an olefin raw material, so as to obtain an aldehyde main product. Specifically, after the bidentate phosphite polymer and the acetylacetone dicarbonyl rhodium are introduced into the system, the two undergo a chemical reaction to form a modified rhodium-based substance of formula (I), which, as a catalyst, not only ensures the catalytic performance of the olefin carbonyl synthesis reaction, but also improves the solvent swelling resistance of the polymer, thereby being conducive to ensuring the stability of the catalyst form and further being conducive to the stable production of the olefin carbonyl synthesis aldehyde.

[0116] The experimental results show that the bidentate phosphite polymer of formula (I) obtained by the present application can make the conversion rate of the olefin raw material reach more than 83% and the selectivity of the aldehyde main product reach more than 96% in the catalysis of the olefin carbonyl synthesis reaction, thereby ensuring good catalytic performance. Meanwhile, the bidentate phosphite polymer of formula (I) obtained by the present application has a good particle morphology after being soaked in a solvent and exhibits excellent solvent swelling resistance, that is, the bidentate phosphite polymer catalyst of formula (I) provided by the present application improves the solvent swelling resistance of the material on the basis of ensuring the catalytic performance, thereby being conducive to the stable production of the olefin carbonyl synthesis aldehyde.

[0117] In order to further understand the present application, the preferred embodiments of the present application are described below in conjunction with examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present application, and are not a limitation on the claims of the present application.

[0118] The instruments used for material characterization in the following examples are as follows: (1) Thermogravimetric-differential scanning calorimeter: Model TGA-2, manufactured by Mettler Toledo. (2) Scanning electron microscope: Model Apreo S HiVac, manufactured by Thermo Fisher. (3) Physical adsorption instrument: Model QDS-MP-30, manufactured by Quantachrome.

[0119] Example 1

[0120] 1. Sample preparation

[0121] a) Under nitrogen protection, 13.9 g of compound A and 60 mL of toluene were added to a 100 mL four-necked flask, stirring was started, and 13.1 mL of phosphorus trichloride was added dropwise to the four-necked flask using a constant-pressure dropping funnel, and the temperature was raised to 80°C for 6 h of reaction. Then, excess phosphorus trichloride and toluene were distilled out under reduced pressure to obtain 15.2 g of an oily liquid, which was compound B.

[0122]

[0123] b) In 80 g of an aqueous sodium hydroxide solution (2% by mass concentration), 26.4 g of compound C was added, and then 30 mL of hydrogen peroxide was added, and the temperature was raised to 70°C for 2 h of oxidative coupling reaction. Then, filtration, washing, and drying were performed to obtain 21.6 g of a white solid, which was compound D.

[0124]

[0125] c) Under nitrogen protection, 60 mL of tetrahydrofuran, 17.5 g of compound D, and 15 g of triethylamine acid acceptor were added to a 250 mL four-necked flask, stirring was started, and the temperature was lowered to 5°C using a cold bath. Then, 12.5 g of compound B was dissolved in 20 mL of tetrahydrofuran to form a compound B solution, and the compound B solution was slowly added to the four-necked flask using a constant-pressure dropping funnel, and after the addition was completed, the temperature was raised to 30°C for 1 h of reaction. Then, extraction was performed twice with ethyl acetate, the organic phase was collected, rotary evaporation was performed, and column chromatography separation was performed to obtain 22 g of a solid, which was compound E.

[0126]

[0127] d) Under nitrogen protection, 10 g of compound E, 8 g of 2-vinyl naphthalene, 0.28 g of azobisisoheptane nitrile initiator, and 100 mL of tetrahydrofuran were added to a 200 mL reaction kettle, stirring was started, the temperature was raised to 100°C for 24 h of reaction. Then, the temperature was lowered to room temperature, and vacuum drying was performed to obtain 18 g of a white solid, which was a bidentate phosphite polymer represented by formula (I).

[0128]

[0129] 2. Sample characterization

[0130] The bidentate phosphite polymer obtained in Example 1 was subjected to nuclear magnetic spectrum analysis, and the results are shown in Table 1. Figures 1-2 Figure 1 The bidentate phosphite polymer obtained in Example 1 was subjected to nuclear magnetic spectrum analysis, and the results are shown in Table 1. Figure 2 The bidentate phosphite polymer obtained in Example 1 was subjected to nuclear magnetic spectrum analysis, and the results are shown in Table 1.

[0131] The bidentate phosphite polymer obtained in Example 1 was subjected to BET detection, and the adsorption analysis curve is shown in Table 2. Figure 3 The results show that the specific surface area of the bidentate phosphite polymer obtained in Example 1 is 582 m 2 / g, and the pore volume is 0.909 cm 3 / g.

[0132] The bidentate phosphite polymer obtained in Example 1 was subjected to thermal gravimetric analysis, and the results are shown in Table 3. Figure 4 Figure 4 The bidentate phosphite polymer obtained in Example 1 was subjected to thermal gravimetric analysis, and the results are shown in Table 3.

[0133] The bidentate phosphite polymer obtained in Example 1 was subjected to scanning electron microscope observation, and the results are shown in Table 4. Figure 5 Figure 5 The bidentate phosphite polymer obtained in Example 1 was subjected to scanning electron microscope observation, and the results are shown in Table 4.

[0134] 3. Sample anti-swelling test

[0135] Test sample: The bidentate phosphite polymer obtained in Example 1 of the present application.

[0136] Comparative sample: The polymer obtained in Example 1 of patent application CN104707663.

[0137] Test process: 3 g of polymer sample was weighed and placed in 50 mL of toluene, sealed and soaked at room temperature for 24 h, and then the polymer morphology was observed.

[0138] After the above soaking, the morphologies of the test sample and the comparative sample are shown in Table 5. Figures 6-7 Figure 6 The anti-swelling test effect of the test sample of Example 1 is shown in Table 5. Figure 7 The anti-swelling test effect of the test sample of Example 1 is shown in Table 5.It can be seen that the particle morphology of the test sample is well preserved, and the anti-solvent swelling effect is excellent; while the comparative sample swells seriously and disperses into a flocculent shape in the solvent, and cannot maintain stable morphology.​​​

[0139] Application Example 1

[0140] Take 1.2 g of the bidentate phosphite polymer obtained in Example 1, 12.5 mg of acetylacetone dicarbonyl rhodium, 5.6 g of 1-butene and 50 mL of toluene, and add them to a 100 mL high-pressure reaction kettle. Replace the nitrogen three times, stir at room temperature for 24 h, replace the synthesis gas three times, pressurize the synthesis gas to 1.5 MPa, and stir at 80°C for 6 h. Then cool, depressurize the reaction kettle, replace the nitrogen two times, open the reaction kettle, take samples, and analyze by gas chromatography.

[0141] Result: The conversion rate of 1-butene is 96.2%, the selectivity of n-pentanal is 56.2%, the selectivity of 2-methylbutanal is 42.3%, and the selectivity of n-butane is 1.5%.

[0142] Application Example 2

[0143] Take 0.3 g of the bidentate phosphite polymer obtained in Example 1, 6.25 mg of acetylacetone dicarbonyl rhodium, 7.0 g of 2-methyl-2-butene and 50 mL of toluene, and add them to a 100 mL high-pressure reaction kettle. Replace the nitrogen three times, stir at room temperature for 24 h, replace the synthesis gas three times, pressurize the synthesis gas to 2.5 MPa, and stir at 100°C for 8 h. Then cool, depressurize the reaction kettle, replace the nitrogen two times, open the reaction kettle, take samples, and analyze by gas chromatography.

[0144] Result: The conversion rate of 2-methyl-2-butene is 83.4%, the selectivity of 3-methylpentanal is 62.8%, the selectivity of 4-methylpentanal is 33.7%, and the selectivity of 2-methylbutane is 3.5%.

[0145] Application Example 3

[0146] Take 0.6 g of the bidentate phosphite polymer obtained in Example 1, 9.2 mg of acetylacetone dicarbonyl rhodium, 11.2 g of 2,4,4-trimethyl-1-pentene and 50 mL of toluene, and add them to a 100 mL high-pressure reaction kettle. Replace the nitrogen three times, stir at room temperature for 24 h, replace the synthesis gas three times, pressurize the synthesis gas to 5.0 MPa, and stir at 110°C for 9 h. Then cool, depressurize the reaction kettle, replace the nitrogen two times, open the reaction kettle, take samples, and analyze by gas chromatography.

[0147] Result: The conversion rate of 2,4,4-trimethyl-1-pentene is 92.5%, the selectivity of 3,5,5-trimethylhexanal is 97.2%, and the selectivity of 2,2,4-trimethylpentane is 2.8%.

[0148] Application Example 4

[0149] Take 1.4 g of the bidentate phosphite polymer obtained in Example 1, 15.6 mg of acetylacetone rhodium dicarbonyl, 10.4 g of styrene and 50 mL of toluene into a 100 mL high-pressure reaction kettle, replace with nitrogen for 3 times, stir at room temperature for 24 h, replace with synthesis gas for 3 times, charge the synthesis gas to 3.0 MPa, stir at 120℃ for 12 h. Then cool down, release the pressure of the reaction kettle, replace with nitrogen for 2 times, open the reaction kettle, take sample, and analyze by gas chromatography.

[0150] Result: the conversion rate of styrene is 88.2%, the selectivity of phenylpropanal is 68.3%, the selectivity of 2-phenylpropanal is 28.1%, and the selectivity of ethylbenzene is 3.6%.

[0151] The catalytic reaction effects of the application examples 1-4 are summarized in Table 1:

[0152] Table 1: catalytic reaction effects of the application examples 1-4

[0153] Olefin feedstock Olefin feedstock conversion, % Aldehyde main product selectivity, % Other product selectivity, % Application Example 1 1-butene 96.2 98.5 1.5 Application Example 2 2-methyl-2-butene 83.4 96.5 3.5 Application Example 3 2,4,4-trimethyl-1-pentene 92.5 97.2 2.8 Application Example 4 styrene 88.2 96.4 3.6

[0154] The above test results show that the bidentate phosphite polymer represented by formula (I) obtained by the present application can make the conversion rate of olefin raw material reach more than 83% and the selectivity of aldehyde main product reach more than 96% in the catalytic olefin carbonyl synthesis reaction, which ensures good catalytic performance. At the same time, the bidentate phosphite polymer represented by formula (I) obtained by the present application has good particle morphology after solvent soaking, which shows excellent anti-solvent swelling effect. That is, the bidentate phosphite polymer catalyst represented by formula (I) provided by the present application improves the anti-swelling performance of the material on the basis of ensuring the catalytic performance, thereby being conducive to the stable production of olefin carbonyl synthesis aldehyde.

[0155] The principles and implementation modes of the present application are described by applying specific examples in this paper. The above examples are only used to help understand the method of the present application and its core idea, including the best mode, and also enable any person skilled in the art to practice the present application, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make some improvements and modifications to the present application without departing from the principles of the present application, and these improvements and modifications also fall within the protection scope of the claims of the present application. The scope of patent protection of the present application is defined by the claims, and can include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A bidentate phosphite polymer characterized in that, having a structure shown in formula (I): wherein, m and n are polymerization degrees, and a copolymerization ratio of m:n is (0.1-10):(0.1-10).

2. The bidentate phosphite polymer of claim 1, wherein, The weight average molecular weight is 70000-110000 g / mol.

3. The bidentate phosphite polymer of claim 1, wherein, The copolymerization ratio of m:n is (0.5-5):(0.5-5).

4. The bidentate phosphite polymer of claim 1, wherein, The copolymerization ratio of m:n is (0.8-2):(0.8-2).

5. A process for the preparation of the bidentate phosphite polymer of any one of claims 1 to 4, characterized in that, The method comprises the following steps: a) reacting compound A with phosphorus trichloride to obtain compound B; b) under alkaline conditions, compound C undergoes oxidative coupling to obtain compound D; c) reacting compound B with compound D to obtain compound E; d) copolymerizing compound E with 2-vinyl naphthalene to obtain the bidentate phosphite polymer shown in formula (I); wherein, steps a) and b) have no order limitation; The structures of the compounds A-E are as follows:

6. The preparation method according to claim 5, characterized in that, In step a), the reaction temperature is 40-100 DEG C, and the reaction time is 2-8 h; In step b), the oxidative coupling reaction temperature is 50-100 DEG C, and the reaction time is 1-5 h.

7. The preparation method according to claim 5, characterized in that, In step c), the reaction temperature is -20-20 DEG C, and the reaction time is 1-20 h; In step d), the reaction temperature is 60-120 DEG C, and the reaction time is 10-30 h.

8. Use of the bidentate phosphite polymer of any one of claims 1-4 in an olefin carbonyl synthesis reaction.

9. A method of olefin carbonylation synthesis reaction, characterized by, The method comprises the following steps: mixing the bidentate phosphite polymer, acetylacetone dicarbonyl rhodium, an olefin and a solvent to react; wherein, the bidentate phosphite polymer is the bidentate phosphite polymer of any one of claims 1-4.

10. The method of claim 9, wherein, The olefin is at least one of an alpha-olefin, a linear internal olefin, a branched internal olefin, a branched terminal olefin, a cyclic olefin, a vinyl aromatic hydrocarbon, a diene and a polyene.

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