Vinyl-functionalized phosphine ligands, their preparation and use

Abstract

The present application belongs to the field of organic chemistry and chemical engineering, and particularly relates to a method for high-yield and macro-production of a vinyl-functionalized phosphine ligand. The prepared vinyl-functionalized phosphine ligand can be used as a carrier of a heterogeneous catalyst for preparing a high-performance olefin hydroformylation catalyst after polymerization. By creatively adding a polymerization inhibitor in the process of preparing a vinyl-functionalized triphenylphosphine monomer, the polymerization of the vinyl group is effectively prevented, the monomer yield is improved, the micro-environment of the pores around the triphenylphosphine after polymerization is regulated by changing the position of the vinyl group on the benzene ring, the steric hindrance around the triphenylphosphine in the polymer skeleton is changed by introducing a large steric hindrance group on the benzene ring, and the production cost of the vinyl-functionalized phosphine ligand is greatly reduced by using p-(o,m)-chlorostyrene which is cheap and can be obtained in large quantities in industry as a starting material.

Description

Technical Field

[0001] This invention relates to a method for high-yield, large-scale production of vinyl-functionalized phosphine ligands, belonging to the fields of organic chemistry and chemical engineering. Background Technology

[0002] Triphenylphosphine has a lone pair of electrons on its phosphorus atom, making it a relatively strong Lewis base. It readily forms complexes with transition metals; for example, Pd(PPh3)4 is an important transition metal complex catalyst widely used in catalytic coupling reactions that construct carbon-carbon bonds. Currently, the most important application of triphenylphosphine in the chemical industry is in the preparation of rhodium-phosphine complex catalysts (Wilkinson Catalysts). These catalysts are indispensable for the hydroformylation reactions that produce high-value-added aldehydes and alcohols.

[0003] Since rhodium phosphine complexes are homogeneously dissolved in the hydroformylation reaction system, the precious metal Rh suffers significant loss during actual industrial operations. To address this issue, the academic community has conducted extensive research on the immobilization of homogeneous hydroformylation catalysts. Common inorganic supports (SiO2, activated carbon, molecular sieves) and organic supports (polystyrene, etc.) can all serve as supports for immobilized hydroformylation catalysts. For example, the He Dehua research group at Tsinghua University (Green Chem., 2009, 11(8): 1146-1154; Chem. Commun., 2008, 44(44): 5839-5841) grafted triphenylphosphine ligands onto SiO2 and MCM supports, achieving the immobilization of homogeneous hydroformylation catalysts through the coordination bonds between the triphenylphosphine ligands and the active metal Rh. The Reek research group abroad (Chem. Commun., 2010, 46(35): 6587-6589.) reported the immobilization of Rh-Xantphos catalysts by grafting Xantphos ligands onto SBA-15. The Ding Yunjie research group at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, prepared catalysts in which active metal Rh and ligands were simultaneously immobilized on SiO2 support (Appl. Catal. A-Gen., 2009, 353(2): 266-270; Appl. Catal. A-Gen., 2015, 492: 127-132). These methods have achieved some success, but compared with homogeneous catalytic complex catalysts, the decrease in catalyst activity and the low selectivity of aldehydes are still problems that need to be solved. There are also no industrial examples of this type of catalyst (Eur. J. Org. Chem., 2012, 2012(32): 6309-6320).

[0004] In recent years, porous organic polymers (POPs) have attracted increasing attention from researchers due to their diverse synthetic pathways, rich pore structures, good thermal stability, and the ability to introduce multifunctional functionalization sites at specific sites. POPs materials have shown promising application prospects in gas adsorption, separation and storage, sensor fabrication, catalysis and other fields (Chem.Soc.Rev.,2012,41(6):2083-2094). The rapid development of POPs materials has also provided an opportunity for the heterogeneity of hydroformylation homogeneous catalysts. The research groups of Ding Yunjie at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, and Xiao Fengshou at Zhejiang University have worked together (ZL201310235002.4; Chem. Commun., 2014, 50(80): 11844-11847; J. Mol. Catal. A-Chem., 2015, 404: 211-217) to successfully introduce three vinyl functional groups on the triphenylphosphine ligand, prepare the vinyl-functionalized 3vPPh3 ligand, and then prepare the polymer formed by the self-polymerization of 3vPPh3 by solvothermal polymerization. We named this type of ligand polymer POLs (Porous organic ligands). Unlike other polymer materials, the POL-PPh3 polymer bulk contains a high phosphorus concentration (2.94 mmol·g⁻¹), a large specific surface area and total pore volume (1086 m²·g⁻¹ and 1.70 cm³·g⁻¹, respectively), and exhibits good thermal stability (thermogravimetric analysis shows that the polymer only decomposes above 440℃). Furthermore, the POLs polymer is obtained through solvothermal polymerization with a 100% polymer yield, and the resulting polymer is exceptionally pure, free of impurities such as metals. Based on the excellent properties of the POL-PPh3 polymer, the final Rh / POL-PPh3 catalyst exhibits superior performance in the hydroformylation reaction.

[0005] Introducing vinyl groups onto triphenylphosphine monomers provides a feasible approach for achieving heterogeneous rhodium-phosphine complexes. However, how to effectively control the steric hindrance and microenvironment around the triphenylphosphine monomer within the polymer backbone to improve the yield of specific aldehydes in the hydroformylation reaction? How to reduce the preparation cost of vinyl-functionalized triphenylphosphine to facilitate its industrial application? How to improve the yield of vinyl-functionalized triphenylphosphine? How to enhance the performance (activity, selectivity, and stability) of the prepared catalyst? These are all pressing issues that need to be addressed. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide a method for the high-yield, large-scale production of vinyl-functionalized phosphine ligands. The prepared vinyl-functionalized phosphine ligands, after polymerization, can be used as supports for heterogeneous catalysts in the preparation of reactions such as olefin hydroformylation, Suzuki coupling, Heck coupling, Stille coupling, Negishi coupling, hydrogenation, and amination.

[0007] Specifically, by creatively adding polymerization inhibitors during the preparation of vinyl-functionalized triphenylphosphine monomers, the polymerization of vinyl groups is effectively prevented and the monomer yield is increased. By changing the position of vinyl groups on the benzene ring, the microenvironment of the pores around the triphenylphosphine after polymerization is controlled. By introducing large steric hindrance groups on the benzene ring, the steric hindrance around the triphenylphosphine in the polymer backbone is changed. By using inexpensive and industrially available p-(ortho-, meta-)chlorostyrene as a starting material, the production cost of vinyl-functionalized phosphine ligands is greatly reduced.

[0008] The method for synthesizing vinyl-functionalized organophosphorus ligand polymer monomers provided by this invention includes the following specific preparation steps:

[0009] a) Under an inert gas atmosphere at 273–373 K (preferably 273–353 K), the polymerization inhibitor and p-chlorostyrene (or one or more of o-chlorostyrene or m-chlorostyrene) are dissolved in an organic solvent and stirred for 0.1–12 hours to obtain a mixed solution.

[0010] b) At 273-433K (preferably 293K-403K), the above mixed solution is added to magnesium. After the addition is completed, the mixture is kept at 303-403K for 0.1-24 hours to obtain the Grignard reagent solution.

[0011] c) At 223–373 K (preferably 253 K–333 K), the Grignard reagent from step b) above is added to a solution of diphenylphosphine (or phenylphosphine, or one or more of phosphorus trichloride) in an organic solvent; after the addition is completed, the solution is kept at 253–333 K for 0.1–24 hours.

[0012] d) At 243–373 K (preferably 253–373 K), add a 0.1–10% hydrochloric acid solution to the solution from step c, and adjust the pH to 3–10 to fully annihilate the reaction. After standing for 0.1–24 hours, the mixture separates into two layers. The upper oil layer is removed, filtered through diatomaceous earth, and then distilled at 273–403 K to remove the solvent. Recrystallization with n-heptane yields the vinyl-functionalized phosphine ligand.

[0013] The vinyl-functionalized phosphine ligands designed and synthesized in this invention include the AUs mentioned in the claims, but are not limited to these functional monomers. Attached Figure Description

[0014] Figure 1 It is a tri(3-vinylphenyl)phosphine ligand 1 H NMR spectrum.

[0015] Figure 2 It is a tri(3-vinylphenyl)phosphine ligand 13 C10 NMR spectrum.

[0016] Figure 3 It is a tri(3-vinylphenyl)phosphine ligand 31 P NMR spectrum.

[0017] Figure 4 It is a tri(2-vinylphenyl)phosphine ligand 1 H NMR spectrum.

[0018] Figure 5 It is a tri(2-vinylphenyl)phosphine ligand 13 C10 NMR spectrum.

[0019] Figure 6 It is a tri(2-vinylphenyl)phosphine ligand 31 P NMR spectrum.

[0020] Figure 7 The N2 physical adsorption curves of the polymer prepared by tris(3-vinylphenyl)phosphine ligand are shown.

[0021] Figure 8 This is a pore size distribution diagram of polymers prepared from tris(3-vinylphenyl)phosphine ligands.

[0022] Figure 9 Thermogravimetric curves of polymers prepared from tris(3-vinylphenyl)phosphine ligands are shown.

[0023] Figure 10 This is a scanning electron microscope image of a polymer prepared from tris(3-vinylphenyl)phosphine ligands. Detailed Implementation

[0024] The following embodiments provide a better illustration of the present invention, but do not limit the scope of protection of the present invention.

[0025] Example 1

[0026] Under an inert gas atmosphere at 273 K, 207 kg of m-chlorostyrene (1.5 kmol) and 2.07 kg of hydroquinone (polymerization inhibitor) were dissolved in 1000 L of 2-methyltetrahydrofuran. After stirring for 1 hour, the solution was transferred to the upper tank (material storage tank, located on the upper part of one side of the reactor) of an enamel-lined reactor. The reactor temperature was raised to 333 K, and 38 kg of magnesium shavings were placed in a 3000 L enamel-lined reactor. Approximately 100 L of the mixed solution of m-chlorostyrene and 2-methyltetrahydrofuran was added dropwise to the reactor. After Grignard reagent initiation, the mixed solution was continued to be added dropwise, maintaining the addition temperature at T1℃. After the addition was completed, the mixture was kept at this temperature for 1 hour to obtain a Grignard reagent solution of m-chlorostyrene.

[0027] Under inert gas protection, the prepared Grignard reagent was transferred to the high-level tank of an enamel-lined reactor. 70 kg of phosphorus trichloride and 700 L of 2-methyltetrahydrofuran were added to the enamel-lined reactor. The reactor temperature was adjusted to T2 degrees Celsius. The prepared m-chlorostyrene Grignard reagent was added dropwise at T2 degrees Celsius. After the addition was completed, the reaction continued for 1 hour.

[0028] Under inert gas protection at 298K, the pH of the reaction solution was adjusted to 5 with a 2% hydrochloric acid solution. The mixture was stirred for 1 hour to ensure complete annihilation of the reaction. After standing for 2 hours, the mixture separated into two layers. The upper oil layer was removed and filtered through 10cm thick diatomaceous earth. The solvent was then removed by distillation at 60℃ to obtain a pale yellow oily liquid. 80kg of n-heptane was added to heat the mixed solvent to 60℃ to fully dissolve it. The mixture was then cooled to 0℃, recrystallized, and dried to obtain the vinyl-functionalized phosphine ligand.

[0029] Figure 1 Tris(3-vinylphenyl)phosphine ligand 1 H NMR spectrum, Figure 2 Tris(3-vinylphenyl)phosphine ligand 13 CNMR spectrum Figure 3 Tris(3-vinylphenyl)phosphine ligands 31 P NMR spectrum.

[0030] When temperatures T1 and T2 are different, the following weights of tris(3-vinylphenyl)phosphine ligands were obtained (the product has been confirmed by NMR, and the theoretical yield of the ligands is 170 kg):

[0031] T1 / ℃ T2 / ℃ Calculate the ligand weight / kg 65 25 80 60 15 79 60 5 91 60 0 105 60 -10 108 65 0 101 55 0 103 45 0 90 40 0 86

[0032] Example 2

[0033] Under an inert gas atmosphere at 273 K, 207 kg of o-chlorostyrene (1.5 kmol) and 2.07 kg of hydroquinone (polymerization inhibitor) were dissolved in 1000 L of 2-methyltetrahydrofuran. After stirring for 1 hour, the solution was transferred to the high-level tank of an enamel-lined reactor. The reactor temperature was raised to 333 K, and 38 kg of magnesium shavings were placed in a 3000 L enamel-lined reactor. Approximately 100 L of a mixed solution of o-chlorostyrene and 2-methyltetrahydrofuran was added dropwise to the reactor. After Grignard reagent initiation, the mixed solution was continued to be added dropwise, maintaining the addition temperature at T1℃. After the addition was completed, the mixture was kept at this temperature for 1 hour to obtain the Grignard reagent solution.

[0034] Under inert gas protection, the prepared Grignard reagent was transferred to the high-level tank of an enamel-lined reactor. 70 kg of phosphorus trichloride and 700 L of 2-methyltetrahydrofuran were added to the enamel-lined reactor. The reactor temperature was adjusted to T2 degrees Celsius. The prepared Grignard reagent was added dropwise at T2 degrees Celsius. After the addition was completed, the reaction continued for 1 hour.

[0035] Under inert gas protection at 298K, the pH of the reaction solution was adjusted to 5 with a 2% hydrochloric acid solution. The mixture was stirred for 1 hour to ensure complete annihilation of the reaction. After standing for 2 hours, the mixture separated into two layers. The upper oil layer was removed and filtered through 10cm thick diatomaceous earth. The solvent was then removed by distillation at 60℃ to obtain a pale yellow oily liquid. 80kg of n-heptane was added to heat the mixed solvent to 60℃ to fully dissolve it. The mixture was then cooled to 0℃, recrystallized, and dried to obtain the vinyl-functionalized phosphine ligand.

[0036] Figure 4 Tris(2-vinylphenyl)phosphine ligand 1 H NMR spectrum, Figure 5 Tris(2-vinylphenyl)phosphine ligand 13 CNMR spectrum Figure 6 Tris(2-vinylphenyl)phosphine ligands 31 P NMR spectrum.

[0037] When temperatures T1 and T2 are different, the following weights of tris(2-vinylphenyl)phosphine ligands were obtained (the product has been confirmed by NMR, and the theoretical yield of the ligands is 170 kg):

[0038] T1 / ℃ T2 / ℃ Calculate the ligand weight / kg 65 25 66 60 15 71 60 5 89 60 0 103 60 -10 103 65 0 94 55 0 94 45 0 84 40 0 80

[0039] Example 3

[0040] Under an inert gas atmosphere at 273 K, 207 kg of p-chlorostyrene (1.5 kmol) and 2.07 kg of hydroquinone (polymerization inhibitor) were dissolved in 1000 L of 2-methyltetrahydrofuran. After stirring for 1 hour, the solution was transferred to the high-level tank of an enamel-lined reactor. The reactor temperature was raised to 333 K, and 38 kg of magnesium shavings were placed in a 3000 L enamel-lined reactor. Approximately 100 L of the mixed solution of p-chlorostyrene and 2-methyltetrahydrofuran was added dropwise to the reactor. After Grignard reagent initiation, the mixed solution was continued to be added dropwise, maintaining the addition temperature at T1℃. After the addition was completed, the mixture was kept at this temperature for 1 hour to obtain the Grignard reagent solution.

[0041] Under inert gas protection, the prepared Grignard reagent was transferred to the high-level tank of an enamel-lined reactor. 70 kg of phosphorus trichloride and 700 L of 2-methyltetrahydrofuran were added to the enamel-lined reactor. The reactor temperature was adjusted to T2 degrees Celsius. The prepared Grignard reagent was added dropwise at T2 degrees Celsius. After the addition was completed, the reaction continued for 1 hour.

[0042] Under an inert gas atmosphere at 298K, the pH of the reaction solution was adjusted to 5 with 2% hydrochloric acid solution. The mixture was stirred for 1 hour to ensure complete annihilation of the reaction. After standing for 2 hours, the mixture separated into two layers. The upper oil layer was removed and filtered through 10cm thick diatomaceous earth. The solvent was then removed by distillation at 60℃ to obtain a pale yellow oily liquid. 80kg of n-heptane was added to heat the mixed solvent to 60℃ to fully dissolve it. The mixture was then cooled to 0℃, recrystallized, and dried to obtain the vinyl-functionalized phosphine ligand.

[0043] When temperatures T1 and T2 are different, the following weights of tris(4-vinylphenyl)phosphine ligands were obtained (the product has been confirmed by NMR, and the theoretical yield of the ligand is 170 kg):

[0044] T1 / ℃ T2 / ℃ Calculate the ligand weight / kg 65 25 83 60 15 85 60 5 97 60 0 108 60 -10 116 65 0 108 55 0 111 45 0 94 40 0 91

[0045] Example 4

[0046] According to the scheme of Example 4 in ZL201310235002.4, the material is fed into an enamel-lined reactor. 1.5 kmol of p-bromostyrene can finally produce 50 kg of tris(4-vinylbenzene)phosphine ligand, which is lower than the scheme of Example 3 of this patent.

[0047] Example 5

[0048] Except for replacing 2-methyltetrahydrofuran with the same volume of tetrahydrofuran solvent, the other conditions and procedures were the same as in Example 1. When the temperatures T1 and T2 were different, the following weights of tris(3-vinylphenyl)phosphine ligands were obtained (the product has been confirmed by NMR, and the theoretical yield of the ligand is 170 kg):

[0049] T1 / ℃ T2 / ℃ Calculate the ligand weight / kg 65 25 68 60 15 70 60 5 80 60 0 94 60 -10 98 65 0 86 55 0 90 45 0 78 40 0 74

[0050] Example 6

[0051] Except for replacing the polymerization inhibitor with the same weight of p-tert-butylcatechol, the other conditions and procedures were the same as in Example 1. When the temperatures T1 and T2 were different, the following weights of tris(3-vinylphenyl)phosphine ligands were obtained (the product has been confirmed by NMR, and the theoretical yield of the ligand is 170 kg):

[0052]

[0053]

[0054] Example 7

[0055] Except for replacing the polymerization inhibitor with the same weight of p-benzoquinone, the other conditions and procedures were the same as in Example 1. When T1 was 60°C and T2 was -10°C, 55 kg of tri(3-vinylbenzene)phosphine ligand was obtained.

[0056] Example 8

[0057] Except for replacing the polymerization inhibitor with the same weight of methylhydroquinone, the other conditions and procedures were the same as in Example 1. When T1 was 60°C and T2 was -10°C, 52 kg of tris(3-vinylphenyl)phosphine ligand was obtained.

[0058] Example 9

[0059] Except for replacing the polymerization inhibitor with the same weight of p-hydroxyanisole, the other conditions and procedures were the same as in Example 1. When T1 was 60°C and T2 was -10°C, 50 kg of tris(3-vinylphenyl)phosphine ligand was obtained.

[0060] Example 10

[0061] Except for replacing the polymerization inhibitor with the same weight of 2-tert-butylhydroquinone, the other conditions and procedures were the same as in Example 1. When T1 was 60°C and T2 was -10°C, 55 kg of tris(3-vinylphenyl)phosphine ligand was obtained.

[0062] Example 11

[0063] Except for replacing the polymerization inhibitor with the same weight of 2,5-di-tert-butylhydroquinone, the other conditions and procedures were the same as in Example 1. When T1 was 60°C and T2 was -10°C, 53 kg of tris(3-vinylphenyl)phosphine ligand was obtained.

[0064] Example 12

[0065] Under an inert gas atmosphere at 273 K, 207 kg of m-chlorostyrene (1.5 kmol) was dissolved in 1000 L of 2-methyltetrahydrofuran. After stirring for 1 hour, the solution was transferred to the upper tank (material storage tank, located on the upper part of one side of the reactor) of an enamel-lined reactor. The reactor temperature was raised to 333 K, and 38 kg of magnesium shavings were placed into a 3000 L enamel-lined reactor. Approximately 100 L of a mixed solution of m-chlorostyrene and 2-methyltetrahydrofuran was added dropwise to the reactor. After Grignard reagent initiation, the mixed solution was continued to be added dropwise, maintaining the adding temperature at T1℃. After the addition was completed, the mixture was kept at this temperature for 1 hour to obtain a Grignard reagent solution of m-chlorostyrene.

[0066] Under inert gas protection, the prepared Grignard reagent was transferred to the high-level tank of an enamel-lined reactor. 70 kg of phosphorus trichloride, 700 L of 2-methyltetrahydrofuran, and 2.07 kg of hydroquinone (polymerization inhibitor) were added to the enamel-lined reactor. The reactor temperature was adjusted to T2 degrees Celsius. The prepared m-chlorostyrene Grignard reagent was added dropwise at T2 degrees Celsius. After the addition was completed, the reaction was continued for 1 hour.

[0067] Under inert gas protection at 298K, the pH of the reaction solution was adjusted to 5 with a 2% hydrochloric acid solution. The mixture was stirred for 1 hour to ensure complete annihilation of the reaction. After standing for 2 hours, the mixture separated into two layers. The upper oil layer was removed and filtered through 10cm thick diatomaceous earth. The solvent was then removed by distillation at 60℃ to obtain a pale yellow oily liquid. 80kg of n-heptane was added to heat the mixed solvent to 60℃ to fully dissolve it. The mixture was then cooled to 0℃, recrystallized, and dried to obtain the vinyl-functionalized phosphine ligand.

[0068] When T1 is 60℃ and T2 is -10℃, the weight of tris(3-vinylphenyl)phosphine ligand (the product has been confirmed by NMR, and the theoretical yield of the ligand is 170kg) is 56kg.

[0069] Example 13

[0070] Except for the absence of a polymerization inhibitor, the other conditions and procedures were the same as in Example 1. When T1 was 60°C and T2 was -10°C, 53 kg of tris(3-vinylphenyl)phosphine ligands were obtained.

[0071] Example 14

[0072] The remaining conditions and procedures are the same as in Example 1. When T1 is 60°C and T2 is -10°C, different amounts of hydroquinone polymerization inhibitor are added, and the weights of the tris(3-vinylbenzene) phosphine ligands (the product has been confirmed by NMR, and the theoretical yield of the ligand is 170 kg) are as follows:

[0073]

[0074]

[0075] Example 15

[0076] Under an inert gas atmosphere at 273 K, 69 kg of m-chlorostyrene (0.5 kmol) and 0.69 kg of hydroquinone (polymerization inhibitor) were dissolved in 330 L of 2-methyltetrahydrofuran. After stirring for 1 hour, the solution was transferred to the high-level tank of an enamel-lined reactor. The reactor temperature was raised to 333 K, and 13 kg of magnesium shavings were placed in the 3000 L enamel-lined reactor. Approximately 50 L of the mixed solution of m-chlorostyrene and 2-methyltetrahydrofuran was added dropwise to the reactor. After Grignard reagent initiation, the mixed solution was continued to be added dropwise, maintaining the addition temperature at 60 °C. After the addition was completed, the mixture was kept at this temperature for 1 hour to obtain a Grignard reagent solution of m-chlorostyrene.

[0077] Under inert gas protection, the prepared Grignard reagent was transferred to the high-level tank of an enamel-lined reactor. 110 kg of diphenylphosphine chloride and 1100 L of 2-methyltetrahydrofuran were added to the enamel-lined reactor. The reactor temperature was adjusted to 0 °C, and the prepared m-chlorostyrene Grignard reagent was added dropwise at 0 °C. After the addition was completed, the reaction continued for 1 hour.

[0078] Under an inert gas atmosphere at 298 K, the pH of the reaction solution was adjusted to 5 with a 2% hydrochloric acid solution. The mixture was stirred for 1 hour to ensure complete annihilation of the reaction. After standing for 2 hours, the mixture separated into two layers. The upper oil layer was removed and filtered through a 10 cm thick layer of diatomaceous earth. The solvent was then removed by distillation at 60 °C to obtain a pale yellow oily liquid. 80 kg of n-heptane was added to heat the mixed solvent to 60 °C to dissolve it completely. The mixture was then cooled to 0 °C, recrystallized, and dried to obtain 100 kg of vinyl-functionalized phosphine ligands.

[0079] Example 16

[0080] Under an inert gas atmosphere at 273 K, 138 kg of m-chlorostyrene (1.0 kmol) and 1.38 kg of hydroquinone (polymerization inhibitor) were dissolved in 660 L of 2-methyltetrahydrofuran. After stirring for 1 hour, the solution was transferred to the high-level tank of an enamel-lined reactor. The reactor temperature was raised to 333 K. 27 kg of magnesium shavings were added to the 3000 L enamel-lined reactor. Approximately 100 L of the mixed solution of m-chlorostyrene and 2-methyltetrahydrofuran was added dropwise to the reactor. After Grignard reagent initiation, the mixed solution was continued to be added dropwise, maintaining the adding temperature at 60 °C. After the addition was completed, the mixture was kept at this temperature for 1 hour to obtain a Grignard reagent solution of m-chlorostyrene.

[0081] Under inert gas protection, the prepared Grignard reagent was transferred to the high-level tank of an enamel-lined reactor. 89 kg of phenyl phosphorus dichloride and 890 L of 2-methyltetrahydrofuran were added to the enamel-lined reactor. The reactor temperature was adjusted to 0 °C, and the prepared m-chlorostyrene Grignard reagent was added dropwise at 0 °C. After the addition was completed, the reaction continued for 1 hour.

[0082] Under an inert gas atmosphere at 298 K, the pH of the reaction solution was adjusted to 5 with a 2% hydrochloric acid solution. The mixture was stirred for 1 hour to ensure complete annihilation of the reaction. After standing for 2 hours, the mixture separated into two layers. The upper oil layer was removed and filtered through a 10 cm thick layer of diatomaceous earth. The solvent was then removed by distillation at 60 °C to obtain a pale yellow oily liquid. 80 kg of n-heptane was added to heat the mixed solvent to 60 °C to dissolve it completely. The mixture was then cooled to 0 °C, recrystallized, and dried to obtain 101 kg of vinyl-functionalized phosphine ligands.

[0083] Example 17

[0084] Under an inert gas atmosphere at 273 K, 138 kg of m-chlorostyrene (1.0 kmol) and 1.38 kg of hydroquinone (polymerization inhibitor) were dissolved in 660 L of 2-methyltetrahydrofuran. After stirring for 1 hour, the solution was transferred to the high-level tank of an enamel-lined reactor. The reactor temperature was raised to 333 K, and 27 kg of magnesium shavings were placed in a 3000 L enamel-lined reactor. Approximately 100 L of the mixed solution of m-chlorostyrene and 2-methyltetrahydrofuran was added dropwise to the reactor. After Grignard reagent initiation, the mixed solution was continued to be added dropwise, maintaining the addition temperature at 60 °C. After the addition was completed, the mixture was kept at this temperature for 1 hour to obtain a Grignard reagent solution of m-chlorostyrene.

[0085] Under inert gas protection, the prepared Grignard reagent was transferred to the high-level tank of an enamel-lined reactor. 97 kg of m-methylphenyl phosphorus dichloride and 970 L of 2-methyltetrahydrofuran were added to the enamel-lined reactor. The reactor temperature was adjusted to 0 °C, and the prepared m-chlorostyrene Grignard reagent was added dropwise at 0 °C. After the addition was completed, the reaction continued for 1 hour.

[0086] Under an inert gas atmosphere at 298 K, the pH of the reaction solution was adjusted to 5 with a 2% hydrochloric acid solution. The mixture was stirred for 1 hour to ensure complete annihilation of the reaction. After standing for 2 hours, the mixture separated into two layers. The upper oil layer was removed and filtered through a 10 cm thick layer of diatomaceous earth. The solvent was then removed by distillation at 60 °C to obtain a pale yellow oily liquid. 80 kg of n-heptane was added to heat the mixed solvent to 60 °C to dissolve it completely. The mixture was then cooled to 0 °C, recrystallized, and dried to obtain 97 kg of vinyl-functionalized phosphine ligands.

[0087] Example 18

[0088] Under an inert gas atmosphere at 273 K, 69 kg of m-chlorostyrene (0.5 kmol) and 0.69 kg of hydroquinone (polymerization inhibitor) were dissolved in 330 L of 2-methyltetrahydrofuran. After stirring for 1 hour, the solution was transferred to the high-level tank of an enamel-lined reactor. The reactor temperature was raised to 333 K. 13 kg of magnesium shavings were added to the 3000 L enamel-lined reactor. Approximately 50 L of the mixed solution of m-chlorostyrene and 2-methyltetrahydrofuran was added dropwise to the reactor. After Grignard reagent initiation, the mixed solution was continued to be added dropwise, maintaining the adding temperature at 60 °C. After the addition was completed, the mixture was kept at this temperature for 1 hour to obtain a Grignard reagent solution of m-chlorostyrene.

[0089] Under inert gas protection, the prepared Grignard reagent was transferred to the high-level tank of an enamel-lined reactor. 166 kg of di-,--tert-butylphenyl phosphorus chloride and 1600 L of 2-methyltetrahydrofuran were added to the enamel-lined reactor. The reactor temperature was adjusted to 0 °C, and the prepared m-chlorostyrene Grignard reagent was added dropwise at 0 °C. After the addition was completed, the reaction continued for 1 hour.

[0090] Under inert gas protection at 298K, the pH of the reaction solution was adjusted to 5 with 2% hydrochloric acid solution, and the mixture was stirred for 1 hour to ensure complete annihilation of the reaction. After standing for 2 hours, the mixture separated into two layers. The upper oil layer was removed and filtered through 10cm thick diatomaceous earth. The solvent was then removed by distillation at 60℃ to obtain a pale yellow oily liquid. 80kg of n-heptane was added to heat the mixed solvent to 60℃ to fully dissolve it. The mixture was then cooled to 0℃, recrystallized, and dried to obtain 90kg of vinyl-functionalized phosphine ligands.

[0091] Example 19

[0092] Following the steps provided in claims 1-10 and the operation process of Example 1, when T1 is 60℃ and T2 is -10℃, the following weights of monomers A, B, G, H, I, K, M, O, P, Q, R, S, T, and U were obtained respectively (the products have been confirmed by NMR):

[0093] monomer Calculate the ligand weight / kg A 103 B 108 G 99 H 105 I 95 K 94 M 92 O 89 P 97 Q 90 R 106 S 100 T 111 U 105

[0094] Example 20

[0095] Under an inert gas atmosphere at 298 K, in a 100 L enamel-lined stirred reactor, 50 kg of the vinyl-functionalized phosphine ligand prepared in Example 1 and 0.1 kg of benzoyl peroxide were dissolved in 50 L of xylene. Then, 200 L of a 1.5% polyvinyl alcohol solution (suspending agent) was added to the enamel-lined stirred reactor and stirred thoroughly. The reactor temperature was raised to 90 °C and reacted for 2 hours. After cooling to room temperature, the particulate matter was filtered, washed with 500 L of deionized water, and then vacuum dried at 60 °C for 5 hours to obtain a polymer of the vinyl phosphine ligand.

[0096] Under an inert gas atmosphere at 298 K, 157 g of rhodium carbonyl acetylacetonate was dissolved in 80 L of diethyl ether and added to 50 kg of the prepared vinylphosphine ligand polymer (equal volume impregnation). The mixture was stirred thoroughly and then the solvent was removed under vacuum at 70 °C to obtain the catalyst for the hydroformylation reaction of olefins.

[0097] Example 21

[0098] In Example 21, except that bulk polymerization was used instead of suspension polymerization, the rest of the methods and catalyst synthesis process were the same as in Example 20.

[0099] Example 22

[0100] In Example 22, the method and catalyst synthesis process were the same as in Example 20, except that the same number of molar amounts of cobalt diacetylacetone were used instead of rhodium carbonyl acetylacetone.

[0101] Example 23

[0102] In Example 23, the method and catalyst synthesis process were the same as in Example 20, except that the same number of moles of acetylacetone tricarbonyl iridium were used instead of acetylacetone carbonyl rhodium.

[0103] Example 24

[0104] Following the steps of Example 20, by replacing the monomers with AD and FU, the corresponding catalysts prepared from the monomers AD and FU can be obtained respectively.

[0105] Example 25

[0106] Five kg of the catalyst prepared according to the methods in Examples 20-24 was loaded into a 50 L slurry bed reactor, and 10 L of pentanal was added to form a slurry. A reaction mixture (H2:CO:C3H6 = 1:1:1) was introduced, and the hydroformylation reaction was carried out at 393 K, 1.0 MPa, a gas hourly space velocity (GHSV) of 2000 h⁻¹, and a stirring rate of 750 rpm. The reaction was collected in a collection tank containing 6 L of cooled deionized water, and all reaction products and slurry entrained in the tail gas were dissolved in the water in the collection tank. The obtained aqueous solution was analyzed by gas chromatography using an HP-7890N equipped with an HP-5 capillary column and an FID detector, with ethanol as an internal standard. The reaction tail gas after water absorption was analyzed online by gas chromatography using an HP-7890N equipped with a Porapak-QS column and a TCD detector. The data are listed in Table 1.

[0107] Table 1. Specific surface area of ​​catalysts prepared from monomer AU and propylene reaction data.

[0108]

[0109]

[0110] *The experimental conditions were 120℃, 1MPa, gas mixture (propylene:CO:H2=1:1:1), and space velocity 2000h⁻¹. -1 In the TOF calculation, all Rh sites are considered to be active sites. **The reaction temperature is 230℃, and the active component is Co.** ***The reaction temperature is 120℃, and the active component is Ir.

[0111] Experimental results show that when the vinyl group is located at the ortho or meta position, or when there are sterically hindered groups at the ortho or meta position on the benzene ring, the resulting catalyst has higher selectivity for n-butyraldehyde.

Claims

1. A method for preparing a vinyl-functionalized phosphine ligand, characterized in that: 1) In an organic solvent in which the polymerization inhibitor is present, one or more of p-chlorostyrene, o-chlorostyrene, and m-chlorostyrene are reacted with magnesium to obtain a Grignard reagent solution; 2) By adding a Grignard reagent solution to a solution of one or more organic solvents selected from diphenylchlorophosphine, phenyl dichlorophosphine, and phosphorus trichloride, a vinyl-functionalized phosphine ligand is obtained; The specific preparation steps for vinyl-functionalized phosphine ligands are as follows: a) At 273-353 K, under an inert gas atmosphere, dissolve the polymerization inhibitor and one or more of p-chlorostyrene, o-chlorostyrene, and m-chlorostyrene in an organic solvent, and stir for 0.1-12 hours to obtain a mixed solution; b) At 328K-333K, the above mixed solution is added to magnesium. After the addition is complete, the mixture is kept at 303-403K for 0.1-24 hours to obtain the Grignard reagent solution. c) At 263-273 K, add the Grignard reagent from step b) above to a solution of one or more organic solvents selected from diphenylphosphine, phenylphosphine, and phosphorus trichloride; after the addition is completed, keep the solution at 253-333 K for 0.1-24 hours. d) At 253-373 K, add 0.1-10% hydrochloric acid solution to the solution in step c, adjust the pH to 3-10 to fully annihilate the reaction, let stand for 0.1-24 hours and the mixture will separate into two layers. Take out the upper oil layer, filter the oil layer through diatomaceous earth, and then distill at 273-403 K to remove the solvent. Add n-heptane and recrystallize to obtain the vinyl-functionalized phosphine ligand. In step 1), the weight ratio of one or more of p-chlorostyrene, o-chlorostyrene, and m-chlorostyrene, the polymerization inhibitor, and the organic solvent is 1:(0.01~0.5):(2~20). Hydroquinone was selected as the polymerization inhibitor; tetrahydrofuran was selected as the organic solvent.

2. The preparation method according to claim 1, characterized in that: The synthetic route for a typical vinyl-functionalized phosphine ligand AE is as follows: ， The synthetic routes for vinyl-functionalized phosphine ligands F, G, J, and K are as follows: ， 。 3. The preparation method according to claim 1, characterized in that: In step b), the weight ratio of magnesium to one or more of the following in step a) is (0.02~1):

1.

4. The preparation method according to claim 1, characterized in that: In step c), the weight of one or more of diphenylphosphine, phenyl dichlorophosphine, or phosphorus trichloride is equal to the weight of the organic solvent. The weight ratio of one or more of p-chlorostyrene, o-chlorostyrene, and m-chlorostyrene in step a) is (0.02~1):(0.1~5):1; the organic solvent is tetrahydrofuran.

Images