Organophosphorous ligand polymer and its preparation method and application

Abstract

The application provides an organic phosphine ligand polymer, a preparation method and application thereof, and a structure of the organic phosphine ligand polymer is shown in a general formula (I), wherein R1 and R2 are selected from same or different phosphorus-containing groups, m is 35-45, and n is 35-1350. The organic phosphine ligand polymer of the application forms a heterogeneous rhodium catalyst system, so that the organic phosphine ligand polymer not only has high activity and high selectivity of a homogeneous catalyst, but also has the convenience of separation of the catalyst and the product, and the production cost can be greatly reduced.

Description

Technical Field

[0001] This invention relates to the field of olefin hydroformylation technology, specifically to an organophosphorus ligand polymer, its preparation method, and its application. Background Technology

[0002] Hydroformylation of olefins is a reaction that uses transition metal catalysts to convert olefins, hydrogen, and carbon monoxide into aldehydes. It has become one of the most important industrial homogeneous catalytic reactions. It is estimated that the global capacity for producing aldehydes and alcohols through hydroformylation has reached over 10 million tons per year.

[0003] Hydroformylation is characterized by its high atom economy and wide applicability of products. However, to date, the olefin substrates used in industrial production have mainly focused on α-olefins and internal olefins. The dihydroformylation of butadiene remains challenging, primarily due to its relatively complex mechanism, involving multiple reaction pathways such as 1,4-addition carbonylation, 1,2-addition carbonylation, and carbon-carbon double bond isomerization. Furthermore, it suffers from slow reaction rates, difficulty in controlling regioselectivity, and the simultaneous formation of over a dozen isomerization products and byproducts. Therefore, butadiene is an extremely challenging substrate for hydroformylation, and the design and synthesis of phosphine ligands with different structural types is crucial for the development of this technology.

[0004] Based on the above situation, researchers have designed and synthesized some novel phosphine ligands and ligand polymers, and applied them to hydroformylation reactions, achieving the recycling of ligands and catalysts through heterogeneous catalysis. EP33554A2 discloses a carbonylation method for conjugated dienes, with pentanal as the main product and almost no dialdehyde formation; US4769498A discloses that polyphosphite ligand polymers and rhodium catalysts can be used for the hydroformylation of 1,4-hexadiene and 1,7-octadiene; WO9740003A discloses a class of bidentate phosphite ligands, which are applied to the hydroformylation of 1,3-butadiene with a hexadial selectivity of 22%; CN1087078A discloses a class of polyphosphite ligands, in which the optimal ligand at 110℃ and 900 psig achieves a 99% conversion of 1,3-butadiene and a 30% hexadial selectivity; CN108137451... CN110343209A and CN109942750A disclose a diacetal of a phosphorus amide-based didentate phosphine ligand for the hydroformylation of 1,3-butadiene, which accounts for 73% of the total product under the conditions of 3 MPa, 120 °C, and 18 h. CN110343209A and CN109942750A disclose a phosphorus amide-based didentate phosphine ligand copolymer with a conversion rate of nearly 100%, a selectivity of 90% for linear aldehydes, and an l / b value of around 150. CN109836318A discloses an organophosphine ligand polymer containing Xantphos, and applies this ligand to the fixed-bed catalytic hydroformylation of 1-octene, achieving a TOF value of over 700 and an l / b value of around 30 under optimal conditions.

[0005] In addition, many published studies have reported on the preparation of 1,6-hexanedialdehyde by hydroformylation of 1,3-butadiene. For example, J. Mol. Catal. A: Chem., 1998, 133, 289 screened a series of phosphine ligands and found that DIOP had the best selectivity for the hydroformylation of 1,3-butadiene, with 1,6-hexanedialdehyde reaching 37%; Organometallics, 2015, 34, 841; ACS Catal. 2016, 6, 2802; Mol. Catal., 2020, 484, 110721 also obtained similar results, and the selectivity of 1,6-hexanedialdehyde could be increased to 40% through condition optimization; Organometallics, 2011, 30, 3643-3651; ACS The optimal structure of adipic aldehyde in phosphonite ligands reported in Catal., 2014, 4, 3593-3604; Organometallics, 2015, 34, 4102-4108, etc., shows a selectivity of nearly 50%.

[0006] Among them, WO9740003A and CN1087078A disclose a class of bidentate and polyphosphite ligands for phosphite esters, which are applied to the hydroformylation of 1,3-butadiene, with a selectivity of less than 30% for hexadialdehyde. The drawback of this technology or its deficiency relative to the present invention is that the ligand has low catalytic efficiency for the hydroformylation of butadiene. CN110343209A, CN109942750A and CN109836318A disclose a bidentate phosphine ligand copolymer and organophosphine ligand polymerization, which forms a catalytic system with transition metal salts for the hydroformylation of terminal olefins or the isomerization-hydroformylation of internal olefins. The drawback of this technology or its deficiency relative to the present invention is that the ligand is used for the hydroformylation of terminal olefins or the isomerization-hydroformylation of internal olefins.

[0007] Despite years of research and exploration, the technology for preparing adipaldehyde by hydroformylation of butadiene still suffers from problems such as low reaction rate, poor regioselectivity, and difficulty in product separation, and has not yet achieved industrial-scale production, remaining in the laboratory stage. Based on this situation, developing novel heterogeneous catalytic systems that possess the high activity and selectivity of homogeneous catalysts while also offering advantages in catalyst-product separation is the key research focus and main development direction for the future directional preparation of adipaldehyde by hydroformylation of butadiene. Summary of the Invention

[0008] To address the aforementioned technical problems, the present invention aims to provide an organophosphorus ligand polymer, its preparation method, and its application. By forming a heterogeneous rhodium catalyst system, it not only possesses the high activity and high selectivity of a homogeneous catalyst but also enjoys the convenience of catalyst-product separation, thereby significantly reducing production costs.

[0009] To achieve the above objectives, the present invention provides an organophosphorus ligand polymer, the structure of which is shown in general formula (I).

[0010]

[0011] R1 and R2 are selected from the same or different phosphorus-containing groups. R1 and R2 are each independently selected from the following structures, where "." indicates the connection position, and the same applies below.

[0012]

[0013] R3 is selected from

[0014] m is 35-45, and n is 35-1350.

[0015] According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, R1 and R2 are each independently selected from...

[0016] According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, R3 is selected from...

[0017] According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, the organophosphine ligand polymer is copolymerized from a bidentate phosphine monomer and a vinyl monomer, wherein the structure of the bidentate phosphine monomer is as shown in general formula (II), and the structure of the vinyl monomer is as follows:

[0018]

[0019] According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, the vinyl monomer is selected from one or more of the following structures.

[0020]

[0021] According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, the molar ratio of the bidentate phosphine monomer and the vinyl monomer is 1:(1-30).

[0022] According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, m:n is 1:(1-30), more preferably 1:10.

[0023] According to a specific embodiment of the present invention, preferably, the molecular weight range of the organophosphorus ligand polymer is 50,000-200,000 g / mol.

[0024] According to a specific embodiment of the present invention, preferably, the degree of polymerization of the organophosphine ligand polymer is 35-55.

[0025] According to a specific embodiment of the present invention, preferably, the organophosphine ligand polymer is selected from L1 or L2, and its structural formula is as follows.

[0026]

[0027]

[0028] Where m is 35-45 and n is 35-1350.

[0029] The present invention also provides a method for preparing the above-mentioned organophosphorus ligand polymer, comprising the following steps:

[0030] S1: Under an inert gas atmosphere and in the presence of triethylamine, R1-Cl and / or R2-Cl and compound 2 are brought into full contact in the first solvent to react, the reaction is quenched, the reaction product is collected and purified to obtain the bidentate phosphine monomer;

[0031] S2: Under an inert gas atmosphere and in the presence of azobisisobutyronitrile, the bidentate phosphine monomer and the vinyl monomer are brought into full contact in a second solvent to carry out a copolymerization reaction. The reaction is then terminated, and the reaction product is collected and purified to obtain the organophosphine ligand polymer.

[0032] Wherein, the structure of compound 2 is

[0033] According to a specific embodiment of the present invention, in the above preparation method, preferably, in S2, the copolymerization reaction temperature is 60-100℃ and the reaction time is 2-6h.

[0034] According to a specific embodiment of the present invention, in the above preparation method, preferably, in S2, the second solvent is selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, and toluene.

[0035] According to a specific embodiment of the present invention, in the above preparation method, preferably, in S1, the reaction temperature is 0-30℃ and the reaction time is 5-10h.

[0036] According to a specific embodiment of the present invention, in the above preparation method, preferably, in S1, the first solvent is selected from one or more of tetrahydrofuran, toluene, and N,N-dimethylformamide.

[0037] According to a specific embodiment of the present invention, preferably, the above preparation method further includes the step of preparing compound 2, wherein the preparation method of compound 2 includes: under a nitrogen atmosphere and the action of a catalyst, allowing compound 1 and an ethyleneizing agent to fully contact in a third solvent to carry out an ethyleneization reaction, collecting and purifying the reaction product to obtain compound 2.

[0038] According to a specific embodiment of the present invention, in the preparation method of compound 2, preferably, the ethyleneation reaction temperature is 10-60°C and the reaction time is 5-10 h.

[0039] According to a specific embodiment of the present invention, in the preparation method of compound 2, preferably, the ethyleneizing agent is selected from... One or more of them.

[0040] According to a specific embodiment of the present invention, in the preparation method of compound 2, preferably, the catalyst is selected from one or more of tetrakis(triphenylphosphine)palladium, PdCl2(dppf) or PdCl2(PPh3)2.

[0041] According to a specific embodiment of the present invention, in the preparation method of compound 2, preferably, the third solvent is selected from one or more of toluene, tetrahydrofuran, and 1,4-dioxane.

[0042] According to a specific embodiment of the present invention, preferably, as shown in reaction formula 1, the above preparation method includes the following steps:

[0043]

[0044] (1) Compound 1 and solvent were added to the reactor, followed by the addition of ethylene reagent and catalyst. The mixture was refluxed overnight under nitrogen protection, cooled to room temperature, and the solvent was removed by vacuum distillation. The mixture was then purified by column chromatography to obtain compound 2.

[0045] (2) Under nitrogen protection, add phosphine chloride compounds (R1-Cl and / or R2-Cl) and solvent to the reactor, cool down to 0°C, and dissolve compound 2 and triethylamine in solvent. Add this mixture dropwise to the reactor at 0°C, allow it to rise to room temperature naturally, quench the reaction with water, extract with ethyl acetate, dry the organic phase with anhydrous sodium sulfate, and separate by column chromatography to obtain the didentate phosphine monomer shown in general formula (II).

[0046] (3) Add didentate phosphine monomer and comonomer to the reactor. AIBN, solvent, was reacted under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, precipitated with methanol, filtered, washed with methanol, and dried under vacuum to obtain the organophosphine ligand polymer shown in general formula (I).

[0047] The present invention also provides an application of the above-mentioned organophosphine ligand polymer in the hydroformylation reaction of olefins.

[0048] According to a specific embodiment of the present invention, in the above applications, preferably, the olefin is selected from C4-C6. 10 Olefins, more preferably butadiene.

[0049] According to a specific embodiment of the present invention, in the above application, preferably, the organophosphine ligand polymer forms a heterogeneous rhodium catalyst system.

[0050] The organophosphine ligand polymer of the present invention forms a heterogeneous rhodium catalyst system and is applied to the hydroformylation reaction of low-carbon olefins, replacing the currently widely used industrial low-pressure carbonyl synthesis liquid-phase recycling process, simplifying the process flow and significantly reducing production costs.

[0051] The organophosphine ligand polymer of the present invention forms a heterogeneous rhodium catalyst system and is applied to the hydroformylation reaction of high carbon olefins, thus completely solving the technical problem of catalyst separation in the process of hydroformylation of high carbon olefins by homogeneous catalysts.

[0052] (1) The preparation process of organophosphine polymer ligands is simple and the raw materials are readily available. The phosphine ligands used in the copolymer ligand synthesis method provided by this invention can be directly purchased or synthesized, and the copolymerized bidentate phosphine ligand monomers can be copolymerized with inexpensive and commercially available vinyl compounds, which are readily available and inexpensive. The aforementioned raw materials can be directly reacted in one step to generate a bidentate phosphine ligand copolymer containing a phosphite structure;

[0053] (2) The preparation method of the present invention has high yield and good product quality. The bidentate phosphine ligand copolymer containing phosphite structure prepared by the method provided by the present invention has a product yield and purity of over 95%, and does not require recrystallization, which is a level that existing preparation technologies cannot achieve;

[0054] (3) The preparation method of the present invention can achieve the preparation of copolymer ligands of various scales. The method provided by the present invention can prepare several grams to hundreds of grams of bidentate phosphite ligand copolymers containing phosphite structures in a single step;

[0055] (4) The application of the organophosphorus ligand polymer of the present invention simplifies the carbonyl synthesis process and reduces production costs. Industrial carbonyl synthesis equipment typically employs a rhodium low-pressure carbonyl synthesis liquid-phase circulation process, which is widely used, but this process suffers from complex procedures and high operating costs. Using the organophosphorus ligand polymer developed in this invention as a carrier and ligand, the traditional carbonyl synthesis process is altered in terms of the reaction system, separation system, and circulation system, thereby significantly reducing production costs.

[0056] (5) The application of the organophosphorus ligand polymer of the present invention solves the stability problems of homogeneous catalyst separation and recycling. In the hydroformylation reaction of high-carbon olefins, to overcome the technical difficulty of separating homogeneous catalysts, a two-phase water-oil catalyst is usually used. However, to improve the miscibility of the water and oil phases and increase the reaction efficiency of the catalyst, a certain amount of surfactant is usually added to the reaction system, which causes emulsification of the reaction system, thus increasing the difficulty of subsequent product separation. The organophosphorus ligand polymer developed in this invention serves as both a support and ligand, forming a single-point coordination structure for catalysis, which can improve activity and solve the problems of catalyst separation and recycling. Attached Figure Description

[0057] Figure 1 The liquid nuclear magnetic resonance hydrogen spectrum of compound 2 in Example 2;

[0058] Figure 2 The liquid nuclear magnetic resonance hydrogen spectrum of compound 3 in Example 3;

[0059] Figure 3 The liquid NMR phosphorus spectrum of compound 3 in Example 3;

[0060] Figure 4 The 1H NMR spectrum of organophosphine ligand polymer L1 in Example 4;

[0061] Figure 5 The phosphorus NMR spectrum of organophosphine ligand polymer L1 in Example 4;

[0062] Figure 6 The NMR phosphorus spectrum of organophosphorus ligand polymer L2 in Example 8. Detailed Implementation

[0063] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0064] This invention provides a method for preparing two organophosphorus ligand polymers, L1 and L2, whose chemical structures are as follows:

[0065]

[0066] Where m is 35-45 and n is 35-1350.

[0067] The synthetic route of organophosphine ligand polymer L1 is shown in reaction formula 2, and the synthetic route of organophosphine ligand polymer L2 is shown in reaction formula 3; wherein, compound 3 is a bidentate phosphine monomer.

[0068]

[0069] Example 1

[0070] Compound 1 was synthesized in this embodiment, and the synthesis method is described in reference CN113004326A.

[0071] Example 2:

[0072] In this embodiment, compound 2 is synthesized using the following method:

[0073] Add 5g of compound 1 to a reactor, add 100ml of toluene, then add 12g of vinyltri-n-butyltin and 0.73g of tetrakis(triphenylphosphine)palladium, and reflux overnight under nitrogen protection. Cool to room temperature, remove the solvent by vacuum distillation, and purify by column chromatography with petroleum ether:ethyl acetate = 2:1 as the eluent to obtain compound 2.

[0074] like Figure 1 As shown, its NMR data is as follows: 1H NMR(400MHz,DMSO)δ9.39(s,1H),7.16(dt,J=11.2,8.2Hz,2H),6.60(d,J=8.5Hz,1H),5 .56(d,J=1.4Hz,1H),5.18(dd,J=11.0,1.4Hz,1H),5.10(d,J=1.7Hz,1H),1.51(s,2H).

[0075] Example 3

[0076] In this embodiment, compound 3 is synthesized using the following method:

[0077] Take 1.27g of the phosphine chloride from step 3 above. Add the compound to the reactor, and under nitrogen protection, add 6 ml of ultra-dry tetrahydrofuran, then cool to 0°C. Separately, dissolve 400 mg of compound 2 and 418 mg of triethylamine in 2 ml of ultra-dry tetrahydrofuran, and add this mixture dropwise to the reactor at 0°C. Allow the mixture to naturally warm to room temperature and react for 1 h. Quench the reaction with 20 ml of water, extract with 20 ml of ethyl acetate, dry the organic phase with anhydrous sodium sulfate, and separate by column chromatography to obtain compound 3.

[0078] like Figure 2 and Figure 3 As shown, its NMR data is as follows: 1 H NMR (400MHz, CDCl3) δ7.22(d,J=8.5Hz,2H),7.14(dd,J=17.4,11.0Hz,2H),7.03(d,J=3.8Hz,5H),6.97(d,J=8.5Hz,2H),6.92(d,J=8.3Hz,5H),5.61( dd,J=17.4,1.2Hz,2H),5.42(s,1H),5.34(dd,J=11.0,1.2Hz,2H),5.15(s, 0H), 2.31 (d, J = 7.2Hz, 12H), 2.21 (d, J = 3.6Hz, 12H), 1.67 (q, J = 9.1Hz, 4H).

[0079] Example 4

[0080] In this embodiment, the organophosphine ligand polymer L1 is synthesized using the following method:

[0081] 400 mg of compound 3 was added to a reactor, along with 450 mg of styrene, 50 mg of AIBN, and 9 mL of ultra-dry tetrahydrofuran. The reaction was carried out at 100 °C for 4 h under nitrogen protection. After cooling to room temperature, 20 mL of methanol was added to precipitate the compound. The precipitate was filtered, washed with methanol, and dried under vacuum to obtain organophosphorus polymer L1. Its 1H NMR and 1N M NMR spectra are shown below. Figure 4 and Figure 5 As shown.

[0082] The ratio of m:n is 1:6, the polymer molecular weight is 70,000 g / mol, the product yield is 97.8%, and the purity is 98.2%.

[0083] Example 5

[0084] In this embodiment, the organophosphine ligand polymer L1 is synthesized using the following method:

[0085] 400 mg of compound 3 was added to a reactor, along with 500 mg of styrene, 45 mg of AIBN, and 9 ml of ultra-dry tetrahydrofuran. The reaction was carried out at 100 °C for 4 h under nitrogen protection. After cooling to room temperature, 20 ml of methanol was added to precipitate the compound. The precipitate was filtered, washed with methanol, and dried under vacuum to obtain organophosphorus polymer L1.

[0086] The ratio of m:n is 1:10, the polymer molecular weight is 95000 g / mol, the product yield is 97.6%, and the purity is 99.3%.

[0087] Example 6

[0088] In this embodiment, the organophosphine ligand polymer L1 is synthesized using the following method:

[0089] 400 mg of compound 3 was added to a reactor, along with 600 mg of styrene, 45 mg of AIBN, and 9 ml of ultra-dry tetrahydrofuran. The reaction was carried out at 100 °C for 4 h under nitrogen protection. After cooling to room temperature, 20 ml of methanol was added to precipitate the compound. The precipitate was filtered, washed with methanol, and dried under vacuum to obtain organophosphorus polymer L1.

[0090] The ratio of m:n is 1:20, the polymer molecular weight is 140,000 g / mol, the product yield is 97.3%, and the purity is 98.8%.

[0091] Example 7

[0092] In this embodiment, the organophosphine ligand polymer L1 is synthesized using the following method:

[0093] 400 mg of compound 3 was added to a reactor, along with 600 mg of styrene, 40 mg of AIBN, and 9 ml of ultra-dry tetrahydrofuran. The reaction was carried out at 90 °C for 4 h under nitrogen protection. After cooling to room temperature, 20 ml of methanol was added to precipitate the compound. The precipitate was filtered, washed with methanol, and dried under vacuum to obtain organophosphorus polymer L1.

[0094] The ratio of m:n is 1:30, the polymer molecular weight is 180,000 g / mol, the product yield is 97.5%, and the purity is 99.0%.

[0095] Example 8

[0096] In this embodiment, the organophosphine ligand polymer L2 is synthesized using the following method:

[0097] 300 mg of compound 3 was added to a reactor, along with 1.0 g of tris(4-vinylphenyl)phosphine, 35 mg of AIBN, and 15 mL of ultra-dry tetrahydrofuran. The reaction was carried out at 100 °C for 4 h under nitrogen protection. After cooling to room temperature, 30 mL of methanol was added to precipitate the compound. The precipitate was filtered, washed with methanol, and dried under vacuum to obtain the organophosphine ligand polymer L2. Its phosphorus NMR spectrum is shown below. Figure 6 As shown.

[0098] The ratio of m:n is 1:6, the polymer molecular weight is 85000 g / mol, the product yield is 96.8%, and the purity is 98.9%.

[0099] Example 9

[0100] In this embodiment, the organophosphine ligand polymer L2 is synthesized using the following method:

[0101] 300 mg of compound 3 was added to a reactor, along with 1.22 g of tris(4-vinylphenyl)phosphine, 35 mg of AIBN, and 15 ml of ultra-dry tetrahydrofuran. The reaction was carried out at 100 °C for 4 h under nitrogen protection. After cooling to room temperature, 30 ml of methanol was added to precipitate the compound. The precipitate was filtered, washed with methanol, and dried under vacuum to obtain the organophosphine ligand polymer L2.

[0102] The ratio of m:n is 1:10, the polymer molecular weight is 11000 g / mol, the product yield is 97.1%, and the purity is 99.1%.

[0103] Example 10

[0104] In this embodiment, the organophosphine ligand polymer L2 is synthesized using the following method:

[0105] 300 mg of compound 3 was added to a reactor, along with 1.50 g of tris(4-vinylphenyl)phosphine, 35 mg of AIBN, and 15 ml of ultra-dry tetrahydrofuran. The reaction was carried out at 95 °C for 4 h under nitrogen protection. After cooling to room temperature, 30 ml of methanol was added to precipitate the compound. The precipitate was filtered, washed with methanol, and dried under vacuum to obtain the organophosphine ligand polymer L2.

[0106] The ratio of m:n is 1:20, the polymer molecular weight is 165,000 g / mol, the product yield is 96.8%, and the purity is 98.8%.

[0107] Example 11

[0108] In this embodiment, the organophosphine ligand polymer L2 is synthesized using the following method:

[0109] 300 mg of compound 3 was added to a reactor, along with 1.80 g of tris(4-vinylphenyl)phosphine, 30 mg of AIBN, and 15 ml of ultra-dry tetrahydrofuran. The reaction was carried out at 85 °C for 4 h under nitrogen protection. After cooling to room temperature, 30 ml of methanol was added to precipitate the compound. The precipitate was filtered, washed with methanol, and dried under vacuum to obtain the organophosphine ligand polymer L2.

[0110] The ratio of m:n is 1:30, the polymer molecular weight is 195,000 g / mol, the product yield is 96.2%, and the purity is 98.6%.

[0111] Example 12

[0112] This embodiment provides an application of organophosphorus ligand polymer L2 (m=36, n=52, m:n=1:1.44) in the hydroformylation reaction of butadiene, as detailed below:

[0113] In a glove box, 20 mg of organophosphorus ligand polymer L2 and 1 mg of rhodium precursor Rh(acac)(CO)2 were added to an autoclave, followed by 3 ml of toluene. The autoclave was sealed, and a mixture of H2 and CO at a pressure of 2 MPa and a volume ratio of 1:1 was introduced. The mixture was stirred at 80 °C for 2 h to prepare the catalyst. The temperature was lowered, and 1 ml of 3 mol / L 1,3-butadiene toluene solution was added. The pressure was increased to 4 MPa, and the mixture was stirred at 80 °C for 12 h to prepare 1,6-hexanedialdehyde.

[0114] The conversion rate of 1,3-butadiene was 99.5% and the selectivity of 1,6-hexanedialdehyde was 53.4%, as determined by gas chromatography with internal standard method.

[0115] Example 13

[0116] Similar to Example 12, this example provides an application of organophosphorus ligand polymer L2 in olefin polymerization, the only difference being that in this example, the organophosphorus ligand polymer L2 has m = 25, n = 52, and m:n = 0.48. Details are as follows:

[0117] In a glove box, 20 mg of organophosphorus ligand polymer L2 and 1 mg of rhodium precursor Rh(acac)(CO)2 were added to an autoclave, followed by 3 ml of toluene. The autoclave was sealed, and a mixture of H2 and CO at a pressure of 2 MPa and a volume ratio of 1:1 was introduced. The mixture was stirred at 80 °C for 2 h to prepare the catalyst. The temperature was lowered, and 1 ml of 3 mol / L 1,3-butadiene toluene solution was added. The pressure was increased to 4 MPa, and the mixture was stirred at 80 °C for 12 h to prepare 1,6-hexanedialdehyde.

[0118] The conversion rate of 1,3-butadiene was 93.2% and the selectivity of 1,6-hexanedialdehyde was 40.2%, as determined by gas chromatography with internal standard method.

[0119] Comparative Example 1

[0120] Similar to Example 12, this comparative example provides an application of organophosphorus ligand polymer L3 in olefin polymerization. The only difference between organophosphorus ligand polymer L3 and organophosphorus ligand polymer L2 is that m = 36, n = 1440, and m:n = 1:40; all other structures are the same. Details are as follows:

[0121] In a glove box, 20 mg of organophosphorus ligand polymer L3 and 1 mg of rhodium precursor Rh(acac)(CO)2 were added to an autoclave, followed by 3 ml of toluene. The autoclave was sealed, and a mixture of H2 and CO at a pressure of 2 MPa and a volume ratio of 1:1 was introduced. The mixture was stirred at 80 °C for 2 h to prepare the catalyst. The temperature was lowered, and 1 ml of 3 mol / L 1,3-butadiene toluene solution was added. The pressure was increased to 4 MPa, and the mixture was stirred at 80 °C for 12 h to prepare 1,6-hexanedialdehyde.

[0122] The conversion rate of 1,3-butadiene was 50.5% and the selectivity of 1,6-hexanedialdehyde was 13.7%, as determined by gas chromatography with internal standard. In this comparative example, the m:n value of the organophosphorus ligand polymer L3 was too small, resulting in poor performance in olefin hydroformylation reactions.

Claims

1. An organophosphorus ligand polymer, characterized in that, Its structure is shown in general formula (I). Wherein, R1 and R2 are selected from the same or different phosphorus-containing groups, and R1 and R2 are each independently selected from the following structures: R3 is selected from m is 35-45, and n is 35-1350.

2. The organophosphine ligand polymer according to claim 1, characterized in that, R1 and R2 are each independently selected 3. The organophosphine ligand polymer according to claim 1, characterized in that, R3 is selected from 4. The organophosphine ligand polymer according to claim 1, characterized in that, The organophosphine ligand polymer is copolymerized from a bidentate phosphine monomer and a vinyl monomer. The structure of the bidentate phosphine monomer is shown in general formula (II), and the structure of the vinyl monomer is as follows:

5. The organophosphine ligand polymer according to claim 1, characterized in that, m:n is 1:(1-30).

6. The organophosphine ligand polymer according to claim 1, characterized in that, The molecular weight range of the organophosphorus ligand polymer is 50,000-200,000 g / mol.

7. The organophosphine ligand polymer according to claim 1, characterized in that, The degree of polymerization of the organophosphine ligand polymer is 35-55.

8. A method for preparing the organophosphorus ligand polymer according to any one of claims 1-7, characterized in that, Includes the following steps: S1: Under an inert gas atmosphere and in the presence of triethylamine, R1-Cl and / or R2-Cl and compound 2 are brought into full contact in the first solvent to react, the reaction is quenched, the reaction products are collected and purified to obtain the bidentate phosphine monomer. S2: Under an inert gas atmosphere and in the presence of azobisisobutyronitrile, the bidentate phosphine monomer and vinyl monomer are fully contacted in a second solvent to carry out a copolymerization reaction. The reaction is then terminated, and the reaction product is collected and purified to obtain the organophosphine ligand polymer. Wherein, the structure of compound 2 is 9. The preparation method according to claim 8, characterized in that, In S2, the copolymerization reaction temperature is 60-100℃ and the reaction time is 2-6h.

10. The preparation method according to claim 8, characterized in that, In S2, the second solvent is selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, and toluene.

11. The preparation method according to claim 8, characterized in that, In S1, the reaction temperature is 60-100℃ and the reaction time is 2-6h.

12. The preparation method according to claim 8, characterized in that, In S1, the first solvent is selected from one or more of tetrahydrofuran, toluene, and N,N-dimethylformamide.

13. The preparation method according to claim 8, characterized in that, The preparation method further includes the step of preparing compound 2, wherein the preparation method of compound 2 includes: under a nitrogen atmosphere and the action of a catalyst, compound 1 and an ethyleneizing agent are fully contacted in a third solvent to carry out an ethyleneization reaction, and the reaction product is collected and purified to obtain compound 2; Wherein, the structure of compound 1 is as follows:

14. The preparation method according to claim 13, characterized in that, The ethyleneation reaction temperature is 10-60℃, and the reaction time is 5-10h.

15. The preparation method according to claim 13, characterized in that, The ethyleneizing agent is selected from... One or more of them.

16. The preparation method according to claim 13, characterized in that, The catalyst is selected from one or more of tetra(triphenylphosphine)palladium, PdCl2(dppf) or PdCl2(PPh3)2.

17. The preparation method according to claim 13, characterized in that, The third solvent is selected from one or more of toluene, tetrahydrofuran, and 1,4-dioxane.

18. The use of the organophosphine ligand polymer according to any one of claims 1-7 in the hydroformylation reaction of olefins.

19. The application according to claim 18, characterized in that, The olefin is selected from C4-C6. 10 Olefins.

20. The application according to claim 19, characterized in that, The olefin is butadiene.

21. The application according to claim 18, characterized in that, The organophosphine ligand polymer forms a heterogeneous rhodium catalyst system.

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