Hypercrosslinked microporous polymer phosphine ligand as well as preparation method and application thereof

Abstract

The invention relates to a super-crosslinked microporous polymer phosphine ligand as well as a preparation method and application thereof, and belongs to the technical field of heterogeneous catalysts. The structure of the phosphine ligand is shown as a formula (I), the ligand is provided with a plurality of coordination sites, the ligand is internally provided with a hypercrosslinked microporous framework with a highly ordered crystal structure, and the phosphine ligand has a large surface area and clear porosity, can effectively adsorb H2 / CO, and provides more reaction sites. When the ligand is used for preparing the catalyst which is easy to separate, high in conversion rate and high in selectivity, the conversion rate of isooctene and the generation selectivity of isononanal can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of heterogeneous catalysts, and in particular to a super-crosslinked microporous polymer phosphine ligand and a preparation method and application thereof. Background Art

[0002] Isononanal is an important organic chemical raw material for many high value-added fine chemical products. For example, isononanal can be oxidized to obtain isononanoic acid. Its unique properties such as excellent wettability, permeability and emulsification make high-branched isononanoic acid have important uses in lubricants, industrial detergents and other industries.

[0003] At present, isononanoic acid is mainly imported from abroad, and the domestic isononanoic acid / isononanal industrial production technology is still basically in the laboratory stage. Tsinghua University, China University of Petroleum and Wanhua Chemical have reported related production processes, including homogeneous catalytic systems, water / oil two-phase catalytic systems, and multiphase solid-supported catalytic systems.

[0004] Ma Zhanhua's research group at China University of Petroleum loaded Rh on activated carbon to prepare a solid-supported Rh-based catalyst, which was then applied to the hydroformylation of mixed isooctene. Under the conditions of Rh loading of 0.90wt%, reaction time of 5.0h, temperature of 107℃, and pressure of 5.0MPa, the conversion rate of mixed octene reached 63.6% and the aldehyde yield was 48.5%.

[0005] Tsinghua University C1 National Laboratory for Chemical Engineering uses a rhodium catalyst with triphenylphosphine oxide as a ligand to homogeneously catalyze the hydroformylation of mixed octenes obtained by butene polymerization. At 140°C and 10.5MPa, the yield of isononanal reaches over 85%.

[0006] Song Jinbo et al. studied the hydroformylation of mixed C8 olefins using a water / oil two-phase catalytic system. The reaction conditions were: reaction time 5h, reaction temperature 105-120°C, total reaction pressure 5MPa, CO / H2=2 / 3. Under these reaction conditions, the conversion rate of olefins to aldehydes reached 54% and the selectivity was 96%.

[0007] In summary, the prior art has problems such as low conversion rate and product selectivity of isooctene hydroformylation, high catalyst production cost and difficulty in catalyst separation. Summary of the invention

[0008] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a hyper-crosslinked microporous polymer phosphine ligand and a preparation method thereof, as well as a multiphase catalyst containing the ligand and a preparation method and application thereof. The use of a specific ligand to prepare a catalyst with easy separation, high conversion rate and high selectivity is very important for the conversion rate of isooctene and the generation selectivity of isononanal. The use of a hyper-crosslinked microporous polymer phosphine ligand-Rh catalyst can effectively solve the above-mentioned problems. On the one hand, the controllable ordered pore structure of the hyper-crosslinked microporous polymer phosphine ligand is conducive to the material transmission process; on the other hand, the regular pores of the hyper-crosslinked microporous polymer phosphine ligand can also provide type selectivity. Therefore, the hyper-crosslinked microporous polymer phosphine ligand-Rh catalyst has great potential in the hydroformylation reaction of high-carbon olefins. It can not only realize the separation and recycling of the catalyst and the reaction liquid, but also provide more reaction sites and adsorb H2 / CO to improve the conversion rate of olefins, and can also improve the selectivity of aldehydes through the pore size.

[0009] To achieve the above object, the technical solution adopted by the present invention is:

[0010] In a first aspect, the present invention provides a hyper-crosslinked microporous polymer phosphine ligand having a structure shown in formula (I):

[0011]

[0012] Among them, R1 is at least one of a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl group, a heterocyclic group, a heterocyclic alkyl group, an aryl group, a substituted aryl group, and a substituted aryl derivative group; R2 is at least one of a hydrogen, a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl group, a heterocyclic group, a heterocyclic alkyl group, an aryl group, a substituted aryl group, and a substituted aryl derivative group.

[0013] The hyper-crosslinked microporous polymer phosphine ligand has multiple coordination sites, which makes the ligand have a hyper-crosslinked microporous skeleton with a highly ordered crystal structure, and also has a large surface area and clear porosity, which can effectively adsorb H2 / CO and provide more reaction sites. This can solve the problems of reduced activity and loss of active components, that is, the problem of poor reaction stability.

[0014] Preferably, the R1 is at least one of a methyl group, an ethyl group, and a tert-butyl group; and the R2 is at least one of a hydrogen group and a methoxy group.

[0015] In a second aspect, the present invention provides a method for preparing the hyper-crosslinked microporous polymer phosphine ligand, comprising the following steps:

[0016] (1) using a substituted diphenyl chlorophosphite compound and 4-hydroxystyrene as raw materials, reacting in the presence of an acid binding agent to synthesize a triphenyl phosphite compound containing an unsaturated double bond; wherein the acid binding agent is triethylamine;

[0017] (2) An aqueous solution containing hydroxyethyl cellulose, gelatin and sodium chloride is used as a reaction solvent, triphenyl phosphite compound containing unsaturated double bonds and divinylbenzene are copolymerized monomers, benzoyl peroxide is used as an initiator, and toluene and heptane are dispersed oil phases; after polymerization, the super-crosslinked microporous polymer phosphine ligand is obtained. The mass ratio of hydroxyethyl cellulose, gelatin and sodium chloride is (0.5-5): (0.1-2): (0.5-3), and the above components are mixed in 50 mL of water to prepare a reaction solvent. The mass ratio of triphenyl phosphite compound containing unsaturated double bonds, divinylbenzene and initiator is (0.5-20.0): (0.1-1): (0.05-0.5). The volume ratio of toluene to heptane is (5-100): (5-100).

[0018] Preferably, the substituted diphenyl chlorophosphite compound is one of di(2,6-dimethyl)phenyl chlorophosphite, di(2,6-diethyl)phenyl chlorophosphite, di(2,6-di-tert-butyl)phenyl chlorophosphite and di(2,6-di-tert-butyl-4-methoxy)phenyl chlorophosphite.

[0019] Preferably, in step (1), the reaction temperature is 50-150° C. After the reaction is completed, the mixture is cooled to room temperature, and the solvent is removed by distillation under reduced pressure to obtain a crude product, which is then purified to obtain a solid triphenyl phosphite compound containing an unsaturated double bond.

[0020] In a third aspect, the present invention provides an application of a hyper-crosslinked microporous polymer phosphine ligand in the preparation of a heterogeneous catalyst.

[0021] In a fourth aspect, the present invention provides a multiphase catalyst, comprising the above-mentioned hyper-crosslinked microporous polymer phosphine ligand and a metal active component supported on the hyper-crosslinked microporous polymer phosphine ligand.

[0022] Preferably, the mass ratio of the hyper-crosslinked microporous polymer phosphine ligand to the metal active component is (10-100):1.

[0023] The catalyst belongs to a microporous multiphase catalyst. The catalyst has a ligand with a specific structure and a metal active component loaded on the ligand, which makes the catalyst have a super-crosslinked microporous structure, and has the advantages of easy separation, high conversion rate and high selectivity. The specific advantages are as follows: 1) The catalyst can be separated by suction filtration after the reaction, so that the catalyst can be reused; 2) The super-crosslinked microporous polymer phosphine ligand with a highly ordered crystal structure has a large surface area and a clear porosity, which can effectively adsorb H2 / CO, provide more reaction sites, and is conducive to the hydroformylation reaction of high-carbon chain olefins (above C6), thereby improving the catalytic performance.

[0024] Preferably, the metal active component is rhodium.

[0025] Specifically, the present invention provides a method for preparing a heterogeneous catalyst, comprising the following steps:

[0026] The super-crosslinked microporous polymer phosphine ligand is placed in a solution containing metal active components for reaction, and the solvent is removed after the reaction to obtain a multiphase catalyst.

[0027] Preferably, the reaction parameters are: temperature of 25 to 100° C., stirring time of 1 to 100 h, reaction under argon atmosphere, and removal of solvent by reduced pressure distillation.

[0028] Preferably, the solution containing the metal active component is a tetrahydrofuran solution of acetylacetonato dicarbonyl rhodium.

[0029] In a fifth aspect, the present invention provides the use of a multiphase catalyst in catalyzing the hydroformylation reaction of higher carbon olefins to prepare higher aldehydes, wherein the catalytic performance for preparing isononanal is the best.

[0030] Preferably, the application is to prepare isononanal by using isooctene, carbon monoxide and hydrogen under the action of a heterogeneous catalyst. Preferably, the feed mass ratio of isooctene:carbon monoxide:hydrogen is 1:1-2:1-2; preferably, isooctene, carbon monoxide and hydrogen are contacted and reacted with the catalyst in an organic solvent; more preferably, the organic solvent includes at least one of cyclohexane, benzene, toluene, ether, tetrahydrofuran and isononanal.

[0031] The catalyst is suitable for the hydroformylation reaction of high-carbon olefins, can improve the conversion rate of olefins, can improve the selectivity of aldehydes, and can realize the repeated use of the catalyst.

[0032] Preferably, the reaction parameters for preparing isononanal are: the amount of the heterogeneous catalyst added is 0.05% to 10% of the mass of isooctene; the reaction is carried out at a temperature of 50 to 280° C. and a pressure of 0.5 to 20 MPa for 0.5 to 100 h. More preferred reaction conditions are: 90 to 160° C., 2 to 6 MPa, and 8 to 18 h.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The structure of the hyper-crosslinked microporous polymer phosphine ligand of the present invention is shown in formula (I), and the ligand has multiple coordination sites. The ligand has a hyper-crosslinked microporous skeleton with a highly ordered crystal structure, which has a large surface area and a clear porosity and can effectively adsorb H2 / CO, providing more reaction sites.

[0035] (2) The multiphase catalyst of the present invention comprises a hyper-crosslinked microporous polymer phosphine ligand and a metal active component supported on the hyper-crosslinked microporous polymer phosphine ligand, so the catalyst belongs to a hyper-crosslinked microporous catalyst, and the catalyst has the following advantages: 1) the hyper-crosslinked microporous polymer phosphine ligand-Rh multiphase catalyst can be separated by suction filtration after the reaction, so that the catalyst can be reused; 2) the hyper-crosslinked microporous polymer phosphine ligand with a highly ordered crystal structure has a large surface area and a clear porosity, which can effectively adsorb H2 / CO, provide more reaction sites, and is conducive to the hydroformylation reaction of high-carbon chain olefins (above C6), thereby improving the catalytic performance; 3) the controllable ordered pore structure thereof is conducive to the material transmission process, and can also improve the selectivity of aldehydes by controlling the pore size. Therefore, the hyper-crosslinked microporous polymer phosphine ligand-Rh catalyst has great potential in the hydroformylation reaction of high-carbon olefins, which can not only realize the separation and recycling of the catalyst and the reaction liquid, but also provide more reaction sites and adsorb H2 / CO to improve the conversion rate of olefins, and can also improve the selectivity of aldehydes by the pore size.

[0036] (3) The catalyst of the present invention adopts an impregnation method to load the metal active component on the super-crosslinked microporous polymer phosphine ligand. The preparation method is simple and suitable for large-scale preparation.

[0037] (4) Preferably, a hyper-crosslinked microporous polymer phosphine ligand-Rh catalyst having a structure shown in formula (1) is used in a multiphase catalytic reaction of preparing isononanal by hydroformylation of isooctene, which can improve the conversion rate of isooctene and the selectivity and conversion rate of isononanal. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The relationship between the number of times the catalyst Rh-4 in Example 4 is reused and its catalytic performance. DETAILED DESCRIPTION

[0039] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0040] The Rh catalyst including the hyper-crosslinked microporous polymer phosphine ligand having the structure shown in formula (1) is applied to the multiphase catalytic reaction of preparing isononanal by hydroformylation of isooctene, which can improve the conversion rate of isooctene and the selectivity of isononanal. The catalyst and its preparation method and application are shown in Examples 1 to 4, and the application examples based on the catalyst separation and reuse experiment of Example 4 are shown in Application Examples 1 to 9. The comparative examples corresponding to the catalysts of Examples 1 to 4 are Comparative Examples 1 to 3.

[0041]

[0042] Example 1

[0043] The method for preparing a hyper-crosslinked microporous polymer ligand comprises the following steps:

[0044] 1) Synthesis of bis(2,6-dimethylphenyl)(4-vinylphenyl)phosphite: The specific reaction route is shown in formula (2). Di(2,6-dimethylphenyl)chlorophosphite (10 g, 32.4 mmol), 4-hydroxystyrene (4.28 g, 35.6 mmol) and toluene (100 mL) were placed in a 250 mL two-necked flask, followed by the addition of Et3N (3.6 g, 35.6 mmol). The resulting mixture was stirred at 90° C. for 16 h, cooled to room temperature after the reaction was complete, and the solvent was removed by vacuum distillation to obtain a crude product. The crude product was redissolved in CH2Cl2 (100 mL), filtered through diatomaceous earth to remove the Et3N·HCl precipitate, and the solvent was removed by vacuum distillation to obtain a crude product. Bis(2,6-dimethylphenyl)(4-vinylphenyl)phosphite (10.8 g, 85%) was obtained as a colorless solid by recrystallization (isopropanol). 1 H NMR (400MHz, CDCl3) δ: 7.45 (d, J=8.0Hz, 2H, ArH), 6.99 (t, J=7.6Hz, 2H, ArH), 6.89 (dd, J1=7.6Hz, J2=1.6Hz, 4H, ArH), 6.76 ( d,J=8.0Hz,2H,ArH),6.72(dd,J1=17.6,J2=10.9Hz,1H),5.75(d,J=17.6Hz,1H),5.22(d,J=10.9Hz,1H),2.15(s,12H,CH3).

[0045]

[0046] 2) Synthesis of hyper-crosslinked microporous polymer ligands:

[0047] Take a certain amount of water and add a certain amount of hydroxyethyl cellulose under stirring, and continue stirring for 24 hours to obtain a clear solution; take another certain amount of water and heat it to 50°C, add a certain amount of gelatin under continuous stirring, and cool it to room temperature after dissolving; take another certain amount of water and add a certain amount of sodium chloride, and mix the above three solutions to form an aqueous phase after dissolving. Add the aqueous phase to a three-necked flask equipped with a stirrer, a condenser and a nitrogen tube, take 10g of bis(2,6-dimethylphenyl)phosphite (4-vinylphenyl) ester and 0.4g of divinylbenzene, and then take 0.1g of benzoyl peroxide and add it under stirring, and then add a certain amount of toluene and heptane to form a dispersed oil phase; pass nitrogen for 30 minutes to drive away the air; start the stirrer, add the oil phase to the aqueous phase, and stir for 10 minutes; adjust the speed to 500r / min, and heat the oil bath to 60°C for 24 hours. After the reaction is completed, the reaction mixture is cooled to room temperature and filtered under reduced pressure. The obtained polymer is transferred to a flask filled with distilled water, heated to 50°C with stirring, and filtered under reduced pressure while hot; then transferred to a flask filled with ethanol twice the volume of the polymer, heated to 50°C with stirring, and filtered under reduced pressure while hot after 1 hour. This operation is repeated until the unreacted monomers and solvent are completely washed away to obtain a super-crosslinked microporous polymer phosphine ligand 1 containing phosphite.

[0048] Heterogeneous Catalyst Products

[0049] The method for preparing a heterogeneous catalyst comprises the following steps:

[0050] At 25°C and in an Ar gas atmosphere, 1.0 g of the above-prepared phosphite-containing hyper-crosslinked microporous polymer phosphine ligand 1 was added to a tetrahydrofuran (100 mL) solution containing 30 mg of acetylacetonato dicarbonyl rhodium and stirred for 24 h. Subsequently, the solvent was removed in vacuo at 50°C to obtain a heterogeneous catalyst (Rh-1) in which a phosphite-containing hyper-crosslinked microporous polymer phosphine ligand coordinated / loaded with a Rh metal component.

[0051] Application of the heterogeneous catalyst of this embodiment

[0052] Isooctene Hydroformylation Process

[0053] Rh-1 is suitable for the hydroformylation reaction of C6-C14 high carbon olefins to prepare C7-C15 high carbon aldehydes. This embodiment takes isooctene as an example.

[0054] 40 mL of isooctyl, 0.1 g of catalyst Rh-1 and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. The carbon monoxide / hydrogen cylinder was connected and quickly heated to 90 ° C. At the same time, the system pressure was adjusted to 1.5 MPa, the stirring rate was 800 rpm, and maintained for 18 hours. After the reaction was completed, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction liquid was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0055] Example 2

[0056] The structure of the hyper-crosslinked microporous polymer ligand of the compound of Example 2 is shown in formula (I):

[0057]

[0058] The preparation method of the super cross-linked microporous polymer phosphine ligand comprises the following steps:

[0059] 1) Synthesis of bis(2,6-diethylphenyl)(4-vinylphenyl)phosphite: The specific route is shown in formula (3). Di(2,6-diethyl)phenyl chlorophosphite (10 g, 27.40 mmol), 4-hydroxystyrene (3.6 g, 30.14 mmol) and toluene (100 mL) were placed in a 250 mL two-necked flask, followed by the addition of Et3N (3.1 g, 30.14 mmol). The resulting mixture was stirred at 90°C for 16 h, cooled to room temperature after the reaction was complete, and the solvent was removed by vacuum distillation to obtain a crude product, which was redissolved in CH2Cl2 (100 mL), filtered through diatomaceous earth to remove the Et3N·HCl precipitate, and the solvent was removed by vacuum distillation to obtain a crude product, which was recrystallized (isopropanol) to obtain the compound bis(2,6-diethylphenyl)(4-vinylphenyl)phosphite (11.2 g, 91%) as a colorless solid. 1 H NMR (400MHz, CDCl3) δ: 7.47 (d, J=8.0Hz, 2H, ArH), 6.97 (t, J=7.6Hz, 2H, ArH), 6.91 (dd, J1=7.6Hz, J2=1.6Hz, 4H, ArH), 6.77 (d, J=8.0Hz, 2H, ArH) H), 6.77 (dd, J1 = 17.6, J2 = 10.9Hz, 1H), 5.72 (d, J = 17.6Hz, 1H), 5.25 (d, J = 10.9Hz, 1H), 2.16 (q, J = 6.8Hz, 8H, CH2), 1.25 (t, J = 7.2Hz, 12H, CH3).

[0060]

[0061] 2) Synthesis of hyper-crosslinked microporous polymer phosphine ligands:

[0062] Take a certain amount of water and add a certain amount of hydroxyethyl cellulose under stirring, and continue stirring for 24 hours to obtain a clear solution; take another certain amount of water and heat it to 50°C, add a certain amount of gelatin under continuous stirring, and cool it to room temperature after dissolving; take another certain amount of water and add a certain amount of sodium chloride, and mix the above three solutions to form an aqueous phase after dissolving. Add the aqueous phase to a three-necked flask equipped with a stirrer, a condenser and a nitrogen tube, take 10g of the compound bis(2,6-diethylphenyl)phosphite (4-vinylphenyl) ester and 0.4g of divinylbenzene, and then take 0.1g of benzoyl peroxide and add it under stirring, and then add a certain amount of toluene and heptane to form a dispersed oil phase; pass nitrogen for 30 minutes to drive away the air; start the stirrer, add the oil phase to the aqueous phase, and stir for 10 minutes; adjust the speed to 500r / min, and heat the oil bath to 60°C for 24 hours. After the reaction is completed, the reaction mixture is cooled to room temperature and filtered under reduced pressure. The obtained polymer is transferred to a flask filled with distilled water, heated to 50°C with stirring, and filtered under reduced pressure while hot; then transferred to a flask filled with ethanol twice the volume of the polymer, heated to 50°C with stirring, and filtered under reduced pressure while hot after 1 hour. This operation is repeated until the unreacted monomers and solvents are completely washed away to obtain the super-crosslinked microporous polymer phosphine ligand 2.

[0063] The method for preparing a heterogeneous catalyst comprises the following steps:

[0064] At 25°C and in an Ar gas atmosphere, 1.0 g of the above-prepared phosphite-containing hyper-crosslinked microporous polymer ligand 2 was added to a tetrahydrofuran (100 mL) solution containing 30 mg of acetylacetonato dicarbonyl rhodium and stirred for 24 h. Subsequently, the solvent was removed in vacuo at 50°C to obtain a heterogeneous catalyst (Rh-2) in which a phosphite-containing hyper-crosslinked microporous polymer phosphine ligand coordinated / loaded with a Rh metal component.

[0065] Application of the heterogeneous catalyst of this example

[0066] Isooctene Hydroformylation Process

[0067] Rh-2 is suitable for the hydroformylation reaction of C6-C14 high carbon olefins to prepare C7-C15 high carbon aldehydes. This embodiment takes isooctene as an example.

[0068] 40 mL of isooctyl, 0.1 g of catalyst Rh-2 and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. The carbon monoxide / hydrogen cylinder was connected and quickly heated to 90 ° C. At the same time, the system pressure was adjusted to 1.5 MPa, the stirring rate was 800 rpm, and maintained for 18 hours. After the reaction was completed, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction liquid was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0069] Example 3

[0070] The preparation method of the super cross-linked microporous polymer phosphine ligand comprises the following steps:

[0071] 1) Synthesis of bis(2,6-di-tert-butylphenyl)(4-vinylphenyl)phosphite: The specific synthetic route is shown in formula (4): Di(2,6-di-tert-butyl)phenyl chlorophosphite (15 g, 31.40 mmol), 4-hydroxystyrene (4.15 g, 34.59 mmol) and toluene (100 mL) were placed in a 250 mL two-necked flask, followed by the addition of Et3N (3.58 g, 34.59 mmol). The resulting mixture was stirred at 90° C. for 16 h, cooled to room temperature after the reaction was complete, and the solvent was removed by vacuum distillation to obtain a crude product, which was redissolved in CH2Cl2 (100 mL), filtered through diatomaceous earth to remove the Et3N·HCl precipitate, and the solvent was removed by vacuum distillation to obtain a crude product, which was recrystallized (isopropanol) to obtain the compound bis(2,6-di-tert-butylphenyl)(4-vinylphenyl)phosphite (14.1 g, 80%) as a colorless solid. 1 H NMR (400MHz, CDCl3) δ: 7.47 (d, J = 8.0 Hz, 2H, ArH), 6.97 (t, J = 7.6 Hz, 2H, ArH), 6.91 (dd, J1 = 7.6 Hz, J2 = 1.6 Hz, 4H, ArH), 6.77 ( d,J=8.0Hz,2H,ArH),6.77(dd,J1=17.6,J2=10.9Hz,1H),5.72(d,J=17.6Hz,1H),5.25(d,J=10.9Hz,1H),1.25(s,36H,CH3).

[0072]

[0073] 2) Synthesis of hyper-crosslinked microporous polymer phosphine ligands:

[0074] Take a certain amount of water and add a certain amount of hydroxyethyl cellulose under stirring, and continue stirring for 24 hours to obtain a clear solution; take another certain amount of water and heat it to 50°C, add a certain amount of gelatin under continuous stirring, and cool it to room temperature after dissolving; take another certain amount of water and add a certain amount of sodium chloride, and mix the above three solutions to form an aqueous phase after dissolving. Add the aqueous phase to a three-necked flask equipped with a stirrer, a condenser and a nitrogen tube, take 10g of the compound bis(2,6-di-tert-butylphenyl)phosphite (4-vinylphenyl) ester and 0.4g of divinylbenzene, and then take 0.1g of benzoyl peroxide and add it under stirring, and then add a certain amount of toluene and heptane to form a dispersed oil phase; pass nitrogen for 30 minutes to drive away the air; start the stirrer, add the oil phase to the aqueous phase, and stir for 10 minutes; adjust the speed to 500r / min, and heat the oil bath to 60°C for 24 hours. After the reaction is completed, the reaction mixture is cooled to room temperature and filtered under reduced pressure. The obtained polymer is transferred to a flask filled with distilled water, heated to 50°C with stirring, and filtered under reduced pressure while hot; then transferred to a flask filled with ethanol twice the volume of the polymer, heated to 50°C with stirring, and filtered under reduced pressure while hot after 1 hour. This operation is repeated until the unreacted monomers and solvents are completely washed away to obtain a super-crosslinked microporous polymer phosphine ligand 3 containing phosphite.

[0075] The method for preparing a heterogeneous catalyst comprises the following steps:

[0076] At 25°C and in an Ar gas atmosphere, 1.0 g of the above-prepared phosphite-containing hyper-crosslinked microporous polymer phosphine ligand 3 was added to a tetrahydrofuran (100 mL) solution containing 30 mg of acetylacetonato dicarbonyl rhodium and stirred for 24 h. Subsequently, the solvent was removed in vacuo at 50°C to obtain a heterogeneous catalyst (Rh-3) in which the phosphite-containing hyper-crosslinked microporous polymer phosphine ligand coordinated / loaded with Rh metal components.

[0077] Application of the heterogeneous catalyst of this embodiment

[0078] Isooctene Hydroformylation Process

[0079] Rh-3 is suitable for the hydroformylation reaction of C6-C14 high carbon olefins to prepare C7-C15 high carbon aldehydes. This embodiment takes isooctene as an example.

[0080] 40 mL of isooctyl, 0.1 g of catalyst Rh-3 and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. The carbon monoxide / hydrogen cylinder was connected and quickly heated to 90 ° C. At the same time, the system pressure was adjusted to 1.5 MPa, the stirring rate was 800 rpm, and maintained for 18 hours. After the reaction was completed, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction liquid was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0081] Example 4

[0082] The preparation method of the super cross-linked microporous polymer phosphine ligand comprises the following steps:

[0083] 1) Synthesis of bis(2,6-dimethoxyphenyl)(4-vinylphenyl)phosphite: The specific synthetic route is as shown in formula (5). Di(2,6-dimethoxy-4-methoxy)phenyl chlorophosphite (15 g, 27.93 mmol), 4-hydroxystyrene (3.69 g, 30.72 mmol) and toluene (100 mL) were placed in a 250 mL two-necked flask, followed by the addition of Et3N (3.13 g, 30.72 mmol). The resulting mixture was stirred at 90° C. for 16 h, cooled to room temperature after the reaction was complete, and the solvent was removed by vacuum distillation to obtain a crude product. The crude product was redissolved in CH2Cl2 (100 mL), filtered through diatomaceous earth to remove the Et3N·HCl precipitate, and the solvent was removed by vacuum distillation to obtain a crude product. The compound bis(2,6-dimethoxyphenyl)(4-vinylphenyl)phosphite (14.02 g, 81%) was obtained as a colorless solid by recrystallization (isopropanol). 1 H NMR (400MHz, CDCl3) δ: 7.47 (d, J=8.0Hz, 2H, ArH), 6.97 (t, J=7.6Hz, 2H, ArH), 6.91 (dd, J1=7.6Hz, J2=1.6Hz, 4H, ArH), 6.77 (d, J=8.0H z, 2H, ArH), 6.77 (dd, J1 = 17.6, J2 = 10.9Hz, 1H), 5.72 (d, J = 17.6Hz, 1H), 5.25 (d, J = 10.9Hz, 1H), 3.46 (s, 6H, -OCH3), 1.25 (s, 36H, CH3).

[0084]

[0085] 2) Synthesis of hyper-crosslinked microporous polymer phosphine ligands:

[0086] Take a certain amount of water and add a certain amount of hydroxyethyl cellulose under stirring, and continue stirring for 24 hours to obtain a clear solution; take another certain amount of water and heat it to 50°C, add a certain amount of gelatin under continuous stirring, and cool it to room temperature after dissolving; take another certain amount of water and add a certain amount of sodium chloride, and mix the above three solutions to form an aqueous phase after dissolving. Add the aqueous phase to a three-necked flask equipped with a stirrer, a condenser and a nitrogen tube, take 10g of the compound bis(2,6-dimethoxyphenyl)phosphite (4-vinylphenyl) ester and 0.4g of divinylbenzene, mix them, take 0.1g of benzoyl peroxide and add it under stirring, then add a certain amount of toluene and heptane to form a dispersed oil phase; pass nitrogen for 30 minutes to drive away the air; start the stirrer, add the oil phase to the aqueous phase, and stir for 10 minutes; adjust the speed to 500r / min, and heat the oil bath to 60°C for 24 hours. After the reaction is completed, the reaction mixture is cooled to room temperature and filtered under reduced pressure. The obtained polymer is transferred to a flask filled with distilled water, heated to 50°C with stirring, and filtered under reduced pressure while hot; then transferred to a flask filled with ethanol twice the volume of the polymer, heated to 50°C with stirring, and filtered under reduced pressure while hot after 1 hour. This operation is repeated until the unreacted monomers and solvent are completely washed away to obtain a super-crosslinked microporous polymer phosphine ligand 4 containing phosphite.

[0087] The method for preparing a heterogeneous catalyst comprises the following steps:

[0088] At 25°C and in an Ar gas atmosphere, 1.0 g of the above-prepared phosphite-containing super-crosslinked microporous polymer phosphine ligand 4 was added to a tetrahydrofuran (100 mL) solution containing 30 mg of acetylacetonato dicarbonyl rhodium and stirred for 24 h. Subsequently, the solvent was removed in vacuo at 50°C to obtain a heterogeneous catalyst (Rh-4) in which the phosphite-containing super-crosslinked microporous polymer phosphine ligand coordinated / loaded with Rh metal components.

[0089] Application of the heterogeneous catalyst of this embodiment

[0090] Isooctene Hydroformylation Process

[0091] Rh-4 is suitable for the hydroformylation reaction of C6-C14 high carbon olefins to prepare C7-C15 high carbon aldehydes. This embodiment takes isooctene as an example.

[0092] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. The carbon monoxide / hydrogen cylinder was connected and quickly heated to 90 ° C. At the same time, the system pressure was adjusted to 1.5 MPa, the stirring rate was 800 rpm, and maintained for 18 hours. After the reaction was completed, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction liquid was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0093] Application Example 1

[0094] Catalyst separation and reuse experiment

[0095] In order to study the reusability of the Rh metal catalyst coordinated / loaded by the phosphite-containing hyper-crosslinked microporous polymer phosphine ligand, the catalyst Rh-4 of Example 4 was taken as an example. In a glove box filled with argon, the catalyst Rh-4 was separated from the reaction solution by suction filtration to obtain the catalyst Rh-4. The separated catalyst was put into the second to tenth isooctene hydroformylation reactions without any treatment.

[0096] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the first reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0097] Application Example 2

[0098] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the second reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0099] Application Example 3

[0100] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the third reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0101] Application Example 4

[0102] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the fourth reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0103] Application Example 5

[0104] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the fifth reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0105] Application Example 6

[0106] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the sixth reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0107] Application Example 7

[0108] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the 7th reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0109] Application Example 8

[0110] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the 8th reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0111] Application Example 9

[0112] 40 mL of isooctyl, 0.1 g of catalyst Rh-4 (isolated from the reaction solution of the 9th reaction) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. Connect the carbon monoxide / hydrogen cylinder, heat quickly to 90 ° C, adjust the system pressure to 1.5 MPa, stir at 800 rpm, and maintain for 18 hours. After the reaction, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0113] Comparative Example 1

[0114] 40 mL of isooctane, catalyst Rh2Cl2(CO)4 (200 ppm) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. The carbon monoxide / hydrogen cylinder was connected and quickly heated to 90°C. At the same time, the system pressure was adjusted to 1.5 MPa, the stirring rate was 800 rpm, and maintained for 18 hours. After the reaction was completed, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction liquid was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0115] Comparative Example 2

[0116] 40 mL of isooctane, catalyst Rh2Cl2(CO)4 (200 ppm), triphenylphosphine (600 ppm) and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. The carbon monoxide / hydrogen cylinder was connected and quickly heated to 90°C. At the same time, the system pressure was adjusted to 1.5 MPa, the stirring rate was 800 rpm, and maintained for 18 hours. After the reaction was completed, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction solution was extracted and treated for gas chromatography analysis. The data results are recorded in Table 1.

[0117] Comparative Example 3

[0118] In order to verify that the hyper-crosslinked microporous polymer phosphine ligand coordinated / loaded Rh metal catalyst has higher catalytic performance, we also prepared its reference polymer ligand (non-microporous polymer phosphine ligand), the preparation method is as follows:

[0119] At 25°C and in an inert gas Ar protective atmosphere, 10.0 grams of compound 4 was dissolved in 100 mL of tetrahydrofuran solvent, and 2.5 g of comonomer p-divinylbenzene was added at the same time. 0.1 grams of free radical initiator azobisisobutyronitrile was added to the above solution, and stirred for 2 hours to obtain a prepolymer. The prepolymer was transferred to an autoclave and polymerized by solvent thermal polymerization at 100°C and in an inert gas Ar protective atmosphere for 24 hours. After the polymerization autoclave was cooled to room temperature, the solvent was vacuumed away at room temperature to obtain a phosphine-containing organic polymer phosphine ligand copolymerized by compound 4 and p-divinylbenzene organic monomer. The corresponding non-microporous polymer phosphine ligand coordinated / loaded Rh catalyst Rh-5 was prepared according to a similar preparation method to Rh-4, and applied to the hydroformylation reaction of isooctene. The specific details are as follows:

[0120] 40 mL of isooctyl, 0.1 g of catalyst Rh-5 and 30 mL of toluene were added to a 200 mL autoclave, and then the air was replaced with N2. The carbon monoxide / hydrogen cylinder was connected and quickly heated to 90 ° C. At the same time, the system pressure was adjusted to 1.5 MPa, the stirring rate was 800 rpm, and maintained for 18 hours. After the reaction was completed, the reactor was quickly cooled to room temperature, slowly depressurized to normal pressure, and the reaction liquid was extracted for treatment and then analyzed by gas chromatography. The data results are recorded in Table 1.

[0121] Table 1 Catalytic performance of each group of catalysts in the hydroformylation of isooctene

[0122]

[0123]

[0124] As shown in Table 1, the catalysts prepared in Examples 1-4 have an isooctene conversion rate of more than 92% and an isononanal selectivity of more than 94% in the reaction of isooctene and CO, H2 hydroformylation to prepare isononanal. In particular, the catalyst Rh-4 prepared in Example 4 has an isooctene conversion rate of 96.8% and a tridecanal selectivity of 96.9% as a catalyst. The isooctene conversion rate and isononanal selectivity are significantly higher than those in Comparative Examples 1-2, indicating that the catalyst prepared in the present invention can be used in the isooctene hydroformylation to prepare isononanal, and can improve the isooctene conversion rate. The catalytic performance of Rh-4 is also better than that of the non-microporous polymer phosphine ligand coordinated / loaded Rh metal catalyst Rh-5 (Comparative Example 3), indicating that the micropores of the hyper-crosslinked microporous polymer phosphine ligand play a positive role. This is mainly attributed to the fact that the hyper-crosslinked polymer phosphine ligand containing micropores has more microchannels and surface area, which can have better coordination with Rh and more effective contact with the reaction liquid isooctene / H2 / CO, which can accelerate the hydroformylation reaction of isooctene, and more micropores can improve the selectivity of iso-nonanal.

[0125] In addition, if Figure 1 As shown, in the 10 repeated experiments of Application Examples 1 to 9, the activity of Rh-4 only decreased slightly (isooctenes conversion rate 96.8% to 93.5%); the selectivity of isononanal increased from 96.9% to 94.5%, indicating that the super-crosslinked microporous polymer phosphine ligand-Rh catalyst containing phosphite can be recycled.

[0126] In summary, the super-crosslinked microporous polymer phosphine ligand-Rh catalyst containing phosphite having the structure of formula (1) can be applied to the preparation of isononanal by isooctene hydroformylation reaction, can improve isooctene conversion rate and isononanal selectivity, and its preparation process is simple and the production cost is low. Most importantly, the super-crosslinked microporous polymer phosphine ligand-Rh catalyst containing phosphite can be separated from the reaction solution by a simple suction filtration operation, so as to realize the recycling of the catalyst, and repeated experimental studies have shown that the catalytic activity of the covalent organic framework phosphine ligand-Rh catalyst containing multiple coordination sites only decreases by 6.0% in 10 repeated experiments.

[0127] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A hyper-crosslinked microporous polymer phosphine ligand, characterized in that: Having the structure shown in formula (I), Among them, R1 is at least one of a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl group, a heterocyclic group, a heterocyclic alkyl group, an aryl group, a substituted aryl group, and a derivative group of a substituted aryl group; R2 is at least one of a hydrogen atom, a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl group, a heterocyclic group, a heterocyclic alkyl group, an aryl group, a substituted aryl group, and a derivative group of a substituted aryl group.

2. The hyper-crosslinked microporous polymer phosphine ligand according to claim 1, characterized in that: The R1 is at least one of a methyl group, an ethyl group, and a tert-butyl group; and the R2 is at least one of a hydrogen group and a methoxy group.

3. The method for preparing the hyper-crosslinked microporous polymer phosphine ligand according to claim 1 or 2, characterized in that: The following steps are involved: (1) using a substituted diphenyl chlorophosphite compound, 4-hydroxystyrene and an acid binding agent as raw materials to synthesize a triphenyl phosphite compound containing an unsaturated double bond; (2) Mixing an aqueous solution containing hydroxyethyl cellulose, gelatin and sodium chloride, the triphenyl phosphite compound containing unsaturated double bonds, divinylbenzene, an initiator and a dispersed oil phase, and polymerizing to obtain the super-crosslinked microporous polymer phosphine ligand.

4. The method for preparing the hyper-crosslinked microporous polymer phosphine ligand according to claim 3, characterized in that: In the step (1), the molar ratio of the substituted diphenyl chlorophosphite compound, 4-hydroxystyrene and the acid binding agent is 1:(1-2):(1-2).

5. The method for preparing the hyper-crosslinked microporous polymer phosphine ligand according to claim 3, characterized in that: In the step (1), the substituted diphenyl chlorophosphite compound, 4-hydroxystyrene and an acid-binding agent are reacted at a temperature of 50 to 150° C. After the reaction is completed, the product is cooled and the solvent is removed to obtain a crude product, which is then purified to obtain a solid triphenyl phosphite compound containing an unsaturated double bond.

6. Use of the hyper-crosslinked microporous polymer phosphine ligand as claimed in claim 1 or 2 in the preparation of a heterogeneous catalyst.

7. A heterogeneous catalyst, characterized in that The invention comprises the hyper-crosslinked microporous polymer phosphine ligand as claimed in claim 1 or 2 and a metal active component loaded on the hyper-crosslinked microporous polymer phosphine ligand.

8. The heterogeneous catalyst according to claim 7, characterized in that The metal active component is rhodium.

9. The heterogeneous catalyst according to claim 7 or 8, characterized in that The mass ratio of the super-crosslinked microporous polymer phosphine ligand to the metal active component is (10-100):

1.

10. Use of the heterogeneous catalyst according to any one of claims 7 to 9 in catalyzing the preparation of isononanal from isooctene.

11. The use according to claim 10, wherein the reaction parameters for preparing isononanal are: the amount of the multiphase catalyst added is 0.05% to 10% of the mass of isooctene; the reaction is carried out at a temperature of 50 to 280°C and a pressure of 0.5 to 20 MPa for 0.5 to 100 hours.

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