Ionic phosphine-containing polymer supported catalyst as well as preparation method and application thereof

Abstract

The invention discloses a method for carrying out olefin hydroformylation reaction by using an ionic phosphine-containing polymer supported catalyst, the metal of the selected catalyst is one or more than two active metal components selected from Rh, Co, Ir, Ru, Pt, Pd and Fe, and is supported on an ionic polymer; the ionic polymer is formed by self-polymerizing a phosphine-containing cation template with vinyl or copolymerizing the phosphine-containing cation template with other components, and then bonding with triphenylphosphine tri-m-sodium sulfonate (TPPTS) with negative charges. The ionic phosphine-containing polymer supported catalyst provided by the invention can be used in reaction systems of hydroformylation reaction, hydroesterification reaction, alcohol carbonylation, hydromethylamination and the like of olefin, and compared with a traditional TPPTS catalyst, the ionic bond is more stable, and the ionic phosphine-containing polymer supported catalyst has higher catalytic activity and better stability.

Description

Technical Field

[0001] The invention belongs to the field of heterogeneous catalysis, and specifically relates to an ionic phosphine-containing polymer supported catalyst and a preparation method and application thereof. Background Art

[0002] With the development of olefin preparation technology in industry, a large amount of raw materials are provided for hydroformylation reaction, which indirectly stimulates the development of hydroformylation technology. Among them, phosphine ligands are more and more widely used in hydroformylation reaction. By modifying them, the target product can be effectively regulated, so that the reaction is easier to occur. At present, five generations of hydroformylation catalysts have appeared in industry, among which the ligand used in the fifth generation catalyst is TPPTS. After loading Rh, the reaction shows good reaction performance under relatively mild conditions, but at the same time, the reaction also faces many problems. First, its ligand TPPTS is a water-soluble substance, which makes the reaction of some oil-soluble substrates, such as high-carbon olefins, difficult to achieve the expected effect. On the other hand, it is a common problem of homogeneous catalysts. After the reaction is completed, the catalyst is difficult to recover, resulting in a large loss of the reaction. These have greatly limited the application and development of TPPTS in industry. Then people gradually carried out heterogeneous catalysts, such as loading TPPTS on SiO2, or embedding it into the interlayer of hydrotalcite to form HRh(CO)(TPPTS)3 complex for hydroformylation of olefins. However, the unification of high selectivity, high stability and high activity has not been solved.

[0003] In recent years, with the rapid development of porous organic materials, their design and research have become hot issues. Considering that TPPTS is a sulfonated salt and has a negative charge, people have gradually combined it with positively charged ions containing vinyl groups, but ultimately locked TPPTS into the skeleton. Although the stability is improved, the selectivity is also reduced. Summary of the invention

[0004] In order to solve the above problems, the present invention provides an ionic phosphine-containing polymer supported catalyst and a preparation method and application thereof.

[0005] The technical solution of the present invention is:

[0006] An ionic phosphine-containing polymer supported catalyst, characterized in that the metal of the catalyst is one or more active metal components selected from Rh, Co, Ir, Mo, Pt, Pd and Fe, and the carrier is bonded by ionic bonds to improve stability;

[0007] The ionic phosphine-containing polymer is prepared by self-polymerization of a cationic template containing a vinyl group or copolymerization with several other components, and then bonding with TPPTS.

[0008] The phosphine-containing cationic template is mainly obtained by salifying all phosphine-containing ligands with vinyl groups, including but not limited to one or two of the following ligands, which are then salified to obtain:

[0009]

[0010]

[0011]

[0012]

[0013]

[0014] The second component monomer containing an olefin group includes but is not limited to one or more of the following ligands:

[0015]

[0016]

[0017] The polymer skeleton is formed by polymerizing one or more phosphine-containing cationic templates and then bonding with the anionic template TPPTS. The carrier has a multi-level pore structure with a specific surface area of ​​20-3000m 2 / g, preferably in the range of 50-1000m 2 / g, pore volume is 0.1-10.0cm 3 / g, preferably 0.2-3.0cm 3 / g, pore size distribution is 0.01-100.0nm, preferably 0.1-10.0nm;

[0018] The active component metal loading in the catalyst ranges from 0.01 to 10 wt%, preferably from 0.1 to 3 wt%. Preparation method of ionic phosphine-containing polymer supported catalyst:

[0019] The preparation process of the cationic template in the ionic phosphine-containing polymer is as follows: dissolving the phosphine-containing polymer containing olefin groups, or subjecting the phosphine-containing polymer containing olefin groups to a salification reaction;

[0020] The preparation process of the ionic phosphine-containing polymer skeleton is as follows: after dissolving the salted phosphine-containing polymer ligand, or dissolving and mixing the salted phosphine-containing polymer ligand and the second component containing olefin groups, a free radical initiator is used to initiate a polymerization reaction of the olefin groups in the organic phosphine ligand to generate an ionic phosphine-containing polymer skeleton with a multi-level pore structure;

[0021] The preparation process of the ionic phosphine-containing polymer is as follows: the polymer is fully dissolved in a solvent, and then TPPTS is added to carry out an ionization reaction, whereby TPPTS becomes negatively charged and forms an ionic bond with the polymer skeleton with a positive charge, thereby generating an ionic phosphine-containing polymer.

[0022] The preparation process of the ionic phosphine-containing polymer supported catalyst is as follows: the precursor of the active metal component and the ionic phosphine-containing polymer carrier are fully stirred and coordinated in a solvent, the active metal component forms a strong chemical bond with the exposed phosphine in TPPTS in the ionic phosphine-containing polymer carrier, and after evaporating the solvent, the ionic phosphine-containing polymer supported catalyst is obtained.

[0023] Specific preparation method of ionic phosphine-containing polymer supported catalyst:

[0024] a) dissolving the phosphine-containing ligand containing an olefin group in an atmosphere of inert gas at 273-500K (most preferably 300K-450K), adding one or more salifying agents to salify the phosphine-containing ligand, and then washing with a solvent, evaporating the solvent to obtain the salified phosphine-containing ligand containing an olefin group.

[0025] b) adding the salted component of step a) to a solvent and then adding an initiator under an inert gas atmosphere at 273-500K (most preferably 300K-450K), and then stirring the mixture for 0.1-100h to obtain a prepolymer solution, preferably in the range of 0.5-20 hours;

[0026] c) transferring the prepolymer mixed solution obtained in step b) to a polymerization reaction vessel, and performing polymerization reaction by bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization for 1-100 hours to obtain an ionic phosphine-containing polymer skeleton;

[0027] d) evaporating the solvent from the polymer obtained in c) to obtain an ionized phosphine-containing polymer skeleton. Then, in an inert gas atmosphere at 273-500K (most preferably 300K-450K), TPPTS is added to the solvent and the mixture is stirred for 0.1-100 hours, preferably 0.5-24 hours. After the stirring is completed, the solvent is added, and the salted phosphine-containing ligand polymer is added and stirred for 5-200 hours, preferably 24-48 hours. Afterwards, the solvent is removed at 273-403K (preferably 303-453K) to obtain an ionic phosphine-containing polymer;

[0028] e) adding the ionic phosphine-containing polymer carrier obtained in step d) to a solvent containing an active metal component precursor under an inert gas atmosphere at 273-473K (preferably 298-453K), stirring for 0.1-100 hours, preferably 0.1-20 hours, and then removing the solvent at 273-403K (preferably 303-453K) to obtain an ionic phosphine-containing polymer supported catalyst; the concentration of the active metal in the precursor solution is in the range of 0.001-1 mol L -1

[0029] The salifying agent in step a) is one or more of ethyl chloride, ethyl bromide, methyl iodide, n-propyl chloride and n-butyl bromide;

[0030] The solvent described in steps a), b), d) and e) is one or more of methanol, ethanol, dichloromethane, chloroform, benzene, toluene, xylene, N,N-dimethylformamide (DMF), water or tetrahydrofuran;

[0031] The free radical initiator in step b) is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, cyclohexanone peroxide or dibenzoyl peroxide;

[0032] The molar ratio of the phosphine-containing ligand containing an olefin group to the second component containing an olefin group in step a) is 0.1:1-200:1, preferably 1:1-1:10, and the ratio of the added vinyl-containing ligand to the salifying agent is 0.01:1-100:1, preferably 0.1:1-1:20.

[0033] The molar ratio of the phosphine-containing ligand after salting to the free radical initiator in step b) is 500:1-10:1, preferably 100:1-10:1; before polymerization into an organic polymer, the concentration range of the phosphine-containing olefin ligand after salting in the solvent is 0.01-1000g / L, preferably 0.1-10g / L; the inert gas in steps a), b), d) and e) is selected from one or more of Ar, He, N2 and CO2.

[0034] The active component is one or more of Rh, Co, Ir, Ru, Pt, Pd or Fe, wherein the precursor of Rh is one or more of RhH(CO)(PPh3)3, Rh(CO)2(acac), RhCl3, Rh(CH3COO)2; the precursor of Co is one or more of Co(CH3COO)2, Co(CO)2(acac), Co(acac)2, CoCl2; the precursor of Ir is I One or more of r(CO)3(acac), Ir(CH3COO)3, Ir(acac)3, Ir2O3, IrO2, and IrCl4; the Ru precursor is dichloro(cyclooctyl-1,5-diene)ruthenium(II), RuCl3, Ru(acac)3, triruthenium dodecacarbonyl, [RuAr2(benzene)]2, [RuAr2(p-cymene)]2, [RuAr2(mesitylene)]2,

[0035] [(π-ally)Ru(cod)]2, [(π-ally)Ru(nbd)]2; the precursor of Pt is one or more of Pt(acac)2, PtCl4, PtCl2(NH3)2; the precursor of Pd is one or more of Pd(CH3COO)2, Pd(acac)2, PdCl2, Pd(PPh3)4, PdCl2(CH3CN)2, H2PtCl6; the precursor of Fe is one or more of Fe(acac)3, FeCl3, FeCl2, FeS, ferrocene, nonacarbonyl iron, and the metal loading range in the catalyst is 0.01-10wt%, preferably 0.1-3wt%. Application of ionic phosphine-containing polymer supported catalyst in hydroformylation, hydroesterification, alcohol carbonylation, hydromethylamination and other reactions; wherein the carbon number of the raw olefin is in the range of C2-C 30 , the carbon number range of the raw alcohols is C1-C 10 .

[0036] The principle of the present invention;

[0037] The present invention creatively salts the phosphine ligand containing vinyl groups, uses the olefin groups on the monomer molecules to carry out polymerization reactions, and obtains a cationic skeleton with positive charges. The skeleton has developed pores, and then bonds it with the negatively charged TPPTS, which not only solves the stability problem of TPPTS, but also releases TPPTS, allowing it to rotate freely in the skeleton, while ensuring stability, it also has a very high degree of freedom. The phosphine ligand in the ionic phosphine-containing polymer-supported catalyst can form a high-performance catalyst suitable for reaction systems such as hydroformylation, hydroesterification, alcohol carbonylation, and hydromethylamination after coordination with the metal. The catalyst protected by this patent is originally heterogeneous, and the catalyst is easy to separate from the reaction system. The catalyst is prepared by a vinyl polymerization scheme, and the catalyst has long-range stability and is suitable for industrial applications.

[0038] The beneficial effects of the present invention are:

[0039] The traditional TPPTS catalyst is a homogeneous system, which is difficult to recycle and reuse after the reaction is completed, which greatly reduces its applicability. For the subsequent multi-phase TPPTS, the synthesized catalyst has poor stability, and it is difficult to achieve a series of problems such as taking both water and oil into consideration at the same time. In addition, the TPPTS degree of freedom in the catalyst is insufficient, which greatly limits its activity and selectivity. The ionic phosphine-containing polymer supported catalyst provided by the present invention fundamentally solves these problems, and the ionic phosphine-containing polymer supported catalyst is insensitive to oxygen, the operating conditions are not harsh, and the catalyst is easy to store. In addition, the catalyst has good solubility in both the aqueous phase and the oil phase, has low requirements for the reaction substrate, and TPPTS can rotate freely in the skeleton. Compared with the traditional catalyst locked in the skeleton, the catalyst provided by this patent has higher activity.

[0040] The supported catalyst of the present invention is suitable for fixed bed, slurry bed, autoclave reactor and trickle bed reactors. The ionic phosphine-containing polymer supported catalyst provided by the present invention can be applied to olefin hydroformylation, hydroesterification, alcohol carbonylation, hydromethylamination and other reactions. Compared with the traditional catalyst with TPPTS as a ligand, the catalytic activity is higher; the catalyst is stable to air and moisture, and the operating conditions do not need to be too harsh. In addition, the catalyst is heterogeneous, and the method for hydroformylation based on the ionic phosphine-containing polymer supported catalyst involved in this patent is green and environmentally friendly, with less pollutant emissions. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is a quaternary phosphonium salt (after salification of the L1 monomer in Example 1) 1 H NMR spectrum

[0042] Figure 2 is a quaternary phosphonium salt (after salification of the L1 monomer in Example 1) 13C NMR spectrum.

[0043] Figure 3 is a quaternary phosphonium salt (after salification of the L1 monomer in Example 1) 31 P NMR spectrum.

[0044] Figure 4 For CPOL-1P + Br - 5DVB-TPPTS physical adsorption diagram.

[0045] Figure 5 For CPOL-1P + Br - 5DVB-TPPTS pore size distribution diagram.

[0046] Figure 6 Rh / CPOL-1P + Br - 5Spherical aberration electron microscopy image of DVB-TPPTS catalyst. DETAILED DESCRIPTION

[0047] The following embodiments are provided to better illustrate the present invention, but are not intended to limit the scope of the present invention.

[0048] Example 1

[0049] The specific preparation steps of the salt A monomer are as follows: under argon protection at 273K, 10g of vinylated triphenylphosphine L1 (ligand L1 in the claim, CAS No. 1321-74-0) is dissolved in 50g of ethyl bromide, and stirred at 313K for 48h to obtain a quaternary phosphonium salt monomer, which is then washed with tetrahydrofuran solvent and dried to obtain 13.8g of the quaternary phosphonium salt monomer (yield of about 80%, the product is confirmed by nuclear magnetic resonance and high-resolution mass spectrometry), attached Figure 1-3 They are respectively the NMR of quaternary phosphonium salt (quaternary phosphonium salt ligand A after salification) 1 H. 13 C and 31 P spectrum.

[0050] Preparation of quaternary phosphonium salt-triphenylphosphine trisulphonate porous organic polymer: 10g of quaternary phosphonium salt ligand A and 50g of the second component divinylbenzene were dissolved in 400ml of tetrahydrofuran solvent + 100ml of N, N-dimethylformamide at 298K and in an inert gas argon protective atmosphere, stirred for 30min to completely dissolve, 0.02g 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 bulk polymerization at 373K and in an inert gas argon protective atmosphere for 24h. After the polymerization autoclave was cooled to room temperature, the solvent was vacuumed off at room temperature to obtain a polymer CPOL-1PIPs&5DVB copolymerized by quaternary phosphonium salt and divinylbenzene, with a yield of 100%. Then, the 20g polymer was dissolved in 200ml ethanol solution, stirred for 30min to completely dissolve, and then 100ml aqueous solution was added to mix thoroughly, and then 5g TPPTS was added, and stirred for 24h at 300K under an inert gas argon protective atmosphere. After stirring, the mixture was washed with toluene 3-5 times (here 4 times), and the solvent was vacuumed to obtain CPOL-1PIPs&5DVB-TPPTS, and 21.4g polymer carrier was obtained, with a yield of about 85.6%. Figure 4 N2 physical adsorption curve of CPOL-1PIPs & 5DVB-TPPTS, attached Figure 5 The pore size distribution diagram of CPOL-1PIPs&5DVB-TPPTS shows that the adsorption curve of CPOL-1PIPs&5DVB-TPPTS presents a multi-level pore structure with a specific surface area of ​​741m 2 / g, and the pore size is mainly distributed in 1-10nm.

[0051] Phosphine oxide polymer-supported highly dispersed Rh metal catalyst: 15.0 mg of (1,5-cyclooctadiene) 2,4-pentanedione rhodium (I) (CAS No. 12245-39-5) was weighed and dissolved in 30.0 ml of tetrahydrofuran solvent, and 1.0 g of the above-prepared CPOL-1PIPs&5DVB-TPPTS polymer was added. The mixture was stirred at 298K for 5 hours, and continued to be stirred for 10 hours under an argon atmosphere at 298K. The solvent was removed in vacuo at 318K to obtain a phosphine oxide polymer-supported highly dispersed Rh-based catalyst Rh / CPOL-1PIPs&5DVB-TPPTS, with an actual Rh loading of 0.497%. Figure 6 This is the spherical aberration electron microscopy image of the Rh / CPOL-1PIPs&5DVB-TPPTS catalyst. It can be observed that the Rh atoms are in a single-atom state and dispersed on the carrier surface.

[0052] Example 2

[0053] In Example 2, except that 50.0 g of the second component divinylbenzene was not added, the rest of the synthesis process and conditions were the same as those of Example 1.

[0054] Example 3

[0055] In Example 3, except that 50.0 g of the second component D was used instead of divinylbenzene, the rest of the synthesis process and conditions were the same as those of Example 1.

[0056] Example 4

[0057] In Example 4, except that the polymerization time was adjusted from 24 hours to 48 hours, the rest of the method and catalyst synthesis process and conditions were the same as those in Example 1.

[0058] Example 5

[0059] In Example 5, except that the same molar number of Co(acac)2 is used to replace (1,5-cyclooctadiene)2,4-pentanedione rhodium (I), the rest of the synthesis process and conditions are the same as in Example 1, and a highly dispersed Co-based catalyst can be obtained.

[0060] Example 6

[0061] In Example 6, except that the same molar number of Ir(acac)3 is used to replace (1,5-cyclooctadiene)2,4-pentanedione rhodium (I), the rest of the synthesis process and conditions are the same as in Example 1, and a highly dispersed Ir-based catalyst can be obtained.

[0062] Example 7

[0063] In Example 7, except that the same molar amount of triruthenium dodecacarbonyl was used to replace (1,5-cyclooctadiene)-2,4-pentanedione rhodium (I), the rest of the synthesis process and conditions were the same as those in Example 1.

[0064] Example 8

[0065] In Example 8, except that the same molar amount of nonacarbonyl iron was used to replace (1,5-cyclooctadiene)-2,4-pentanedione rhodium (I), the rest of the synthesis process and conditions were the same as those in Example 1.

[0066] Example 9

[0067] In Example 9, except that the same molar number of L2 was used to replace the monomer L1 for salification, the rest of the synthesis process and conditions were the same as those in Example 1.

[0068] Example 10

[0069] In Example 10, except that the same molar number of ligand L4 was used to replace monomer L1, the rest of the synthesis process and conditions were the same as those in Example 1.

[0070] Embodiment 11

[0071] In Example 11, except that the same molar number of ligand L7 was used to replace monomer L1, the rest of the synthesis process and conditions were the same as those in Example 1.

[0072] Example 12

[0073] In Example 12, except that the same molar number of ligand L10 was used to replace monomer L1, the rest of the synthesis process and conditions were the same as those in Example 1.

[0074] Example 13

[0075] In Example 13, except that the same molar number of ligand L13 was used to replace monomer L1, the rest of the synthesis process and conditions were the same as those in Example 1.

[0076] Embodiment 14

[0077] In Example 14, except that the same molar number of ligand L17 was used to replace monomer L1, the rest of the synthesis process and conditions were the same as those in Example 1.

[0078] Embodiment 15

[0079] In Example 15, except that the same molar number of ligand L19 was used to replace monomer L1, the rest of the synthesis process and conditions were the same as those in Example 1.

[0080] Example 16

[0081] In Example 16, except that the same molar number of ligand L44 was used to replace monomer L1, the rest of the synthesis process and conditions were the same as in Example 1.

[0082] Embodiment 17

[0083] 0.5 g of the catalysts prepared in Examples 1 to 16 were respectively loaded into a fixed bed reactor, and quartz sand was loaded at both ends of the catalyst bed. A reaction mixture (H2:CO:C2H4=1:1:1, V / V / V) was introduced at 403K, 2.0 MPa, and a space velocity of 4000 h / min. -1 The hydroformylation reaction was carried out under the following conditions. The reaction product was collected by absorption in a collection tank containing 60 ml of cooled deionized water, and the reaction product propionaldehyde was completely dissolved in the water in the collection tank. The obtained aqueous solution was analyzed by HP-7890N gas chromatography equipped with HP-5 capillary column and FID detector, and ethanol was used as internal standard. After water absorption, the reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are listed in Table 1.

[0084] Table 1. Specific surface area, pore size distribution and ethylene hydroformylation performance of catalysts in Examples 1 to 16

[0085]

[0086] Example 1 prepared a Rh catalyst coordinated by a quaternary phosphonium salt-triphenylphosphine trisulfonic acid sodium salt. From the reaction data of ethylene hydroformylation, it can be seen that the Rh catalyst loaded after the salted quaternary phosphonium salt is combined with TPPTS has higher ethylene hydroformylation activity and better aldehyde selectivity. The active metal components of Examples 5, 6, 7, and 8 are Co, Ir, Ru, and Fe, respectively, and the reaction performance is lower than the catalyst whose active metal is Rh.

[0087] Embodiment 18

[0088] Except for replacing (1,5-cyclooctadiene)2,4-pentanedione rhodium (I) with the same molar number of Pd(acac)2, the rest of the catalyst synthesis process and conditions are the same as in Example 1, and a phosphine oxide-supported Pd catalyst can be obtained, and the measured Pd loading amount is 0.514%.

[0089] In a 100 ml autoclave, 20 mg of Pd catalyst supported after polymerization of quaternary phosphonium salt and TPPTS, 2 mmol of NH4Cl, 10 mmol of reactant hexene, and 10 mL of solvent N-methylpyrrolidone (NMP) were added, and then 4 MPa of CO was charged to carry out hydromethylamination reaction.

[0090] The reaction temperature was 24 hours at 413 K. The hexene conversion was 89.3% and the product selectivity was 99.8%.

[0091] Embodiment 19

[0092] In a 100 ml autoclave, 0.6 g of the catalyst prepared in Example 1, 2.0 mmol of p-toluenesulfonic acid, 6 mmol of cyclohexene as reactant, 4 mmol of methyl iodide, and 50 mmol of purified water were added, and then 2 MPa of CO was introduced to carry out a hydrocarboxylation reaction.

[0093] The reaction time was 24 hours, the reaction temperature was 455K, the cyclohexene conversion rate was 94.3, and the product selectivity was 93.5%.

[0094] Embodiment 20

[0095] 0.5 g of the catalyst of Example 1 was placed in a quartz tube at 100°C, air pressure 1.5 bar, and air velocity 1000 h -1 After 6 hours of treatment, the treated catalyst was obtained. 2 g of the treated catalyst was loaded into a fixed bed reactor, and quartz sand was loaded at both ends of the catalyst bed. A reaction mixture (H2:CO:C2H4=1:1:1, V / V / V) was introduced at 393K, 1.0 MPa, and a reaction mixture space velocity of 4000 h -1The hydroformylation reaction was carried out under the following conditions. The reaction product was absorbed and collected by a collection tank containing 60 ml of cooled deionized water, and the reaction product propionaldehyde was completely dissolved in the water in the collection tank. The obtained aqueous solution was analyzed by HP-7890N gas chromatography equipped with HP-5 capillary column and FID detector, and ethanol was used as internal standard. After water absorption, the reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are listed in Table 2.

[0096] Table 2. Specific surface area and ethylene hydroformylation performance of the catalyst after air treatment in Example 1 and the catalyst of untreated Example 1

[0097]

[0098] However, the ethylene hydroformylation performance did not change significantly after the catalyst treatment in Example 1, which indicates that the catalyst is stable to air and moisture, has better catalyst stability, does not require too harsh operating conditions, and is more conducive to industrial production.

[0099] Embodiment 21

[0100] In Example 21, the catalyst obtained in Example 1 was reacted, and the reaction data of reaction time of 20h, 50h, 100h, 200h, 500h, and 700h were recorded, and the records were the same as those in Table 3.

[0101] Table 3. Ethylene hydroformylation data of Example 1 at different reaction times

[0102]

[0103] Embodiment 21

[0104] In Example 21, Example 1-6 was reacted, except that the synthesis was changed (H2:CO:C3H6=1:1:1, V / V / V), and the other conditions were the same as in Example 21.

[0105] Table 4. Propylene hydroformylation data of Examples 1-6

[0106]

[0107] Embodiment 22

[0108] 0.5 g of the catalyst prepared in Example 1 was placed in a fixed bed reactor, and quartz sand was placed at both ends. A micro-feed pump maintained the olefin flow rate at 0.8 ml / min, and a mass flow meter controlled the synthesis gas (H2:CO=1:1) space velocity at 1000 h -1, hydroformylation reaction was carried out under the conditions of 393K and 2MPa. The reaction was collected in a collection tank cooled by an ice bath. The obtained liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, and n-propanol was used as an internal standard. The tail gas from the collection tank was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are listed in Table 5.

[0109] Table 5 Hydroformylation results of different substrates on the catalyst of Example 23

[0110]

[0111]

[0112] Comparative Example 1

[0113] In Comparative Example 1, except that TPPTS was not added, the remaining synthesis steps were the same as those of Example 1.

[0114] Comparative Example 2

[0115] In Comparative Example 2, except for using the same molar number of vinyl monodentate phosphine ligand Except for replacing divinylbenzene (ligand L1), the rest of the synthesis process and conditions are the same as those in Example 1.

[0116] Comparative Example 3

[0117] In Comparative Example 3, except for using the same molar number of vinyl monodentate phosphine ligand Except for replacing divinylbenzene (ligand L1), the rest of the synthesis process and conditions are the same as those in Example 1.

[0118] Comparative Example 4

[0119] In Comparative Example 4, except for using the same molar number of vinyl monodentate phosphine ligand Except for replacing the distyrylphosphine oxide monomer B, the rest of the synthesis process is the same as in Example 1

[0120] Comparative Example 5

[0121] In Comparative Example 5, except for using the same molar number of bidentate phosphine ligand Except for replacing the distyrylphosphine oxide monomer B, the rest of the synthesis process is the same as in Example 1

[0122] Comparative Example 6

[0123] In Comparative Example 6, except for using the same molar number of vinyl secondary phosphine oxide monomer Except for replacing the distyrylphosphine oxide monomer B, the rest of the synthesis process is the same as that of Example 1.

[0124] In Comparative Example 7, except for using the same molar number of vinyl secondary phosphine oxide monomer Except for replacing the distyrylphosphine oxide monomer B, the rest of the synthesis process is the same as that of Example 1.

[0125] 0.5 g of the catalysts prepared in Comparative Example 1 to Example 7 were respectively loaded into a fixed bed reactor, and quartz sand was loaded at both ends of the catalyst bed. A reaction mixture (H2:CO:C3H6=1:1:1, V / V / V) was introduced at 403K, 2.0 MPa, and a space velocity of 4000 h / min. -1 The hydroformylation reaction was carried out under the following conditions. The reaction product was absorbed and collected in a collection tank filled with 60 ml of cooled deionized water, and the reaction product propionaldehyde was completely dissolved in the water in the collection tank. The obtained aqueous solution was analyzed by HP-7890N gas chromatography equipped with HP-5 capillary column and FID detector, and ethanol was used as internal standard. After water absorption, the reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are listed in Table 5

[0126] Table 6. Ethylene hydroformylation data of Examples 1-7

[0127]

[0128]

[0129] As can be seen from the table, when only the quaternary phosphonium salt is polymerized, the halogen atoms are retained in the skeleton and cannot be removed by salting, and the conversion rate is only 28.2%, which is significantly lower than the data in Example 1 (Comparative Example 1). When the first component is selected to contain only one vinyl triphenylphosphine ligand during polymerization, the specific surface area is significantly lower than that in Example 1, which is insufficient during polymerization and will significantly affect the propylene hydroformylation performance of the catalyst prepared (Comparative Examples 2, 3, 6). When there are F atoms on the first component P ligand, the activity of propylene hydroformylation reaction will also be significantly reduced (Comparative Examples 4, 5). The catalyst propylene conversion rate prepared by copolymerization of the monomer and divinylbenzene in Comparative Example 7 is 25.6%, which is significantly lower than the scheme in Example 1 (Table 1, propylene conversion rate 98.2%).

Claims

1. An ionic phosphine-containing polymer supported catalyst, characterized in that: The supported catalyst comprises an active metal component and an ionic phosphine-containing polymer carrier, wherein the active component metal is supported on the carrier; The active component metal is one or more of Rh, Co, Ir, Mo, Pt, Pd and Fe; The ionic phosphine-containing polymer is prepared by polymerizing a cationic template monomer containing a vinyl group, or copolymerizing a cationic template containing a vinyl group with other second component monomers containing an olefin group, and then bonding with TPPTS.

2. The ionic phosphine-containing polymer supported catalyst according to claim 1, characterized in that: The cationic template monomer containing vinyl includes but is not limited to one or two of the following ligands, which are then salified to obtain: The second component monomer containing an olefin group includes but is not limited to one or more of the following ligands:

3. The ionic phosphine-containing polymer supported catalyst according to claim 1 or 2, characterized in that: The ionic phosphine-containing polymer skeleton is formed by polymerizing a cationic template monomer containing a vinyl group, or copolymerizing a cationic template containing a vinyl group with other second component monomers containing an olefin group, and then bonding with an anionic template TPPTS. The carrier has a multi-level pore structure with a specific surface area of ​​20-3000m 2 / g, preferably in the range of 50-1000m 2 / g, pore volume is 0.1-10.0cm 3 / g, preferably 0.2-3.0cm 3 / g, the pore size distribution is 0.01-100.0nm, preferably 0.1-10.0nm; the carrier is bonded with ionic bonds to improve stability.

4. The ionic phosphine-containing polymer supported catalyst according to claim 1, characterized in that: The loading amount of the active component metal in the catalyst is in the range of 0.01-10 wt %, preferably in the range of 0.1-3 wt %.

5. A method for preparing the ionic phosphine-containing polymer supported catalyst according to claim 1, characterized in that: a) Preparation process of cationic template in ionic phosphine-containing polymer: After dissolving a cationic template monomer containing a vinyl group, or mixing and dissolving the cationic template containing a vinyl group and other second component monomers containing an olefin group, a salting reaction is performed to obtain a cationic template; b) The preparation process of the ionic phosphine-containing polymer skeleton is as follows: After the salted cationic template is dissolved, polymerization is initiated by a free radical initiator to generate an ionic phosphine-containing polymer skeleton; c) The preparation process of the ionic phosphine-containing polymer is as follows: The polymer is dissolved in a solvent, and then TPPTS is added to carry out an ionization reaction, whereby TPPTS becomes negatively charged and forms an ionic bond with the polymer backbone with a positive charge, thereby generating an ionic phosphine-containing polymer; d) The preparation process of the ionic phosphine-containing polymer supported catalyst is as follows: The precursor of the active metal component and the ionic phosphine-containing polymer carrier are fully stirred and coordinated in a solvent, and the active metal component forms a strong chemical bond with the exposed phosphine in TPPTS in the ionic phosphine-containing polymer carrier. After evaporating the solvent, an ionic phosphine-containing polymer supported catalyst is obtained.

6. The method for preparing the ionic phosphine-containing polymer supported catalyst according to claim 5, characterized in that: a) dissolving a cationic template monomer containing a vinyl group in an atmosphere of an inert gas at 273-500K (most preferably 300K-450K), adding a salifying agent to salify the monomer, and then washing with a solvent and removing the solvent to obtain a salified olefin-based phosphine-containing ligand; b) adding a salted olefinic phosphine-containing ligand to a solvent, without or with other olefinic second component monomers, adding an initiator, and stirring the mixture for 0.1-100 hours (preferably 0.5-20 hours) in an inert gas atmosphere at 273-500K (most preferably 300K-450K) to obtain a prepolymer solution; c) transferring the prepolymer solution obtained in step b) to a polymerization reaction vessel, performing polymerization reaction by bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization for 1-100 hours, removing the solvent, and obtaining an ionic phosphine-containing polymer skeleton; d) dissolving the ionized phosphine-containing polymer obtained in step c) in a solvent under an inert gas atmosphere at 273-500K (most preferably 300K-450K), stirring for 0.1-100h, preferably 0.5-24h, adding solvent after stirring, and adding TPPTS, stirring for 5-200h, preferably 24-48h; then, removing the solvent at 273-403K (preferably 303-453K) to obtain an ionic phosphine-containing polymer; e) adding the ionic phosphine-containing polymer carrier obtained in step d) to a solvent containing an active component metal precursor under an inert gas atmosphere at 273-473K (preferably 298-453K), stirring for 0.1-100 hours, preferably 0.1-20 hours, and then removing the solvent at 273-403K (preferably 303-453K) to obtain an ionic phosphine-containing polymer supported catalyst; the concentration of the active metal in the precursor solution is in the range of 0.001-1 mol L -1 .

7. The method for preparing the ionic phosphine-containing polymer skeleton according to claim 6, characterized in that: The salifying agent in step a) is one or more of ethyl chloride, ethyl bromide, methyl iodide, n-propyl chloride and n-butyl bromide; The solvent described in steps a), b), d) and e) is one or more of methanol, ethanol, dichloromethane, chloroform, benzene, toluene, xylene, N,N-dimethylformamide (DMF), water or tetrahydrofuran; The free radical initiator in step b) is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, cyclohexanone peroxide or dibenzoyl peroxide.

8. The preparation method according to claim 6, characterized in that: The molar ratio of the cationic template monomer containing vinyl groups and other second component monomers containing olefin groups in step a) is 0.1-200:0-1, preferably 0.1-200:1, more preferably 1-10:1; the molar ratio of the cationic template monomer containing vinyl groups to the salting agent is 0.01:1-100:1, preferably 0.1:1-1:20; The molar ratio of the phosphine-containing ligand after salting to the free radical initiator in step b) is 500:1-10:1, preferably 100:1-10:1; before polymerizing into an organic polymer, the concentration range of the phosphine-containing olefinic ligand after salting in the solvent is 0.01-1000 g / L, preferably 0.1-10 g / L; The inert gas in steps a), b), d) and e) is selected from one or more of Ar, He, N2 and CO2.

9. The preparation method according to claim 6, characterized in that: The active component is one or more of Rh, Co, Ir, Ru, Pt, Pd or Fe, wherein the precursor of Rh is one or more of RhH(CO)(PPh3)3, Rh(CO)2(acac), RhCl3, and Rh(CH3COO)2; the precursor of Co is one or more of Co(CH3COO)2, Co(CO)2(acac), Co(acac)2, and CoCl2; the precursor of Ir is one or more of Ir(CO)3(acac), Ir(CH3COO)3, Ir(acac)3, Ir2O3, IrO2, and IrCl4; the precursor of Ru is dichloro(cyclooctyl-1,5-diene)ruthenium(II), RuCl3, Ru(acac)3, triruthenium dodecacarbonyl, [RuAr2(benzene)]2, [RuAr2(p-cymene)]2, [RuAr2(mesitylene)]2, [(π-ally)Ru(cod)]2, [(π-ally)Ru(nbd)]2; the precursor of Pt is one or more of Pt(acac)2, PtCl4, PtCl2(NH3)2; the precursor of Pd is one or more of Pd(CH3COO)2, Pd(acac)2, PdCl2, Pd(PPh3)4, PdCl2(CH3CN)2, H2PtCl6; the precursor of Fe is one or more of Fe(acac)3, FeCl3, FeCl2, FeS, ferrocene, nonacarbonyl iron, and the metal loading range in the catalyst is 0.01-10wt%, preferably 0.1-3wt%.

10. Use of the ionic phosphine-containing polymer supported catalyst according to claim 1 in catalyzing olefin hydroformylation, olefin hydroesterification, alcohol carbonylation or olefin hydromethylamination, wherein the carbon number of the raw olefin is in the range of C2-C 30 , the carbon number range of the raw alcohols is C1-C 10 .

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