CN114534792B - Method for preparing organic carboxylic acid by olefin hydrocarboxylation - Google Patents

Method for preparing organic carboxylic acid by olefin hydrocarboxylation Download PDF

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CN114534792B
CN114534792B CN202011325544.7A CN202011325544A CN114534792B CN 114534792 B CN114534792 B CN 114534792B CN 202011325544 A CN202011325544 A CN 202011325544A CN 114534792 B CN114534792 B CN 114534792B
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CN114534792A (en
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丁云杰
袁乔
宋宪根
冯四全
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Dalian Institute of Chemical Physics of CAS
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Abstract

A process for the preparation of organic carboxylic acids by hydrocarboxylation of olefins. The invention provides a vinyl functionalized porous organic phosphine ligand polymer supported metal single-atom catalyst which is used for preparing organic carboxylic acid by olefin hydrocarboxylation. Under the action of auxiliary agent halogenated alkane, acid additive, carboxylic acid solvent and a certain temperature and pressure and the action of the catalyst, the alkene, CO and water can be converted into organic carboxylic acid with high activity, high selectivity and high stability.

Description

Method for preparing organic carboxylic acid by olefin hydrocarboxylation
Technical Field
The invention belongs to the technical field of chemical engineering catalysts, and particularly relates to a method for preparing organic carboxylic acid by olefin hydrocarboxylation.
Background
As an important product in organic chemistry and industry, carboxylic acids find important applications in the fields of food, polymers, medicine, cosmetics and other manufacturing. Meanwhile, carboxylic acid is used as an intermediate, and has important application in preparing derivatives such as ester, ketone, amide and alcohol. Thus, the production of organic carboxylic acids is of great significance both in chemical organic synthesis and in industrial scale.
The production process of carboxylic acid is generally divided into paraffin oxidation method, colgate-Emery process method and hydroformylation reoxidation method, but the yield is not high and the selectivity is poor due to paraffin oxidation method; the Colgate-Emery process product is only an even-numbered carboxylic acid; the olefin hydroformylation reoxidation method has complicated steps, so that a direct, effective, convenient and quick carboxylic acid preparation method has to be considered and found. The hydrocarboxylation of olefins has received extensive attention from numerous researchers as a one-step process for the production of organic carboxylic acids (see formula 3).
Figure BDA0002794157510000011
Preparation of organic carboxylic acids by hydrocarboxylation of olefins 3
The hydrocarboxylation reaction was already discovered and put into production by the baschiff chemist Reppe as early as 1953. A series of researchers have subsequently conducted a great deal of research on this. The KutePow finds that Pd can be used for replacing Ni/Co/Fe catalyst to catalyze the hydrocarboxylation reaction well for the first time, and the reaction condition is milder; fenton found PPh 3 The ligand is introduced, so that the activity of the hydrogen carboxylation reaction of the Pd system can be improved to a certain extent; subsequently, scientists have made their own efforts in terms of modification of auxiliaries and optimization of ligands, etc., for improvement of the hydrocarboxylation reaction performance and stability of Pd catalysts.
Despite the history of the whole hydrocarboxylation development, the homogeneous reaction takes up a great chapter, but the homogeneous reaction is always polluted by people, is difficult to separate, is not easy to recycle and the like, and is blocked in the aspect of industrial development; pd (II) -catalyzed hydrocarboxylation systems are susceptible to reduction by ligands and CO to Pd (0) and even agglomeration to palladium black due to the inherent external electronic structural features, leading to instability of the catalytic system. Therefore, the heterogeneous catalysis of the unit point Rh and other bases, which can keep the advantage of high homogeneous activity, can realize the separation of the catalyst and the product and bring good stability to the catalytic system, is generated.
Here we propose a porous organophosphine ligand polymer support loaded Ru, au, ir, re, rh, pt or Cu single atom solid heterogeneous catalyst for olefin hydrocarboxylation to produce organic carboxylic acids. The catalyst system has the advantages of high activity, high selectivity, good stability and the like. And the catalyst and the reaction system are easy to separate, so that the metal utilization rate is greatly increased, the separation cost is reduced, and the method has wide industrial application prospect.
Disclosure of Invention
The invention aims to provide a vinyl functionalized porous organic phosphine ligand polymer supported metal single-atom catalyst which is used for the reaction of preparing organic carboxylic acid by olefin hydrocarboxylation. Under the action of auxiliary agent halogenated alkane, acid additive, carboxylic acid solvent and a certain temperature and pressure and the action of the catalyst, the alkene, CO and water can be converted into organic carboxylic acid with high activity, high selectivity and high stability.
The technical scheme of the invention is as follows:
the adopted solid heterogeneous catalyst consists of two parts of active component metal and a carrier; the active component metal is one or more than two of Ru, au, ir, re, rh, pt, cu; the carrier is a vinyl functionalized porous organic phosphine ligand polymer;
in the presence of solid heterogeneous catalyst, auxiliary agent halogenated alkane, acid additive and carboxylic acid solvent, the raw material olefin, CO and water undergo hydrocarboxylation reaction to prepare the organic carboxylic acid.
The reaction is carried out in a fixed bed, trickle bed, slurry bed or kettle reactor; when a fixed bed or a trickle bed is adopted, the liquid hourly space velocity is 0.01 to 20.0h -1 Preferably 1 to 5 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The gas hourly space velocity is 100 to 20000h -1 Preferably 500 to 2000h -1 。
The auxiliary agent halogenated alkane is one or more than two of methyl chloride, methyl bromide, methyl iodide, diiodomethane, ethyl chloride, ethyl bromide and ethyl iodide, and preferably one or more than two of methyl iodide, ethyl bromide and ethyl iodide;
the acid additive is one or more of trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, nitric acid and hydrochloric acid, preferably one or more of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid;
The carboxylic acid solvent is one or more of formic acid, acetic acid, propionic acid, n-butyric acid and isobutyric acid;
the reaction temperature is 30-250 ℃, preferably 120-200 ℃; the reaction pressure is 0.05-20.0MPa, preferably 0.5-2 MPa;
the raw material olefin is one or more than two of O1-O7 in the compound shown in the formula 1;
Figure BDA0002794157510000031
R 1 and R is 2 Represents H or C 1-16 And the sum of the carbon numbers of the alkyl groups of (2) is not more than 16
Figure BDA0002794157510000032
Formula 1. Raw material olefin type.
The molar ratio of the solid heterogeneous catalyst metal to the auxiliary agent halogenated alkane is 0.0001:1-0.05:1, preferably 0.0005:1-0.001:1; the molar ratio of the solid heterogeneous catalyst metal to the acid additive is 0.001:1 to 0.1:1, preferably 0.005:1 to 0.05:1; the molar ratio of the solid heterogeneous catalyst metal to the carboxylic acid solvent is 0.00001:1 to 0.001:1, preferably 0.00005:1 to 0.0005:1; the molar ratio of the solid heterogeneous catalyst metal to the feed olefin is 0.0001:1 to 0.05:1, preferably 0.0005:1 to 0.001:1; the molar ratio of the solid heterogeneous catalyst metal to the CO is 0.00001:1 to 0.001:1, preferably 0.0001:1 to 0.0008:1; the molar ratio of the solid heterogeneous catalyst metal to water is 0.00001:1 to 0.01:1, preferably 0.0001:1 to 0.001:1.
The active component metal of the solid heterogeneous catalyst is dispersed on a carrier in a single atomic level and is combined with phosphorus atoms in the porous organic phosphine ligand polymer of the carrier in a coordination bond form.
The preparation method of the catalyst comprises the following steps:
1) First, a porous organophosphine ligand polymer carrier is prepared:
under the protection of inert gas, dissolving the vinyl functionalized organic phosphine ligand monomer in a solvent, adding a free radical initiator, and stirring for 0.2-2 h (preferably 0.5 h) at 0-100 ℃ (preferably 25 ℃); subsequently, transferring the mixture into a hydrothermal synthesis kettle, and standing the mixture for 5 to 50 hours (preferably 24 hours) at 50 to 300 ℃ (preferably 100 ℃); finally, taking out the mixture, and vacuum drying the mixture at 30-100 ℃ to remove the solvent;
2) Secondly, preparing a metal precursor solution of the active component;
3) Finally, adding the organic phosphine ligand polymer in 1) into the metal precursor solution in 2) under the protection of inert gas, stirring for 10-50 h (preferably 24 h) at 0-100 ℃ (preferably 25 ℃), and then drying in vacuum for 2-12 h (preferably 6 h) at 25-150 ℃ (preferably 60 ℃), thus obtaining the product catalyst.
The active metal precursor compound is mainly ruthenium acetylacetonate (Ru (acac) 3 ) Triruthenium dodecacarbonyl (Ru) 3 (CO) 12 ) Ruthenium trichloride (RuCl) 3 ) Oxide Jin Shuige (Au) 2 O 3 ·xH 2 O), gold (III) chloride hydrate (HAuCl) 4 ·xH 2 O), iridium oxide (Ir) 2 O 3 ) Ir hydroxide (Ir (OH) 3 ) Iridium chloride (IrCl) 3 ) Perrhenic acid (HReO) 4 ) Ammonium perrhenate (NH) 4 ReO 4 ) Rhenium pentachloride (Recl) 5 ) Rhodium acetylacetonate carbonyl (Rh (acac) (CO)) 2 ) Rhodium (Rh) tetracarbonyl dichloride 2 (CO) 4 Cl 2 ) Rhodium trichloride (RhCl) 3 ) Platinum acetylacetonate (Pt (acac) 2 ) Platinum chloride (PtCl) 2 、PtCl 4 ) Chloroplatinic acid (H) 2 PtCl 6 ) Copper acetylacetonate (Cu (acac)) 2 ) Copper acetate (Cu (OAc)) 2 ) And copper chloride (CuCl) 2 ) One or more of them, preferably Ru 3 (CO) 12 、HAuCl 4 ·xH 2 O、IrCl 3 、HReO 4 、Rh 2 (CO) 4 Cl 2 、H 2 PtCl 6 、Cu(acac) 2 One or two or more of them.
The mass loading of the active component metal in the catalyst is 0.01-10.0%, preferably 0.5-2%; the carrier organic phosphine monomer is one or more than two of compounds L1-L8 in the formula 2, preferably one or more than two of L2, L3 and L6;
Figure BDA0002794157510000041
and (2) an organic phosphine ligand monomer.
The solvent used in the carrier organic phosphine ligand polymer preparation step 1) is one or more of tetrahydrofuran, toluene, benzene, methylene dichloride, chloroform and dimethylformamide, preferably tetrahydrofuran and methylene dichloride; the free radical initiator used in the step 1) is one or more than two of hydrogen peroxide, ammonium persulfate, benzoyl peroxide, cyclohexanone peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and azobisisobutyronitrile and azobisisoheptonitrile composite initiation system, preferably cyclohexanone peroxide and azobisisobutyronitrile; the solvent used in the step 2) is one or more of dioxane, tetrahydrofuran, dichloromethane and dimethylformamide, preferably tetrahydrofuran and dichloromethane.
The mass ratio of the solvent to the organic phosphine ligand monomer in the step 1) is 5:1-300:1, preferably 20:1-100:1; the mass ratio of the free radical initiator to the organic phosphine ligand monomer is 1:5-1:500, preferably 1:20-1:100; the mass ratio of the solvent in the step 2) to the organic phosphine ligand polymer in the step 3) is 6:1-280:1, preferably 15:1-80:1; the specific surface area of the carrier is 200-3000 m 2 Preferably 800 to 1500m 2 /g; pore volume of 0.05-8.0cm 3 Preferably 0.5 to 2.0cm 3 /g; the pore size distribution is 0.05 to 800nm, preferably 0.8 to 400nm.
The beneficial effects of the invention are as follows:
compared with the existing technology for preparing organic carboxylic acid by olefin hydrocarboxylation, the catalyst has the advantages of simple preparation method; the metal and P species on the organic phosphine ligand polymer are firmly combined together in a coordinated form and are highly dispersed on the surface of the carrier in a single atom form, so that excellent catalytic activity is brought; compared with the traditional Pd-based catalytic system, the novel Rh-based hydrogen carboxylation catalytic system has excellent stability; in addition, the solid heterogeneous catalyst has outstanding advantages in the aspects of catalyst recycling, catalyst and reactant product separation and the like, and has wide industrial application prospect.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the Rh/L2 (II) catalyst of example 10;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the Rh/L2 (II) catalyst of example 10;
FIG. 3 is a high angle annular dark field image-scanning transmission electron microscope (HAADF-STEM) image of the Rh/L2 (II) catalyst of example 10.
Discussion of the drawings: to demonstrate the monoatomic dispersion of the active component metal of the catalysts described herein, the Rh/L2 (II) catalysts prepared as described in example 10 below were characterized by XR, TEM and HAADF-STEM. As shown in FIG. 1, in contrast to the POPs-L2 XRD pattern of the organophosphine ligand polymer carrier, the Rh/L2 (II) XRD pattern did not find the sharp peak of the metal Rh. Thus, it can be stated that the metals on the Rh/L2 (II) catalyst do not agglomerate and may take on a single-site or monoatomic dispersed state. As shown in fig. 2, a high-resolution TEM photograph of the Rh/L2 (II) catalyst does not find a metal cluster, and thus it is presumed that the active component metal Rh may be monoatomically dispersed. As shown in FIG. 3, it was clearly found that Rh metal was dispersed on the surface of the carrier in the form of single atoms in a high angle annular dark field image-scanning transmission electron microscope (HAADF-STEM) photograph of Rh/L2 (II) catalyst.
Detailed Description
The following examples illustrate but are not limited to what the invention is intended to protect.
In order to better illustrate the superiority of catalysts such as Rh loaded with monoatomically dispersed porous organic phosphine ligand polymers in olefin hydrocarboxylation reaction and the difference of the process conditions of the olefin hydrocarboxylation reaction, the following specific embodiments are carried out. Loading M/POPs single metal or M such as single-atom dispersed Rh by adopting different types of organic phosphine ligand polymers 1 -M 2 POPs bimetallic catalyst (M, M therein) 1 、M 2 Represents a metal such as Ru, au, ir, re, rh, pt and Cu,and M is 1 And M 2 POPs, unlike each other, represent polymers of L1-L8 vinyl functionalized phosphine ligand monomers, described in the examples below as M, M 1 、M 2 The mass content of the metal is 1.0% for the description problem). For example, ru/L1 is a monoatomically dispersed Ru metal catalyst with a polymer loading mass content of 1.0% formed by the L1 ligand in the invention; ru-Rh/L2 is a Ru and Rh bimetallic catalyst with 1.0% of monoatomically dispersed polymer load mass content formed by the L2 ligand in the invention. The following examples are given by way of example of a kettle reaction, and are analogized to fixed bed, trickle bed and slurry bed. In the following examples, the reaction process conditions were first fixed, and variables such as the single metal of the active component, the metal precursor, the bimetal of the active component, the kind of the phosphine ligand polymer carrier, etc. in the catalyst preparation method were examined (examples 1 to 29); next, the catalyst was fixed, and factors such as haloalkane auxiliary agent, acid additive, temperature, pressure and olefin type in the tank reaction process conditions were examined (examples 30 to 44). The preparation method of the catalyst comprises the following steps: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organic phosphine ligand polymer POPs; weighing a certain amount of metal precursor, and dissolving the metal precursor in 30mL of dichloromethane to form a metal precursor solution; under the protection of inert atmosphere, 1.0g of organic phosphine ligand polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the M/POPs catalyst (the mass content of M is 1.0%) is obtained. The kettle type reaction process comprises the following steps: 0.15g of catalyst, 3mmol of halogenated alkane auxiliary agent, 1mmol of acid auxiliary agent, 5.7mmol of olefin, 30mmol of water and 6.0g of solvent acetic acid are weighed, added into a 150mL zirconium reaction kettle, inert gas is replaced for three times, CO gas with certain pressure is filled, the temperature is raised to a certain temperature, after the reaction is carried out for 16 hours, the ice water quenching reaction is carried out, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 1
Ru/L2 (I) catalysisPreparation of the chemical agent: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0394g Ru (acac) was weighed out 3 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the mixture is dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Ru/L2 (I) catalyst. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g of Ru/L2 (I) catalyst and 3mmol of methyl iodide (CH) 3 I) 1mmol of p-toluenesulfonic acid monohydrate (p-TsOH.H 2 O), 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 2
Preparation of Ru/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0211g Ru is weighed 3 (CO) 12 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the mixture is dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Ru/L2 (II) catalyst. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15gRu/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 3
Preparation of Au/L2 (I) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0112g Au is weighed 2 O 3 ·xH 2 O forms a metal precursor solution in 30mL of methylene chloride; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Au/L2 (I) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Au/L2 (I) catalyst and 3mmol of CH are weighed out 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 4
Preparation of Au/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0209g HAuCl 4 ·xH 2 O forms a metal precursor solution in 30mL of methylene chloride; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Au/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Au/L2 (II) catalyst and 3mmol of CH are weighed out 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 5
Preparation of Ir/L2 (I) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0062g Ir 2 O 3 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Ir/L2 (I) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Ir/L2 (I) catalyst, 3mmol of CH are weighed out 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 6
Preparation of Ir/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0155g IrCl was weighed out 3 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Ir/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Ir/L2 (II) catalyst, 3mmol of CH are weighed out 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 7
Preparation of Re/L2 (I) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weighing 0.0135g of HReO 4 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Re/L2 (I) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g Re/L2 (I) catalystChemoattractant, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 8
Preparation of Re/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0144g NH 4 ReO 4 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Re/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g Re/L2 (II) catalyst and 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 9
Preparation of Rh/L2 (I) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0251g Rh (acac) (CO) 2 In 30mL of dichloroMethane forms a metal precursor solution; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (I) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (I) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 10
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 11
Preparation of Pt/L2 (I) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0204g Pt (acac) 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Pt/L2 (I) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Pt/L2 (I) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 12
Preparation of Pt/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0137g PtCl was weighed out 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Pt/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g of Pt/L2 (II) catalyst and 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 13
Preparation of Cu/L2 (I) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0412g Cu (acac) 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Cu/L2 (I) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Cu/L2 (I) catalyst and 3mmol of CH are weighed 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 14
Preparation of Cu/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0314g Cu (OAc) was weighed out 2 Forming metal precursor in 30mL of dichloromethaneA bulk solution; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Cu/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Cu/L2 (II) catalyst and 3mmol of CH are weighed 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 15
Preparation of Ru-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 And 0.0211g Ru 3 (CO) 12 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the mixture is dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Ru-Rh/L2 catalyst. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g of Ru-Rh/L2 catalyst and 3mmol of CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 16
Preparation of Ru-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0155g IrCl was weighed out 3 And 0.0211g Ru 3 (CO) 12 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the mixture is dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Ru-Ir/L2 catalyst. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g of Ru-Ir/L2 catalyst and 3mmol of CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 17
Preparation of Au-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 And 0.0209g HAuCl 4 ·xH 2 O forms a metal precursor solution in 30mL of methylene chloride; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Au-Rh/L2 catalyst can be obtained. The metal can be seen to disperse in a monoatomic form by an electron microscopeOn a carrier.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Au-Rh/L2 catalyst and 3mmol of CH are weighed 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 18
Preparation of Au-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0155g IrCl was weighed out 3 And 0.0209g HAuCl 4 ·xH 2 O forms a metal precursor solution in 30mL of methylene chloride; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Au-Ir/L2 catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Au-Ir/L2 catalyst and 3mmol of CH are weighed 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 19
Preparation of Re-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, and the mixture is stood for 24h at 100Then taking out, and vacuum drying at 60 ℃ to remove the solvent, thus obtaining the organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 And 0.0135g HReO 4 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the mixture is dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Re-Rh/L2 catalyst. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g Re-Rh/L2 catalyst and 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 20
Preparation of Re-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0155g IrCl was weighed out 3 And 0.0135g HReO 4 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the mixture is dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Re-Ir/L2 catalyst. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g Re-Ir/L2 catalyst and 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is replaced for three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃,after 16h of reaction, quenching the reaction with ice water, taking the reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 21
Preparation of Pt-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 And 0.0137g PtCl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Pt-Rh/L2 catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Pt-Rh/L2 catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 22
Preparation of Pt-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0155g IrCl was weighed out 3 And 0.0137g PtCl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, added with the metal precursor solution, and heated to 25 DEG CAfter stirring for 24 hours, the solvent is removed by vacuum drying at 60 ℃ to obtain the Pt-Ir/L2 catalyst. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Pt-Ir/L2 catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 23
Preparation of Cu-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 And 0.0314g Cu (OAc) 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Cu-Rh/L2 catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g of Cu-Rh/L2 catalyst and 3mmol of CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 24
Preparation of Cu-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomerDissolving the body L2 in 10mL of tetrahydrofuran solvent, adding 25mg of azodiisobutyronitrile, stirring at 25 ℃ for 0.5h, then transferring the mixture into a 50mL hydrothermal synthesis kettle, standing for 24h at 100, taking out the mixture, and vacuum drying at 60 ℃ to remove the solvent to obtain an organic phosphine ligand L2 polymer POPs; 0.0155g IrCl was weighed out 3 And 0.0314g Cu (OAc) 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Cu-Ir/L2 catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weighing 0.15g of Cu-Ir/L2 catalyst and 3mmol of CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 25
Preparation of Rh/L1 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L1 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L1 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L1 polymer POPs is weighed, the metal precursor solution is added, stirring is carried out for 24 hours at 25 ℃, and the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L1 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L1 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene30mmol of water and 6.0g of solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is replaced for three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the conversion rate of olefin and the yield of target product are calculated.
Example 26
Preparation of Rh/L3 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L3 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L3 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L3 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L3 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L3 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 27
Preparation of Rh/L6 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L6 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L6 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; in the idle stateUnder the protection of an air atmosphere, 1.0g of organic phosphine ligand L6 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L6 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L6 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 28
Preparation of Rh/L7 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L7 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L7 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L7 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L7 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L7 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 29
Preparation of Rh/L8 (II) catalystThe preparation method comprises the following steps: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L8 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L8 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L8 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L8 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L8 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 30
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II)Catalyst, 3mmol of bromomethane (CH) 3 Br)、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 31
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2 (II) catalyst, 3mmol of Chloroethane (CH) are weighed out 3 CH 2 Cl)、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 32
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organic phosphine ligand L2 polymerPOPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I. 1mmol of trifluoroacetic acid, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after three times of replacement, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 33
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I. 1mmol of methanesulfonic acid, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is replaced for three times, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 34
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 120 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 35
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 150 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 36
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.0MPaCO gas is filled, the temperature is raised to 200 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 37
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100 ℃ and is vacuumized at 60 DEG CDrying to remove the solvent, thus obtaining the organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 0.8MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 38
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 Adding O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid into a 150mL zirconium reaction kettle, replacing the inert gas for three times, filling 0.6MPaCO gas, heating to 180 ℃, reacting for 16h, quenching with ice water, taking the reaction liquid and feedingGas chromatography was performed and the olefin conversion and target product yield were calculated.
Example 39
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 1.5MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 40
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the mixture is dried in vacuum at 60 ℃ to remove the solvent, thus obtaining Rh/L2 (II)) A catalyst. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Cyclohexene (O3) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after being replaced by three times, 3.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 41
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
An ethylene (O1) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol of ethylene (0.2 MPa), 30mmol of water and 6.0g of solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after three times of replacement, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 42
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, and the mixture is stirred for 0.5h at 25 ℃, followed byThen transferring the organic phosphine ligand L2 polymer POPs into a 50mL hydrothermal synthesis kettle, standing for 24 hours at 100, taking out, and vacuum drying at 60 ℃ to remove the solvent; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
Propylene (O1) hydrocarboxylation reaction process: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol of propylene (0.2 MPa), 30mmol of water and 6.0g of solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after three times of replacement, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
Example 43
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
The hydrocarboxylation reaction process of cyclopentene (O2) comprises the following steps: weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 Adding O, 5.7mmol of cyclopentene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium reaction kettle, and filling after three times of inert gas replacement1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching with ice water, taking the reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 44
Preparation of Rh/L2 (II) catalyst: under the protection of inert gas, 1.0g of vinyl functionalized organic phosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azodiisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the mixture is taken out after being stood for 24h at 100, and the solvent is removed by vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; weigh 0.0189g Rh 2 (CO) 4 Cl 2 Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs is weighed, the metal precursor solution is added, the mixture is stirred for 24 hours at 25 ℃, and then the solvent is removed by vacuum drying at 60 ℃, so that the Rh/L2 (II) catalyst can be obtained. The metal can be seen by electron microscopy to be dispersed in the form of monoatoms on the support.
The hydrocarboxylation reaction process of styrene (O6): weigh 0.15g Rh/L2 (II) catalyst, 3mmol CH 3 I、1mmol p-TsOH·H 2 O, 5.7mmol of styrene, 30mmol of water and 6.0g of solvent acetic acid are added into a 150mL zirconium reaction kettle, inert gas is filled into the reaction kettle after three times of replacement, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, the reaction is quenched by ice water after 16 hours of reaction, the reaction liquid is taken for gas chromatography analysis, and the olefin conversion rate and the target product yield are calculated.
The application case is the application of the prepared catalyst in the reaction of preparing organic carboxylic acid by olefin hydrocarboxylation
Using the catalysts prepared in examples 1-44, the corresponding carboxylic acid products were prepared according to the reaction process conditions in the respective examples, with the conversion of the starting olefins and the yields of the product carboxylic acids as shown in Table 1.
TABLE 1 results of the preparation of organic carboxylic acids by hydrocarboxylation of olefins
Figure BDA0002794157510000231
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Figure BDA0002794157510000241
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Figure BDA0002794157510000251
The results show that: as can be seen from comparative examples 1-29, the activity of the single-atom catalysts such as Ru supported by different organic phosphine ligand polymer carriers in the preparation of organic carboxylic acid by olefin hydrocarboxylation is better, wherein the active component single metal is Rh or bimetal is Re-Rh, the carrier is L2 monomer to form Rh/L2 (II) or Re-Rh/L2 (II) catalysts of the polymer are more prominent, the active single metal is Rh, the bimetal is Re-Rh, and the carrier is L2 monomer to form the polymer. As can be obtained in comparative examples 30-44, when Rh/L2 (II) catalyst is applied to olefin hydrocarboxylation to prepare organic carboxylic acid, haloalkane auxiliary agents, acid additives, temperature, pressure and olefin types in the reaction process have certain influence on the reaction activity, and haloalkane auxiliary agents are preferably methyl iodide and methyl bromide, more preferably methyl iodide; the acid additive is preferably methanesulfonic acid and p-toluenesulfonic acid monohydrate, more preferably p-toluenesulfonic acid monohydrate; the temperature is preferably 180 and 200 ℃, more preferably 180 ℃; the pressure is preferably 1.0 and 1.5MPa, more preferably 1.0MPa; the catalytic system has strong applicability to olefin types, wherein ethylene, propylene and cyclohexene are better in activity, and ethylene and cyclohexene are more preferable.

Claims (15)

1. A process for the preparation of an organic carboxylic acid by hydrocarboxylation of an olefin, characterized by:
the adopted solid heterogeneous catalyst consists of two parts of active component metal and a carrier; the active component metal is one or more than two of Ru, au, ir, re, rh, pt, cu; the carrier is a vinyl functionalized porous organic phosphine ligand polymer;
in the presence of a solid heterogeneous catalyst, auxiliary agent halogenated alkane, acid additive and carboxylic acid solvent, raw material olefin, CO and water undergo hydrocarboxylation reaction to prepare organic carboxylic acid;
the auxiliary agent halogenated alkane is one or more than two of methyl chloride, methyl bromide, methyl iodide, diiodomethane, ethyl chloride, ethyl bromide and ethyl iodide;
the acid additive is one or more than two of trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, nitric acid and hydrochloric acid;
the carboxylic acid solvent is one or more of formic acid, acetic acid, propionic acid, n-butyric acid and isobutyric acid;
the reaction temperature is 30-250 ℃; the reaction pressure is 0.05-20.0 MPa;
the raw material olefin is one or more than two of O1-O7 in the compound shown in the formula 1;
Figure QLYQS_1
formula 1. Raw material olefin type.
2. The method according to claim 1, characterized in that:
The reaction is carried out in a fixed bed, trickle bed, slurry bed or kettle reactor; when a fixed bed or a trickle bed is adopted, the liquid hourly space velocity is 0.01-20.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The gas hourly space velocity is 100-20000 h -1 。
3. The method according to claim 2, characterized in that:
when a fixed bed or a trickle bed is adopted, the liquid hourly space velocity is 1-5 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The gas hourly space velocity is 500-2000 h -1 。
4. The method according to claim 1, characterized in that:
the auxiliary agent halogenated alkane is one or more than two of methyl iodide, bromoethane and ethyl iodide;
the acid additive is one or more than two of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid;
the reaction temperature is 120-200 ℃; the reaction pressure is 0.5-2 MPa.
5. A method according to any one of claims 1-3, characterized in that:
the molar ratio of the active component metal of the solid heterogeneous catalyst to the auxiliary agent halogenated alkane is 0.0001:1-0.05:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to the acid additive is 0.001:1-0.1:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to the carboxylic acid solvent is 0.00001:1-0.001:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to the raw material olefin is 0.0001:1-0.05:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to CO is 0.00001:1-0.001:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to water is 0.00001:1-0.01:1.
6. A method according to any one of claims 1-3, characterized in that:
the molar ratio of the active component metal of the solid heterogeneous catalyst to the auxiliary agent halogenated alkane is 0.0005:1-0.001:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to the acid additive is 0.005:1-0.05:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to the carboxylic acid solvent is 0.00005:1-0.0005:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to the raw material olefin is 0.0005:1-0.001:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to CO is 0.0001:1-0.0008:1; the molar ratio of the active component metal of the solid heterogeneous catalyst to water is 0.0001:1-0.001:1.
7. The method according to claim 1, characterized in that:
the active component metal of the solid heterogeneous catalyst is dispersed on a carrier in a single atomic level and is combined with phosphorus atoms in the porous organic phosphine ligand polymer of the carrier in a coordination bond form.
8. The method according to claim 1, characterized in that:
the preparation method of the catalyst comprises the following steps:
1) First, a porous organophosphine ligand polymer carrier is prepared:
under the protection of inert gas, dissolving a vinyl functionalized organic phosphine ligand monomer in a solvent, adding a free radical initiator, and stirring at 0-100 ℃ for 0.2-2 h; then transferring the mixture into a hydrothermal synthesis kettle, and standing the mixture at 50-300 ℃ for 5-50 hours; finally, taking out the mixture, and vacuum drying at 30-100 ℃ to remove the solvent;
2) Secondly, preparing a metal precursor solution of the active component;
3) And finally, adding the porous organic phosphine ligand polymer carrier in the step 1) into the metal precursor solution in the step 2) under the protection of inert gas, stirring for 10-50 h at 0-100 ℃, and then, drying in vacuum for 2-12 h at 25-150 ℃ to obtain the product catalyst.
9. The method according to claim 8, wherein:
the active metal precursor compound in step 2) is Ru (acac) 3 、Ru 3 (CO) 12 、RuCl 3 、Au 2 O 3 ・xH 2 O、HAuCl 4 ・xH 2 O、Ir 2 O 3 、Ir(OH) 3 、IrCl 3 、HReO 4 、NH 4 ReO 4 、ReCl 5 、Rh(acac)(CO) 2 、Rh 2 (CO) 4 Cl 2 、RhCl 3 、Pt(acac) 2 、PtCl 2 、PtCl 4 、H 2 PtCl 6 、Cu(acac) 2 、Cu(OAc) 2 And CuCl 2 One or more than two of them.
10. The method according to claim 9, wherein: the active metal precursor compound in step 2) is Ru 3 (CO) 12 、HAuCl 4 ・xH 2 O、IrCl 3 、HReO 4 、Rh 2 (CO) 4 Cl 2 、H 2 PtCl 6 、Cu(acac) 2 One or two or more of them.
11. The method according to claim 8, wherein:
the organic phosphine ligand monomer in the step 1) is one or more than two of the compounds L1-L8 in the formula 2;
Figure QLYQS_2
and (2) an organic phosphine ligand monomer.
12. The method according to claim 8, wherein:
the solvent used in the preparation step 1) is one or more than two of tetrahydrofuran, toluene, benzene, methylene dichloride, chloroform and dimethylformamide; the free radical initiator used in the step 1) is one or more than two of hydrogen peroxide, ammonium persulfate, benzoyl peroxide, cyclohexanone peroxide, azodiisobutyronitrile, azodiisoheptanenitrile, dimethyl azodiisobutyrate and azodiisoheptanenitrile composite initiation systems; the solvent used in the step 2) is one or more of dioxane, tetrahydrofuran, dichloromethane and dimethylformamide.
13. The method according to claim 12, wherein:
the solvents used in the preparation step 1) are tetrahydrofuran and methylene dichloride; the free radical initiator used in step 1) is cyclohexanone peroxide and azobisisobutyronitrile; the solvents used in step 2) are tetrahydrofuran and dichloromethane.
14. The method according to claim 12, wherein:
the mass ratio of the solvent to the organic phosphine ligand monomer in the step 1) is 5:1-300:1; the mass ratio of the free radical initiator to the organic phosphine ligand monomer is 1:5-1:500; the mass ratio of the solvent in the step 2) to the porous organic phosphine ligand polymer carrier in the step 3) is 6:1-280:1; the specific surface area of the porous organic phosphine ligand polymer carrier is 200-3000 m 2 /g; pore volume of 0.05-8.0. 8.0 cm 3 /g; the pore size distribution is0.05~800 nm。
15. The method according to claim 14, wherein:
the mass ratio of the solvent to the organic phosphine ligand monomer in the step 1) is 20:1-100:1; the mass ratio of the free radical initiator to the organic phosphine ligand monomer is 1:20-1:100; the mass ratio of the solvent in the step 2) to the porous organic phosphine ligand polymer carrier in the step 3) is 15:1-80:1; the specific surface area of the porous organic phosphine ligand polymer carrier is 800-1500 m 2 /g; the pore volume is 0.5-2.0 cm 3 /g; the pore size distribution is 0.8-400 nm.
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