CN114534792A - 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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CN114534792A
CN114534792A CN202011325544.7A CN202011325544A CN114534792A CN 114534792 A CN114534792 A CN 114534792A CN 202011325544 A CN202011325544 A CN 202011325544A CN 114534792 A CN114534792 A CN 114534792A
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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 method for preparing organic carboxylic acid by olefin hydrocarboxylation. The invention provides a metal monoatomic catalyst loaded by a vinyl functional group porous organic phosphine ligand polymer, 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, a certain temp. and pressure and said catalyst the olefine, 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 have important applications in food, polymer, pharmaceutical, cosmetic and other manufacturing fields. Meanwhile, the carboxylic acid is used as an intermediate and also has important application in the aspect of preparing derivatives such as ester, ketone, amide, alcohol and the like. The production of organic carboxylic acids is therefore of great importance both in chemical organic synthesis and on an industrial level.
The production process of carboxylic acid is generally divided into paraffin oxidation, Colgate-Emery process and hydroformylation reoxidation, but the yield is not high and the selectivity is poor due to the paraffin oxidation; the product of the Colgate-Emery process is only an even number of carbon carboxylic acids; the steps of the olefin hydroformylation reoxidation method are complicated, so that a direct, effective, convenient and quick carboxylic acid preparation method has to be found. The hydrocarboxylation of olefins has received considerable attention from numerous researchers as a one-step process for the production of organic carboxylic acids (see formula 3).
Figure BDA0002794157510000011
Hydrocarboxylation of olefins of formula 3 to organic carboxylic acids
Hydrocarboxylation reactions were discovered and put into production by the basf chemist Reppe as early as 1953. This was followed by a considerable amount of research by a series of researchers. KutePow finds that Pd can well catalyze hydrocarboxylation reaction by replacing a Ni/Co/Fe catalyst for the first time, and the reaction condition is milder; fenton's discovery of PPh3The introduction of the ligand can improve the activity of the hydrocarboxylation reaction of the Pd system to a certain extent; subsequently, scientists have made their efforts to improve the performance of hydrocarboxylation reactions and to stabilize Pd catalysts in the modification of the promoters and the optimization of the ligands.
The homogeneous reaction occupies a large chapter in the whole hydrogen carboxylation development history, but the homogeneous reaction is difficult to separate and difficult to recycle by people and the like, and is hindered by certain defects in industrial development; the Pd (II) catalyzed hydrocarboxylation system is easy to be reduced into Pd (0) by ligand and CO due to the inherent outer layer electronic structure characteristic and even agglomerated into palladium black, which brings instability of the catalytic system. Therefore, the heterogeneous catalysis with single-site Rh and other groups can be produced while retaining the advantage of high homogeneous activity and realizing the separation of the catalyst and the product, and the good stability is brought to the catalytic system.
Here, we propose a solid heterogeneous catalyst with Ru, Au, Ir, Re, Rh, Pt or Cu single atom loaded on porous organic phosphine ligand polymer carrier for the reaction of olefin hydrocarboxylation to prepare organic carboxylic acid. The catalytic 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 a 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 for the reaction of preparing organic carboxylic acid by olefin hydrocarboxylation. Under the action of auxiliary agent halogenated alkane, acid additive, carboxylic acid solvent, a certain temp. and pressure and said catalyst the olefine, 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 active component metal and a carrier; the active component metal is one or more than two of Ru, Au, Ir, Re, Rh, Pt and Cu; the carrier is a vinyl functionalized porous organic phosphine ligand polymer;
in the presence of a solid heterogeneous catalyst, auxiliary agent halogenated alkane, an acid additive and a carboxylic acid solvent, raw material olefin, CO and water are subjected to hydrocarboxylation reaction to prepare organic carboxylic acid.
The reaction is carried out in a fixed bedIn a fluid bed, slurry bed or tank reactor; when a fixed bed or a trickle bed is adopted, the liquid hourly space velocity is 0.01-20.0 h-1Preferably 1 to 5 hours-1(ii) a The gas hourly space velocity is 100-20000 h-1Preferably 500 to 2000h-1。
The auxiliary agent halogenated alkane is one or more of methyl chloride, methyl bromide, methyl iodide, diiodomethane, ethyl chloride, ethyl bromide and ethyl iodide, preferably one or more of methyl iodide, 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, preferably one or more than two of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid;
the carboxylic acid solvent is one or more than two of formic acid, acetic acid, propionic acid, n-butyric acid and isobutyric acid;
the reaction temperature is 30-250 ℃, and 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
R1and R2Represents H or C1-16And the sum of the carbon numbers of the two is not more than 16
Figure BDA0002794157510000032
Formula 1. feed olefin species.
The molar ratio of the solid heterogeneous catalyst metal to the auxiliary 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: 1-0.1: 1, preferably 0.005: 1-0.05: 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 feedstock olefin is from 0.0001:1 to 0.05:1, preferably from 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 the carrier in a monoatomic level and is combined with the phosphorus atom in the porous organic phosphine ligand polymer of the carrier in a coordination bond mode.
The preparation method of the catalyst comprises the following steps:
1) first, a porous organophosphine ligand polymer support 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 for 0.2-2 h (preferably 0.5h) at 0-100 ℃ (preferably 25 ℃); then, transferring the mixture into a hydrothermal synthesis kettle, and standing for 5-50 h (preferably 24h) at 50-300 ℃ (preferably 100 ℃); finally, taking out the mixture, and drying the mixture in vacuum at 30-100 ℃ to remove the solvent;
2) secondly, preparing a metal precursor solution of an active component;
3) and finally, under the protection of inert gas, adding the organic phosphine ligand polymer in the step 1) into the metal precursor solution in the step 2), stirring for 10-50 h (preferably 24h) at 0-100 ℃ (preferably 25 ℃), and then, drying for 2-12 h (preferably 6h) in vacuum at 25-150 ℃ (preferably 60 ℃), thus obtaining the product catalyst.
The active metal precursor compound is mainly ruthenium acetylacetonate (Ru (acac)3) Dodecacarbonyltriruthenium (Ru)3(CO)12) Ruthenium trichloride (RuCl)3) Gold oxide hydrate (Au)2O3·xH2O), gold (III) chloride hydrate (HAuCl)4·xH2O), iridium oxide (Ir)2O3) Iridium hydroxide (Ir (OH)3) Iridium chloride (IrCl)3) Perrhenic acid (HReO)4) Ammonium perrhenate (NH)4ReO4) Rhenium pentachloride (Recl)5) Rhodium acetylacetonate (Rh (acac) (CO)2) Tetracarbonyldirhodium dichloride (Rh)2(CO)4Cl2) Rhodium trichloride (RhCl)3) Platinum acetylacetonate (Pt (acac))2) Platinum chloride (PtCl)2、PtCl4) Chloroplatinic acid (H)2PtCl6) Copper acetylacetonate (Cu (acac)2) Copper acetate (Cu (OAc))2) And copper chloride (CuCl)2) Preferably Ru3(CO)12、HAuCl4·xH2O、IrCl3、HReO4、Rh2(CO)4Cl2、H2PtCl6、Cu(acac)2One or more than two of them.
The mass loading capacity 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 compounds L2, L3 and L6;
Figure BDA0002794157510000041
formula 2. organic phosphine ligand monomer.
The solvent used in the preparation step 1) of the carrier organic phosphine ligand polymer is one or more than two of tetrahydrofuran, toluene, benzene, dichloromethane, trichloromethane and dimethylformamide, preferably tetrahydrofuran and dichloromethane; 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 a compound initiation system of azobisisobutyronitrile and azobisisoheptonitrile, and preferably cyclohexanone peroxide and azobisisobutyronitrile; the solvent used in 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 solvent of step 2) and the organophosphine ligand polymeric material of step 3)The amount ratio is 6: 1-280: 1, preferably 15: 1-80: 1; the specific surface area of the carrier is 200-3000 m2Per g, preferably 800 to 1500m2(ii)/g; the pore volume is 0.05-8.0cm3A/g, preferably 0.5 to 2.0cm3(ii)/g; the pore size distribution is 0.05-800 nm, preferably 0.8-400 nm.
The invention has the beneficial effects that:
compared with the prior art for preparing organic carboxylic acid by olefin hydrocarboxylation, the preparation method of the catalyst is simple; the metal and the P species on the organic phosphine ligand polymer are firmly combined together in a matched 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 hydrocarboxylation 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 catalyst of example 10Rh/L2 (II).
Discussion of the drawings: to demonstrate the monoatomic dispersion of the active component metals of the catalysts described herein, the Rh/L2(II) catalyst prepared as described in example 10 below was characterized by XR, TEM and HAADF-STEM. As shown in figure 1, compared with the XRD spectrum of the organic phosphine ligand polymer carrier POPs-L2, the XRD spectrum of Rh/L2(II) does not have a peak of metal Rh. Thus, it can be shown that the metals on the Rh/L2(II) catalyst did not agglomerate and may be in a single-site or monoatomic dispersion. As shown in fig. 2, the high-resolution TEM photograph of the Rh/L2(II) catalyst did not reveal metal clusters, and therefore it is presumed that the active component metal Rh may be monoatomic. As shown in fig. 3, it can be clearly seen from the high angle annular dark field image-scanning transmission electron microscope (HAADF-STEM) photograph of the Rh/L2(II) catalyst that the metallic Rh is scattered in the form of a single atom on the surface of the support.
Detailed Description
The following examples illustrate but do not limit the invention claimed.
In order to better illustrate the superiority of the catalyst such as the porous organic phosphine ligand polymer loaded with the monoatomic dispersed Rh in the olefin hydrocarboxylation reaction and the difference of the process conditions of the olefin hydrocarboxylation reaction, the following specific embodiments are carried out. Different kinds of organic phosphine ligand polymer are adopted to load M/POPs monometal or M such as Rh and the like with single atom dispersion1-M2/POPs bimetallic catalyst (M, M among them)1、M2Represents a metal such as Ru, Au, Ir, Re, Rh, Pt or Cu, and M1And M2POPs, which are different from each other, represent polymers formed from L1-L8 vinyl-functionalized phosphine ligand monomers, designated M, M in the examples below1、M2The metal contents are all 1.0% by mass, representing illustrative problems). For example, Ru/L1 is a monoatomic Ru metal catalyst with a polymer loading mass content of 1.0% formed by the L1 ligand of the invention; Ru-Rh/L2 is a bimetallic catalyst of Ru and Rh with polymer loading mass content of 1.0% and monoatomic dispersion formed by the L2 ligand in the invention. In the following examples, a tank reaction is taken as an example, and a fixed bed, a trickle bed and a slurry bed are analogized in the same way. In the following examples, the reaction process conditions were first fixed, and variables such as the active component monometallics, the metal precursors, the active component bimetals, and the phosphine ligand polymer carrier species in the catalyst preparation method were investigated (examples 1 to 29); next, the catalyst was immobilized, and the conditions of the tank reaction were examined for halogenated alkane auxiliary, acid additive, temperature, pressure, and kind of olefin (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 organophosphine ligand monomer L is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred for 0.5h at 25 ℃, then the mixture is moved into a 50mL hydrothermal synthesis kettle, and is taken out after being kept stand for 24h at 100 ℃, and the solvent is removed by vacuum drying at 60 ℃, so that the organophosphine ligand polymer POPs can be obtained; 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, stirred for 24 hours at 25 ℃, and then dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the M/POPs catalyst (M mass content is 1.0%). The kettle type reaction process comprises the following steps: weighing 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, adding into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging CO gas with certain pressure, heating to a certain temperature, reacting for 16h, quenching with ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 1
Preparation of Ru/L2(I) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; weighing 0.0394g Ru (acac)3Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Ru/L2(I) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Ru/L2(I) catalyst and 3mmol of iodomethane (CH) were weighed out3I) 1mmol of p-toluenesulfonic acid monohydrate (p-TsOH. H)2O), 5.7mmol of cyclohexene, 30mmol of water and 6.0g of acetic acid solvent are added into a 150mL zirconium material reaction kettle, after three times of inert gas replacement, 1.0MPaCO gas is filled, the temperature is raised to 180 ℃, after 16 hours of reaction, the reaction is quenched by ice water, 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 inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 was dissolved in 10mL of tetrahydroAdding 25mg of azodiisobutyronitrile into a furan solvent, stirring at 25 ℃ for 0.5h, then transferring the mixture into a 50mL hydrothermal synthesis kettle, standing at 100 ℃ for 24h, taking out, and drying at 60 ℃ in vacuum to remove the solvent to obtain organic phosphine ligand L2 polymer POPs; weighing 0.0211g Ru3(CO)12Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Ru/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Ru/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 3
Preparation of Au/L2(I) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0112g of Au was weighed2O3·xH2O in 30mL of dichloromethane to form a metal precursor solution; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Au/L2(I) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Au/L2(I) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2O, 5.7mmol cyclohexene, 30mmol water and 6.0g solvent acetic acid were addedAnd (3) filling 1.0MPaCO gas into a 150mL zirconium material reaction kettle after three times of inert gas replacement, heating to 180 ℃, reacting for 16 hours, quenching the reaction by ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 4
Preparation of Au/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0209g of HAuCl is weighed4·xH2O in 30mL of dichloromethane to form a metal precursor solution; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Au/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Au/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 5
Preparation of Ir/L2(I) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; weighing 0.0062g Ir2O3Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, and addedAdding the metal precursor solution, stirring at 25 ℃ for 24h, and then drying under vacuum at 60 ℃ to remove the solvent, thus obtaining the Ir/L2(I) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g Ir/L2(I) catalyst and 3mmol CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 6
Preparation of Ir/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0155g of IrCl was weighed3Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Ir/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Ir/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 7
Preparation of Re/L2(I) catalyst: under inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 was dissolved in 10mL of tetrakisAdding 25mg of azodiisobutyronitrile into a tetrahydrofuran solvent, stirring at 25 ℃ for 0.5h, then transferring the mixture into a 50mL hydrothermal synthesis kettle, standing at 100 ℃ for 24h, taking out, and drying at 60 ℃ in vacuum to remove the solvent to obtain organic phosphine ligand L2 polymer POPs; weighing 0.0135g of HReO4Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Re/L2(I) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Re/L2(I) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 8
Preparation of Re/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0144g of NH was weighed4ReO4Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Re/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Re/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid are added into a 150mL zirconium material reaction kettle and inertAnd (3) after the sexual gas is replaced for three times, filling 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction by using ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of the olefin and the yield of the target product.
Example 9
Preparation of Rh/L2(I) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0251g of Rh (acac) (CO) are weighed out2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(I) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(I) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 10
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, and the metal precursor is addedStirring the solution at 25 ℃ for 24h, and then drying the solution at 60 ℃ in vacuum to remove the solvent to obtain the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH are weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
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 azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle stands for 24h at 100 ℃ and then is taken out, and the solvent is removed through vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0204g of Pt (acac) is weighed2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Pt/L2(I) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Pt/L2(I) catalyst and 3mmol of CH are weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 12
Preparation of Pt/L2(II) catalyst: under inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 was dissolved in 10mL of tetrahydrofuran solventAdding 25mg of azodiisobutyronitrile, stirring at 25 ℃ for 0.5h, then transferring the mixture into a 50mL hydrothermal synthesis kettle, standing at 100 for 24h, taking out, and drying at 60 ℃ in vacuum to remove the solvent to obtain the organic phosphine ligand L2 polymer POPs; 0.0137g of PtCl was weighed2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Pt/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Pt/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, performing gas chromatography analysis on reaction liquid, and calculating the conversion rate of olefin and the yield of a target product.
Example 13
Preparation of Cu/L2(I) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; weighing 0.0412g Cu (acac)2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Cu/L2(I) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Cu/L2(I) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid are added into a 150mL zirconium material reaction kettle, and after three times of inert gas replacementFilling 1.0MPaCO gas, heating to 180 ℃, reacting for 16h, quenching the reaction by ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of the olefin and the yield of the target product.
Example 14
Preparation of Cu/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0314g Cu (OAc) is weighed2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Cu/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Cu/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 15
Preparation of Ru-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2And 0.0211g Ru3(CO)12Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed and addedAnd stirring the metal precursor solution at 25 ℃ for 24 hours, and then drying the solution at 60 ℃ in vacuum to remove the solvent to obtain the Ru-Rh/L2 catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Ru-Rh/L2 catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 16
Preparation of Ru-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0155g of IrCl was weighed3And 0.0211g Ru3(CO)12Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, the metal precursor solution is added, after stirring for 24 hours at 25 ℃, the solvent is removed by vacuum drying at 60 ℃, and the Ru-Ir/L2 catalyst is obtained. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Ru-Ir/L2 catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 17
Preparation of Au-Rh/L2 catalyst: under inert gas, 1.0g of vinyl functional groupsDissolving the organic phosphine ligand monomer L2 in 10mL tetrahydrofuran solvent, adding 25mg of azodiisobutyronitrile, stirring at 25 ℃ for 0.5h, then transferring the mixture into a 50mL hydrothermal synthesis kettle, standing at 100 ℃ for 24h, taking out, and vacuum-drying at 60 ℃ to remove the solvent to obtain organic phosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2And 0.0209g of HAuCl4·xH2O in 30mL of dichloromethane to form a metal precursor solution; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Au-Rh/L2 catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Au-Rh/L2 catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 18
Preparation of Au-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0155g of IrCl was weighed3And 0.0209g of HAuCl4·xH2O in 30mL of dichloromethane to form a metal precursor solution; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Au-Ir/L2 catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Au-Ir/L2 catalyst was weighed outAgent, 3mmol CH3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 19
Preparation of Re-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2And 0.0135g HReO4Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Re-Rh/L2 catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Re-Rh/L2 catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 20
Preparation of Re-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; weighing 0.0155g IrCl3And 0.0135g HReO4Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Re-Ir/L2 catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g Re-Ir/L2 catalyst and 3mmol CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 21
Preparation of Pt-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2And 0.0137g of PtCl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, the metal precursor solution is added, after stirring for 24 hours at 25 ℃, the solvent is removed by vacuum drying at 60 ℃, and the Pt-Rh/L2 catalyst is obtained. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Pt-Rh/L2 catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, performing gas chromatography analysis on reaction liquid, and calculating the olefin conversion rate and the targetThe product yield.
Example 22
Preparation of Pt-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0155g of IrCl was weighed3And 0.0137g of PtCl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, the metal precursor solution is added, after stirring for 24 hours at 25 ℃, the solvent is removed by vacuum drying at 60 ℃, and the Pt-Ir/L2 catalyst is obtained. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Pt-Ir/L2 catalyst and 3mmol of CH are weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 23
Preparation of Cu-Rh/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2And 0.0314g Cu (OAc)2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, the metal precursor solution is added, after stirring for 24h at 25 ℃, the solvent is removed by vacuum drying at 60 ℃, and the Cu-Rh/L2 catalyst is obtained. Can be seen through an electron microscopeThe metal is dispersed on the carrier in a monoatomic form.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Cu-Rh/L2 catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 24
Preparation of Cu-Ir/L2 catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0155g of IrCl was weighed3And 0.0314g Cu (OAc)2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, the metal precursor solution is added, after stirring for 24h at 25 ℃, the solvent is removed by vacuum drying at 60 ℃, and the Cu-Ir/L2 catalyst is obtained. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Cu-Ir/L2 catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 25
Preparation of Rh/L1(II) catalyst: 1.0g of vinyl-functionalized organophosphine ligand monomer L1 was dissolved in 10mL of tetrahydrofuran solvent under inert gas, 25mg of azobisisobutyronitrile was added, stirred at 25 ℃ for 0.5h, and then transferred to a 50mL hydrothermal synthesis kettleStanding for 24h at 100 ℃, taking out, and vacuum drying at 60 ℃ to remove the solvent to obtain the organic phosphine ligand L1 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L1 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L1(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L1(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 26
Preparation of Rh/L3(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L3 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L3 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L3 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L3(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L3(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol cyclohexene, 30mmol water and 6.0g acetic acid solvent into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, and reactingAfter 16h, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of the olefin and the yield of the target product.
Example 27
Preparation of Rh/L6(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L6 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L6 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L6 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L6(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L6(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 28
Preparation of Rh/L7(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L7 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L7 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L7 polymer POPs are weighed, added with the metal precursor solution, stirred for 24h at 25 ℃, and then stirred at 60 DEG CThe solvent was removed by vacuum drying to obtain Rh/L7(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L7(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 29
Preparation of Rh/L8(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L8 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L8 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L8 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L8(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L8(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 30
Preparation of Rh/L2(II) catalyst: under inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 was dissolved in 10mL of tetrahydrofuran solvent and 25 was addedStirring azodiisobutyronitrile for 0.5h at 25 ℃, then transferring the azodiisobutyronitrile into a 50mL hydrothermal synthesis kettle, standing for 24h at 100 ℃, taking out, and drying in vacuum at 60 ℃ to remove the solvent to obtain organic phosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of methyl bromide (CH) were weighed out3Br)、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of the target product.
Example 31
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried in vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of Chloroethane (CH) were weighed out3CH2Cl)、1mmol p-TsOH·H2O, 5.7mmol cyclohexene, 30mmol water andadding 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, filling 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 32
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I. Adding 1mmol of trifluoroacetic acid, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, filling 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
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 azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is transferred into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle stands for 24h at 100 ℃ and then is taken out, and the solvent is removed through vacuum drying at 60 ℃ to obtain organic phosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; weighing under inert atmosphereAdding 1.0g of organic phosphine ligand L2 polymer POPs into the metal precursor solution, stirring at 25 ℃ for 24h, and drying under vacuum at 60 ℃ to remove the solvent to obtain the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I. Adding 1mmol of methanesulfonic acid, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, filling 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking the reaction solution for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of a target product.
Example 34
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing inert gas for three times, filling 1.0MPaCO gas, heating to 120 ℃, reacting for 16 hours, quenching the reaction by ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of a target product.
Example 35
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0Dissolving a vinyl functionalized organic phosphine ligand monomer 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, and vacuum-drying at 60 ℃ to remove the solvent to obtain organic phosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing inert gas for three times, filling 1.0MPaCO gas, heating to 150 ℃, reacting for 16 hours, quenching the reaction by ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of a target product.
Example 36
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, filling 1.0MPaCO gas, heating to 200 ℃, reacting for 16 hours, quenching the reaction with ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 37
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, filling 0.8MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 38
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2In 30mL twoForming metal precursor solution by using chloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, filling 0.6MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 39
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing inert gas for three times, filling 1.5MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction by ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of a target product.
Example 40
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclohexene (O3) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of cyclohexene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing with inert gas for three times, filling 3.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction with ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
EXAMPLE 41
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Ethylene (O1) hydrogenAnd (3) a carboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of ethylene (0.2MPa), 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing the mixture by inert gas for three times, filling 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction by ice water, taking reaction liquid for gas chromatography analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 42
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh was weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Propylene (O1) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of propylene (0.2MPa), 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing three times by inert gas, filling 1.0MPaCO gas, heating to 180 ℃, quenching the reaction by ice water after reacting for 16 hours, taking reaction liquid for gas chromatographic analysis, and calculating the conversion rate of olefin and the yield of target product.
Example 43
Preparation of Rh/L2(II) catalyst: under the protection of inert gas, 1.0g of vinyl-functionalized organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, the solvent is removed by vacuum drying at 60 ℃, and the organophosphine ligand can be obtainedBulk L2 polymer POPs; 0.0189g of Rh were weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Cyclopentene (O2) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH were weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol cyclopentene, 30mmol water and 6.0g acetic acid solvent into a 150mL zirconium reaction kettle, replacing with inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16h, quenching the reaction with ice water, taking the reaction solution 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 organophosphine ligand monomer L2 is dissolved in 10mL of tetrahydrofuran solvent, 25mg of azobisisobutyronitrile is added, the mixture is stirred at 25 ℃ for 0.5h, then the mixture is moved into a 50mL hydrothermal synthesis kettle, the hydrothermal synthesis kettle is kept stand for 24h at 100 ℃ and then taken out, and the solvent is removed by vacuum drying at 60 ℃ to obtain the organophosphine ligand L2 polymer POPs; 0.0189g of Rh were weighed2(CO)4Cl2Forming a metal precursor solution in 30mL of dichloromethane; under the protection of inert atmosphere, 1.0g of organic phosphine ligand L2 polymer POPs are weighed, added with the metal precursor solution, stirred for 24 hours at 25 ℃, and dried under vacuum at 60 ℃ to remove the solvent, thus obtaining the Rh/L2(II) catalyst. The metal is dispersed on the carrier in the form of a single atom as can be seen by electron microscopy.
Styrene (O6) hydrocarboxylation reaction process: 0.15g of Rh/L2(II) catalyst and 3mmol of CH are weighed3I、1mmol p-TsOH·H2Adding O, 5.7mmol of styrene, 30mmol of water and 6.0g of solvent acetic acid into a 150mL zirconium material reaction kettle, replacing inert gas for three times, charging 1.0MPaCO gas, heating to 180 ℃, reacting for 16 hours, quenching the reaction by ice water, taking the reaction solution for gas chromatography analysis, and calculating the olefin conversionRate and yield of the desired product.
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 conditions in the respective examples, and the conversion of the starting olefin and the yield of the product carboxylic acid are shown in Table 1.
TABLE 1 results of the hydrocarboxylation of olefins to organic carboxylic acids
Figure BDA0002794157510000231
Figure BDA0002794157510000241
Figure BDA0002794157510000251
The results show that: comparative examples 1 to 29 show that the single atom catalysts such as Ru loaded on different organic phosphine ligand polymer carriers have better activity in the reaction of preparing organic carboxylic acid by olefin hydrocarboxylation, wherein the Rh/L2(II) or Re-Rh/L2(II) catalyst of the polymer formed by taking the active component of single metal as Rh or bimetal as Re-Rh and the carrier of L2 monomer is more prominent, the active single metal is preferably Rh, the bimetal is preferably Re-Rh, and the carrier is preferably L2 monomer to form the polymer. Comparative examples 30 to 44 can show that when the Rh/L2(II) catalyst is applied to the hydrocarboxylation of olefins to prepare organic carboxylic acids, the haloalkane auxiliary agent, the acid additive, the temperature, the pressure and the olefin species in the reaction process all have certain influence on the reaction activity, and the haloalkane auxiliary agent is preferably methyl iodide and methyl bromide, and 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 1.0 MPa; the catalyst system has stronger applicability to olefin types, wherein the activity of ethylene, propylene and cyclohexene is better, and the ethylene and cyclohexene are more preferable.

Claims (10)

1. A method for preparing organic carboxylic acid by olefin hydrocarboxylation is characterized in that:
the adopted solid heterogeneous catalyst consists of active component metal and a carrier; the active component metal is one or more than two of Ru, Au, Ir, Re, Rh, Pt and Cu; the carrier is a vinyl functionalized porous organic phosphine ligand polymer;
in the presence of a solid heterogeneous catalyst, auxiliary agent halogenated alkane, an acid additive and a carboxylic acid solvent, raw material olefin, CO and water are subjected to hydrocarboxylation reaction to prepare organic carboxylic acid.
2. The method of claim 1, wherein:
the reaction is carried out in a fixed bed, a trickle bed, a slurry bed or a tank reactor; when a fixed bed or a trickle bed is adopted, the liquid hourly space velocity is 0.01-20.0 h-1Preferably 1 to 5 hours-1(ii) a The gas hourly space velocity is 100-20000 h-1Preferably 500 to 2000 hours-1。
3. The method of claim 1, wherein:
the auxiliary agent halogenated alkane is one or more than two of chloromethane, bromomethane, iodomethane, diiodomethane, chloroethane, bromoethane and iodoethane, preferably one or more than two of iodomethane, bromoethane and iodoethane;
the acid additive is one or more than two of trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, nitric acid and hydrochloric acid, preferably one or more than two of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid;
the carboxylic acid solvent is one or more than two of formic acid, acetic acid, propionic acid, n-butyric acid and isobutyric acid;
the reaction temperature is 30-250 ℃, and 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 FDA0002794157500000011
R1and R2Represents H or C1-16And the sum of the carbon numbers of the two is not more than 16
Figure FDA0002794157500000012
4. A method according to any one of claims 1 to 3, wherein:
the molar ratio of the solid heterogeneous catalyst metal to the auxiliary 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: 1-0.1: 1, preferably 0.005: 1-0.05: 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 feedstock olefin is from 0.0001:1 to 0.05:1, preferably from 0.0005:1 to 0.001: 1; the molar ratio of the solid heterogeneous catalyst metal to 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.
5. The method of claim 1, wherein:
the active component metal of the solid heterogeneous catalyst is dispersed on the carrier in a monoatomic level and is combined with the phosphorus atom in the porous organic phosphine ligand polymer of the carrier in a coordination bond mode.
6. The method of claim 1, wherein:
the preparation method of the catalyst comprises the following steps:
1) first, a porous organophosphine ligand polymer support 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 for 0.2-2 h (preferably 0.5h) at 0-100 ℃ (preferably 25 ℃); then, transferring the mixture into a hydrothermal synthesis kettle, and standing for 5-50 h (preferably 24h) at 50-300 ℃ (preferably 100 ℃); finally, taking out the mixture, and drying the mixture in vacuum at 30-100 ℃ to remove the solvent;
2) secondly, preparing a metal precursor solution of an active component;
3) and finally, under the protection of inert gas, adding the organic phosphine ligand polymer in the step 1) into the metal precursor solution in the step 2), stirring for 10-50 h (preferably 24h) at 0-100 ℃ (preferably 25 ℃), and then, drying for 2-12 h (preferably 6h) in vacuum at 25-150 ℃ (preferably 60 ℃), thus obtaining the product catalyst.
7. The method of claim 6, wherein:
in the step 2), the active metal precursor compound is mainly ruthenium acetylacetonate (Ru (acac)3) Dodecacarbonyltriruthenium (Ru)3(CO)12) Ruthenium trichloride (RuCl)3) Gold oxide hydrate (Au)2O3·xH2O), gold (III) chloride hydrate (HAuCl)4·xH2O), iridium oxide (Ir)2O3) Iridium hydroxide (Ir (OH)3) Iridium chloride (IrCl)3) Perrhenic acid (HReO)4) Ammonium perrhenate (NH)4ReO4) Rhenium pentachloride (Recl)5) Rhodium acetylacetonate (Rh (acac) (CO)2) Tetracarbonyldirhodium dichloride (Rh)2(CO)4Cl2) Rhodium trichloride (RhCl)3) Platinum acetylacetonate (Pt (acac))2) Platinum chloride (PtCl)2、PtCl4) Chloroplatinic acid (H)2PtCl6) Copper acetylacetonate (Cu (acac)2) Copper acetate (Cu (OAc))2) And copper chloride (CuCl)2) Preferably Ru3(CO)12、HAuCl4·xH2O、IrCl3、HReO4、Rh2(CO)4Cl2、H2PtCl6、Cu(acac)2One or more than two of them.
8. The method according to claim 6 or 7, characterized in that:
the mass loading capacity of the active component metal in the step 2) is 0.01-10.0%, preferably 0.5-2%; the carrier organic phosphine monomer in the step 1) is one or more than two of compounds L1-L8 in a formula 2, preferably one or more than two of compounds L2, L3 and L6;
Figure FDA0002794157500000031
9. the method of claim 6, wherein:
the solvent used in the preparation step 1) of the carrier organic phosphine ligand polymer is one or more than two of tetrahydrofuran, toluene, benzene, dichloromethane, trichloromethane and dimethylformamide, preferably tetrahydrofuran and dichloromethane; 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 a compound initiation system of azobisisobutyronitrile and azobisisoheptonitrile, and preferably cyclohexanone peroxide and azobisisobutyronitrile; the solvent used in step 2) is one or more of dioxane, tetrahydrofuran, dichloromethane and dimethylformamide, preferably tetrahydrofuran and dichloromethane.
10. The method of claim 6, wherein:
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 m2Per g, preferably 800 to 1500m2(ii)/g; the pore volume is 0.05-8.0cm3A/g, preferably 0.5 to 2.0cm3(ii)/g; the pore size distribution is 0.05-800 nm, preferably 0.8-400 nm.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2805025A1 (en) * 1978-02-06 1979-08-16 Rybakov Higher fatty acid prodn. from olefin - by catalytic hydrocarboxylation in ketone, ether or ester solvent
US4273936A (en) * 1979-09-28 1981-06-16 Union Carbide Corporation Rhodium-catalyzed oxidation process for producing carboxylic acids
CN102040501A (en) * 2010-10-28 2011-05-04 中国科学院新疆理化技术研究所 Method for preparing pelargonic acid and isononanoic acid by catalyzing 1-octylene through water-soluble palladium-phosphine complex catalyst
CN106631756A (en) * 2016-12-14 2017-05-10 安阳师范学院 Method for synthesizing organic carboxylic acid under catalysis of organic strong acid
CN107790188A (en) * 2016-09-07 2018-03-13 中国科学院大连化学物理研究所 A kind of metal organic copolymer containing phosphine catalyst and its preparation method and application
CN109806911A (en) * 2017-11-21 2019-05-28 中国科学院大连化学物理研究所 A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application
CN110294659A (en) * 2018-03-22 2019-10-01 中国科学院兰州化学物理研究所苏州研究院 A kind of preparation method of organic carboxyl acid

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2805025A1 (en) * 1978-02-06 1979-08-16 Rybakov Higher fatty acid prodn. from olefin - by catalytic hydrocarboxylation in ketone, ether or ester solvent
US4273936A (en) * 1979-09-28 1981-06-16 Union Carbide Corporation Rhodium-catalyzed oxidation process for producing carboxylic acids
CN102040501A (en) * 2010-10-28 2011-05-04 中国科学院新疆理化技术研究所 Method for preparing pelargonic acid and isononanoic acid by catalyzing 1-octylene through water-soluble palladium-phosphine complex catalyst
CN107790188A (en) * 2016-09-07 2018-03-13 中国科学院大连化学物理研究所 A kind of metal organic copolymer containing phosphine catalyst and its preparation method and application
CN106631756A (en) * 2016-12-14 2017-05-10 安阳师范学院 Method for synthesizing organic carboxylic acid under catalysis of organic strong acid
CN109806911A (en) * 2017-11-21 2019-05-28 中国科学院大连化学物理研究所 A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application
CN110294659A (en) * 2018-03-22 2019-10-01 中国科学院兰州化学物理研究所苏州研究院 A kind of preparation method of organic carboxyl acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
何珍红: "钯膦络合物催化烯烃氢羧基化及氢酯基化反应", 《万方学位论文》 *
姚蒙正等: "《精细化工产品合成原理》", 31 December 2000, 中国石化出版社 *

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