CN107790188B

CN107790188B - Metal-phosphine-containing organic copolymer catalyst and preparation method and application thereof

Info

Publication number: CN107790188B
Application number: CN201610806634.5A
Authority: CN
Inventors: 丁云杰; 李存耀; 严丽
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2016-09-07
Filing date: 2016-09-07
Publication date: 2020-09-04
Anticipated expiration: 2036-09-07
Also published as: CN107790188A

Abstract

The invention discloses a metal-phosphine-containing organic copolymer catalyst, a preparation method thereof and application thereof in olefin hydroformylation reaction, wherein the copolymer catalyst takes one or more than two of metals Rh, Co, Pd or Ir as active components, takes a phosphine-containing organic copolymer as a carrier, and the phosphine-containing organic copolymer is prepared by copolymerizing a polydentate organic phosphine ligand containing alkylene and a monodentate organic phosphine ligand containing alkylene. The preparation method is that under the inert gas atmosphere, the organic phosphine ligand is dissolved in the organic solvent, the crosslinking agent and the free radical initiator are added (or not added), and the polymerization reaction is carried out in an autoclave by adopting the solvent thermal polymerization method to obtain the product. Adding the obtained phosphine-containing organic copolymer carrier into a solution containing an active component Rh, Co, Pd or Ir precursor, fully stirring, and vacuumizing an organic solvent to obtain the coordination bond type heterogeneous catalyst, wherein the catalyst is suitable for the hydroformylation reaction of olefins and has high stability, activity and selectivity.

Description

Metal-phosphine-containing organic copolymer catalyst and preparation method and application thereof

Technical Field

The invention belongs to the field of heterogeneous catalysis, and particularly relates to a metal-phosphine-containing organic copolymer catalyst, and a preparation method and application thereof.

Background

The Hydroformylation of olefins (OXO-Synthesis) refers to the reaction of olefin and Synthesis gas (CO/H)₂) The aldehyde produced by the hydroformylation of olefin is a very useful chemical intermediate, which can be used for synthesizing carboxylic acid and corresponding ester, and fatty amine, etc., and the most important application of the aldehyde is that the aldehyde can be hydrogenated and converted into alcohol, and the alcohol can be widely used in the fine chemical field as an organic solvent, a plasticizer, a surfactant, etc. The hydroformylation of olefins is the earliest homogeneous complex catalytic process to achieve commercial production. The catalyst used is a transition metal carbonyl complex.

Table 1 describes the comparison of the production process conditions and catalytic performance of the five-generation catalyst which has been industrially applied, wherein the first four generations of the five-generation catalyst are homogeneous catalytic processes, and the fifth generation is two-phase catalytic processes, but the five processes do not always solve the problem of metal and ligand loss in the reaction process.

TABLE 1 comparison of the production process conditions and catalytic performances of five-generation catalysts already in commercial use

The hydroformylation of olefins is currently considered to be the largest industrially scalable homogeneous reaction process, about 900 million tons of aldehydes and alcohols are produced by the hydroformylation of olefins every year, and the industrial use of homogeneous catalysts is difficult, and the production cost is high. Heterogenisation of homogeneous catalysts for olefin hydroformylation is a natural trend of development. However, the traditional homogeneous catalysis heterogenization method exposes a series of problems to be solved and overcome, particularly poor stability of the catalyst after heterogenization, serious loss of active components and the like.

In patent CN1986055A, bisphosphite and triphenylphosphine are also used to cooperate with Rh to form a composite catalytic system, and in the hydroformylation of propylene, the molar ratio of n-butyraldehyde to i-butyraldehyde is greater than 20, which significantly prolongs the service life of bisphosphite ligand, and significantly reduces the amount of triarylphosphine used, but essentially still is a homogeneous reaction, and also faces the problem of difficult catalyst recycling.

Patent CN1210514A reports Rh complex catalyst for olefin hydroformylation, wherein Rh complex is prepared by using multidentate organic nitrogen compound as ligand, and the ligand contains at least one tertiary nitrogen group capable of being protonated in weak acid, but the catalyst also has the problem of difficult recovery.

Patent CN1319580A describes various bidentate phosphite ligands with larger steric hindrance, and these ligands are coordinated with Rh, Co and the like to form a homogeneous catalyst, and the hydroformylation of high-carbon olefin has selectivity of higher aldehyde normal-iso ratio. However, homogeneous catalysts are not easily recovered and ligand synthesis is difficult.

In patent CN102911021A, a composite catalytic system composed of Rh complex, biphenol skeleton or binaphthyl skeleton diphosphine ligand, and triphenylphosphine or triphenyl phosphite triphenyl ester monophosphine ligand is used as a catalyst, and normal aldehyde has higher selectivity in the linear olefin hydroformylation reaction, so that the dosage of expensive diphosphine ligand is reduced, but the catalytic system is homogeneous, and the catalyst cannot be reused.

In 2003, the diphosphine ligand xanthphos was successfully sulfonated by r.fehrmann (j.cat., 2003,219,452) to prepare a supported ionic liquid phase catalyst, thereby realizing heterogenization of the homogeneous catalysis process, and successfully applying the catalyst to a fixed bed reaction. However, the greatest disadvantage of this process is that the catalyst preparation process is relatively complicated, and the activity of the prepared supported ionic liquid phase catalyst is significantly reduced compared with that of a homogeneous catalyst.

In 2005, e.monflier (Organometallics,2005,24,2070) also sulfonated the diphosphine ligand Xantphos and developed a two-phase hydroformylation catalytic process based on this, which is suitable for the hydroformylation of higher olefins, but the preparation process of the catalyst is complicated and the activity and stability of the catalyst are to be improved.

Disclosure of Invention

In order to solve the above problems, the present invention aims to provide a metal-phosphine-containing organic copolymer catalyst, a preparation method and an application thereof.

The technical scheme of the invention is as follows:

the metal-phosphine-containing organic copolymer catalyst takes one or more than two of metal Rh, Co, Pd or Ir as active components, takes a phosphine-containing organic copolymer as a carrier, and is formed by copolymerizing a polydentate organic phosphine ligand containing alkylene and a monodentate organic phosphine ligand containing alkylene.

The alkenyl is a vinyl functional group, and the metal loading amount of an active component in the catalyst is 0.01-10 wt%;

preferably: the polydentate organic phosphine ligand containing alkylene is a bidentate organic phosphine ligand containing vinyl, and the monodentate organic phosphine ligand containing alkylene is a triphenylphosphine ligand containing vinyl.

The multidentate organic phosphine ligand containing alkylene is as follows:

the monodentate organophosphine ligand containing an alkylene group is selected from:

the metal loading amount of the active component in the catalyst is 0.01-10 wt%, and the preferable range is 0.1-2 wt%; the organic copolymer carrier has a hierarchical pore structure, and the specific surface area is 10-3000 m²A preferred range is 100 to 1000m²The volume of the pores is 0.1-10.0 cm³Preferably 0.5 to 2.0 cm/g³(ii)/g, the pore size distribution is 0.1 to 50.0nm, preferably 0.5 to 5.0 nm.

Preparation of the phosphine-containing organic copolymer carrier of the catalyst: dissolving and mixing a polydentate organic phosphine ligand and a monodentate organic phosphine ligand, and initiating an alkylene group in the organic phosphine ligand to carry out polymerization reaction by a free radical initiator by adopting a solvent thermal polymerization method to generate a phosphine-containing organic copolymer with a hierarchical pore structure as a carrier;

preparation of metal-phosphine containing organic copolymer catalyst: and fully stirring the precursor of the active component and the phosphine-containing organic copolymer carrier in a solvent, forming a firm coordination bond between the active component and the exposed P in the phosphine-containing organic copolymer carrier, and evaporating the solvent to obtain the coordination bond type metal-phosphine-containing organic copolymer catalyst.

The invention also provides a preparation method of the metal-phosphine-containing organic copolymer catalyst, which comprises the following steps:

a) adding a monodentate organophosphine ligand and a polydentate organophosphine ligand, adding or not adding a cross-linking agent, and then adding a free radical initiator into a solvent at 273-473K under an inert gas atmosphere, and stirring the mixture for 0.1-100 hours, wherein the preferable stirring time range is 0.1-20 hours;

b) transferring the mixed solution prepared in the step a) into a synthesis autoclave, standing for 1-100 hours at 273-473K in an inert gas atmosphere by adopting a solvent thermal polymerization method to perform a polymerization reaction to obtain a phosphine-containing organic copolymer;

c) the organic copolymer containing phosphine obtained in the step b) is subjected to vacuum extraction of the solvent at room temperature, so that the organic copolymer containing naked P with a hierarchical pore structure, namely the carrier of the metal-organic copolymer containing phosphine catalyst, is obtained;

d) adding the organic copolymer carrier obtained in the step c) into a solvent containing an active component precursor under the atmosphere of inert gas at 273-473K, stirring for 0.1-100 hours, preferably for 0.1-20 hours, and then, removing the solvent in vacuum to obtain the metal-phosphine-containing organic copolymer catalyst.

The solvent in the steps a) and d) is one or more than two of benzene, toluene, tetrahydrofuran, water, methanol, ethanol, dichloromethane or trichloromethane;

the cross-linking agent in the step a) is one or more than two of ethylene, propylene, butadiene, styrene, divinyl benzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3, 5-triethynyl benzene; the free radical initiator is one or more than two of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile.

The molar ratio of the monodentate organophosphine ligand to the multidentate organophosphine ligand in step a) is 0.01:1 to 100:1, preferably 1:1 to 10:1, the molar ratio of the monodentate organophosphine ligand to the crosslinking agent in the case of addition of the crosslinking agent is 0.01:1 to 10:1, preferably 0.1:1 to 1:1, and the molar ratio of the monodentate organophosphine ligand to the radical initiator is 300:1 to 10:1, preferably 100:1 to 10: 1. Before the polymerization into the organic copolymer, the concentration range of the monodentate organophosphine ligand in the solvent is 0.01-1000g/L, preferably 0.1-10 g/L; the inert gas in steps a), b) and d) is selected from Ar and N₂、CO₂One or more than two of them.

The active component is one or more of Rh, Co, Pd or Ir, wherein the precursor of Rh is Rh (CH)₃COO)₂、RhH(CO)(PPh₃)₃、Rh(CO)₂(acac)、RhCl₃(ii) a The precursor of Co is Co (CH)₃COO)₂、Co(CO)₂(acac)、Co(acac)₂、CoCl₂(ii) a The precursor of Pd is Pd (CH)₃COO)₂、Pd(acac)₂、PdCl2、Pd(PPh₃)₄、PdCl₂(CH₃CN)₂(ii) a The precursor of Ir is Ir (CO)₃(acac)、Ir(CH₃COO)₃、Ir(acac)₃、IrCl₄The metal loading amount in the catalyst is 0.01-10 wt%, preferably 0.1-2 wt%.

The invention also provides an application of the phosphine-containing organic copolymer catalyst in olefin hydroformylation, and particularly controls the performance of the prepared catalyst by modulating various parameters during the preparation of the catalyst so as to be suitable for different olefins and hydroformylation reactions of different processes.

The reaction principle of the invention is as follows:

according to the invention, a Vinyl group (Vinyl) is introduced to an aromatic ring of a typical diphosphine ligand Xantphos, namely a multidentate organic phosphine ligand (Vinyl Xantphos) containing Vinyl is taken as a polymerization monomer, and is copolymerized with a monodentate organic phosphine ligand such as tris (4-Vinyl benzene) phosphine in an autoclave by utilizing a solvothermal polymerization method to form an organic copolymer with a high surface area and a hierarchical pore structure. In the catalyst, the organic phosphine copolymer has double functions of a carrier and a ligand, and the active metal component is highly dispersed in the carrier to form firm multiple coordination bonds with high-concentration naked P. The active metal component is highly dispersed in the organic phosphine copolymer carrier in a single atom form, so that the utilization efficiency of the metal is greatly improved. And the active components are not easy to lose, and the service life of the catalyst is long. In addition, the multidentate phosphine ligand in the framework has obvious three-dimensional effect, and the prepared catalyst can obviously improve the regioselectivity of the product. The invention has the beneficial effects that:

the metal-phosphine-containing organic copolymer catalyst framework simultaneously contains multidentate and monodentate organic phosphine ligand structural units, wherein the monodentate organic phosphine ligand enables higher exposed P to exist on the surface of the copolymer, the multidentate phosphine ligand has a remarkable three-dimensional effect, active metal atoms or ions form firm multiple coordination bonds with the exposed P on the copolymer, and active components are not easy to lose. The active component of the catalyst is Rh, Co, Pd or Ir, the copolymer carrier has a high specific surface area hierarchical pore structure and has double functions of the carrier and a ligand, and the active metal component is highly dispersed in the pore channel or on the surface of the organic phosphine copolymer carrier in a single atom form, so that the utilization efficiency of the metal component is improved, and meanwhile, the catalyst has higher stereoselectivity. The catalyst integrates multiple advantages of multidentate phosphine ligand, monodentate phosphine ligand, solvent thermal polymerization and the like, and the synthesized catalyst has high performance and good stability.

The metal-phosphine organic copolymer catalyst provided by the invention is applied to the olefin hydroformylation reaction, can obviously improve the conversion rate of olefin and the selectivity of normal aldehyde, and can solve the problems of poor stability and selectivity, serious loss of metal components and the like existing in the heterogenization process of the olefin hydroformylation reaction for a long time. Meanwhile, the product of the olefin hydroformylation reaction using the catalyst has higher normal-to-iso ratio, the catalyst has good stability, and the separation of the reactant, the product and the catalyst is simple and efficient, thereby reducing the cost of the industrial production of the olefin hydroformylation and providing a new industrial technology for the production of the olefin hydroformylation.

Drawings

FIG. 1 is a schematic diagram of the structure and synthetic scheme of a typical diphosphine ligand Vinyl Xantphos.

FIG. 2 is a schematic diagram of a Vinyl Xantphos polymerization technique.

FIG. 3 is a schematic representation of typical monodentate organophosphine ligands and multidentate organophosphine ligands and crosslinkers used in polymerization, wherein L1-L13 are monodentate organophosphine ligands, L14-L16 are bidentate organophosphine ligands, and L17 and L18 are crosslinkers.

FIG. 4 is a scheme of a Vinyl Xantphos ligand³¹P spectrum.

FIG. 5 is a scheme of a Vinyl Xantphos ligand¹And (4) H spectrum.

FIG. 6 is N₂Thermogravimetric curves of the catalyst synthesized in example 1 under an atmosphere.

FIG. 7 shows the data of the stability test curve in example 14.

Detailed Description

The following examples illustrate the invention better without limiting its scope.

Example 1

Preparation of the diphosphine ligand Vinyl xanthphos: the synthesis of the 4v-Xantphos ligand was performed in a one-pot manner (scheme shown in FIG. 1). Since hetero atoms O are provided at the 4-position and the 5-position of 9, 9-dimethylxanthene (compound No. 1 in FIG. 1), deprotonation lithiation occurs relatively easily to produce the dilithium reagent 2. Reaction of 2 with bis (diethylamino) chlorophosphine produces compound 3. The reaction of concentrated sulfuric acid with concentrated hydrochloric acid to produce HCl (g) is passed into 3 to convert compound 3 to compound 4. Preparing a Li reagent from p-bromostyrene and n-BuLi, and dripping the prepared No. 4 compound to finally obtain the vinyl functionalized 4v-Xantphos ligand. The total yield of the four steps is about 10 percent, and no purification and separation step is needed in the intermediate preparation process.

Preparation of phosphine-containing organic copolymer support: 10.0g of VinylXantphos monomer (product 1 of the drawing) was dissolved in 100.0ml of tetrahydrofuran under 298K and inert gas atmosphere, while 2.5g of co-monomer tris (4-vinylphenyl) phosphine (L1 in FIG. 3) was added, 1.0 g of free radical initiator azobisisobutyronitrile was added to the above solution and stirred for 2 hours. The stirred solution was transferred to an autoclave and polymerized for 24h by thermal solvent polymerization under 373K and inert gas atmosphere. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic phosphine copolymer copolymerized by Vinyl xanthphos and tri (4-Vinyl benzene) phosphine organic monomers. FIG. 2 is a schematic representation of a scheme of a Vinyl Xantphos organic copolymer support polymerization technique.

Preparation of metal-phosphine containing organic copolymer catalyst: 3.13 mg of acetylacetonatodicarbonylrhodium is weighed and dissolved in 10.0ml of tetrahydrofuran solvent, 1.0 g of the organic copolymer prepared above is added, the mixture is stirred for 24 hours under the protection of 298K and inert gas, and then the solvent is pumped out in vacuum at room temperature, thus obtaining the metal-phosphine-containing organic copolymer catalyst applied to the hydroformylation reaction of olefin, wherein the catalyst is a coordination bond type heterogeneous catalyst.

Example 2

In example 2, the catalyst synthesis procedure was the same as in example 1 except that 10.0g of the co-monomer tris (4-vinylbenzene) ylphosphine (L1) was weighed out in place of 2.5g of the co-monomer tris (4-vinylbenzene) ylphosphine.

Example 3

In example 3, the catalyst preparation was the same as in example 1 except that 0.1 g of the radical initiator azobisisobutyronitrile was weighed instead of 1.0 g of the radical initiator azobisisobutyronitrile.

Example 4

In example 4, the catalyst preparation process was the same as in example 1 except that 50.0ml of tetrahydrofuran solvent was used instead of 100.0ml of tetrahydrofuran solvent.

Example 5

In example 5, the catalyst preparation process was the same as in example 1 except that 100.0ml of a tetrahydrofuran solvent was replaced with 100.0ml of a dichloromethane solvent.

Example 6

In example 6, the catalyst preparation was the same as in example 1 except that 393K instead of 373K polymerization temperature was used.

Example 7

In example 7, the catalyst preparation was the same as in example 1 except that the 24h polymerization time was replaced by 12h polymerization time.

Example 8

In example 8, the catalyst preparation was the same as in example 1 except that 10.0g of L20 was additionally added as a crosslinking agent.

Example 9

In example 9, the catalyst preparation was the same as in example 1 except that 1.0 g of styrene was additionally added as a crosslinking agent.

Example 10

In example 10, 14.05 mg of cobalt acetylacetonate dicarbonyl was weighed out in place of rhodium acetylacetonate tricarbonyl and dissolved in 10.0ml of tetrahydrofuran solvent, and the catalyst synthesis process was the same as in example 1.

Example 11

In example 11, 2.05 mg of iridium tricarbonyl acetylacetonate instead of rhodium tricarbonyl acetylacetonate was weighed out and dissolved in 10.0ml of a tetrahydrofuran solvent, and the catalyst synthesis process was the same as in example 1.

Example 12

In example 12, 10.0g of L-15 of FIG. 3 was weighed out in place of the diphosphine ligand of example 1, and the rest of the catalyst synthesis procedure was the same as in example 1.

Example 13

The catalyst prepared above was charged into a fixed bed reactor of 0.5g, and quartz sand was charged into both ends. 1-octene is pumped in by a micro-feed pump with the flow rate of 0.1ml/min, and the synthesis gas (H) is controlled by a mass flow meter₂CO is 1:1) space velocity of 1000h^-1The hydroformylation is carried out under the condition of 373K and 1 MPa. The reaction was collected via an ice-bath cooled collection tank. The liquid product obtained was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using N-propanol as an internal standard. The off-gas from the collection tank was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.

TABLE 1 specific surface area of catalyst synthesized in examples 1-11 and data on 1-octene reaction

Experimental barThe temperature of the workpiece is 100 ℃, the pressure of the workpiece is 1MPa, the flow rate of 1-octene is 0.1ml/min, and the synthetic gas (CO: H)₂1:1) airspeed of 1000h^-1All metals are considered active sites at the time of TOF calculation. Denotes the reaction temperature of 230 ℃, the active component of example 10 is Co and the active component of example 11 is Ir.

Example 14

The catalyst synthesized in example 1 was placed in a trickle bed continuous reactor with a catalyst loading of 0.2g, and synthesis gas (CO: H) was controlled₂1:1) space velocity of 2000h^-11-octene and toluene are prepared into mixed solution (90ml toluene is mixed with 10ml 1-octene) to be fed, and the liquid speed per hour is controlled at 6h^-1The reaction temperature is controlled at 100 ℃ and the reaction pressure is 1 MPa. The final test results are shown in fig. 7, and in the 400h test, the conversion rate of 1-octene is maintained at about 30% and is basically unchanged; the selectivity of the generated aldehyde is between 80 and 85 percent, and the trend is slightly reduced; the normal-to-iso ratio of the aldehyde product is very stable and is always maintained above 80: 20. The selectivity of the alkane in the product is always kept at a low level and is almost unchanged. The side reactions of isomerization are between 10% and 20%, increasing slightly with the increase of the reaction time. The catalyst showed good activity, selectivity and stability in a stability test of 400 hours.

Claims

1. The metal-phosphine-containing organic copolymer catalyst is characterized in that the copolymer catalyst takes one or more than two of metals Rh, Co, Pd or Ir as active components, takes a phosphine-containing organic copolymer as a carrier, and the phosphine-containing organic copolymer is formed by copolymerizing a polydentate organic phosphine ligand containing alkylene and a monodentate organic phosphine ligand containing alkylene; the alkenyl is a vinyl functional group, and the metal loading amount of an active component in the catalyst is 0.01-10 wt%; the multidentate organic phosphine ligand containing alkylene is as follows:

the monodentate organophosphine ligand containing alkylene is:

2. the metal-phosphine containing organic copolymer catalyst of claim 1 wherein: the polydentate organic phosphine ligand containing alkylene is a bidentate organic phosphine ligand containing vinyl, and the monodentate organic phosphine ligand containing alkylene is a triphenylphosphine ligand containing vinyl.

3. The metal-phosphine containing organic copolymer catalyst of claim 1 wherein: the metal loading range of the active component in the catalyst is 0.01-10 wt%; the organic copolymer carrier has a hierarchical pore structure, and the specific surface area is 10-3000 m²The volume of the pores is 0.1-10.0 cm³The pore size distribution is 0.1-50.0 nm.

4. The metal-phosphine containing organic copolymer catalyst of claim 3 wherein: the metal loading range of the active component in the catalyst is 0.1-2 wt%; the organic copolymer carrier has a hierarchical pore structure and a specific surface area of 100-1000 m²The volume of the pores is 0.5-2.0 cm³The pore size distribution is 0.5-5.0 nm.

5. The metal-phosphine containing organic copolymer catalyst of claim 1 wherein:

preparation of phosphine-containing organic copolymer support: dissolving and mixing a polydentate organic phosphine ligand and a monodentate organic phosphine ligand, and initiating an alkylene group in the organic phosphine ligand to carry out polymerization reaction by a free radical initiator by adopting a solvent thermal polymerization method to generate a phosphine-containing organic copolymer with a hierarchical pore structure as a carrier;

6. A method for preparing the metal-phosphine containing organic copolymer catalyst of any of claims 1 to 5, wherein:

a) adding a monodentate organophosphine ligand and a polydentate organophosphine ligand, adding or not adding a cross-linking agent, and then adding a free radical initiator into a solvent at 273-473K under an inert gas atmosphere, and stirring the mixture for 0.1-100 hours;

d) adding the organic copolymer carrier obtained in the step c) into a solvent containing an active component precursor under the atmosphere of inert gas at 273-473K, stirring for 0.1-100 hours, and then, vacuumizing the solvent to obtain the metal-phosphine-containing organic copolymer catalyst.

7. The method of claim 6, wherein:

the stirring time in the step a) is 0.1-20 hours, and the stirring time in the step d) is 0.1-20 hours.

8. The method of claim 6, wherein: the solvent in the steps a) and d) is one or more than two of benzene, toluene, tetrahydrofuran, water, methanol, ethanol, dichloromethane or trichloromethane;

the cross-linking agent in the step a) is one or more than two of butadiene, styrene, divinylbenzene, dimethoxymethane or 1,3, 5-triethynylbenzene; the free radical initiator is one or more than two of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile.

9. The method of claim 6, wherein: the molar ratio of the monodentate organophosphine ligand to the multidentate organophosphine ligand in the step a) is 0.01: 1-100: 1, the molar ratio of the monodentate organophosphine ligand to the cross-linking agent is 0.01: 1-10: 1 under the condition that the cross-linking agent is added, and the molar ratio of the monodentate organophosphine ligand to the radical initiator is 300: 1-10: 1; before the polymerization into the organic copolymer, the concentration range of the monodentate organophosphine ligand in the solvent is 0.01-1000 g/L; the inert gas in steps a), b) and d) is selected from Ar and N₂、CO₂One or more than two of them.

10. The method of claim 9, wherein: the molar ratio of the monodentate organic phosphine ligand to the multidentate organic phosphine ligand in the step a) is 1: 1-10: 1, the molar ratio of the monodentate organic phosphine ligand to the cross-linking agent is 0.1: 1-1: 1 under the condition that the cross-linking agent is added, and the molar ratio of the monodentate organic phosphine ligand to the radical initiator is 100: 1-10: 1; the concentration of the monodentate organophosphine ligand in the solvent prior to polymerization to the organic copolymer is in the range of 0.1 to 10 g/L.

11. The method of claim 6, wherein: the active component is one or more of Rh, Co, Pd or Ir, wherein the precursor of Rh is Rh (CH)₃COO)₂、RhH(CO)(PPh₃)₃、Rh(CO)₂(acac)、RhCl₃(ii) a The precursor of Co is Co (CH)₃COO)₂、Co(CO)₂(acac)、Co(acac)₂、CoCl₂(ii) a The precursor of Pd is Pd (CH)₃COO)₂、Pd(acac)₂、PdCl₂、Pd(PPh₃)₄、PdCl₂(CH₃CN)₂(ii) a The precursor of Ir is Ir (CO)₃(acac)、Ir(CH₃COO)₃、Ir(acac)₃、IrCl₄The metal loading amount in the catalyst is 0.01-10 wt%.

12. The method of claim 11, wherein: the metal loading range in the catalyst is 0.1-2 wt%.

13. Use of a phosphine-containing organic copolymer catalyst according to any one of claims 1 to 5 in the hydroformylation of olefins.