CN106140303B - One kind is containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation and application - Google Patents

Abstract

The invention discloses a multi-stage porous structure phosphine-containing organic mixed polymer-metal heterogeneous catalyst and its preparation and application in the production of high isotropic aldehyde by hydroformylation of internal olefins. One, two, or three of the metals Rh, Co, or Ir are used as the active component, and the organic phosphine-containing polymer with a hierarchical porous structure is used as the carrier. The organic phosphine-containing polymer is composed of multi-dentate organic phosphine Ligands and monodentate organophosphine ligands are copolymerized. This coordination bond type heterogeneous catalyst is suitable for fixed bed, slurry bed, bubbling bed and trickle bed reactors. The heterogeneous catalyst provided by the present invention has good performance in the hydroformylation reaction of internal olefins. Under the action of this type of catalyst, the internal olefins are first isomerized into terminal olefins, and then the hydroformylation reaction occurs selectively. The corresponding normal aldehyde is generated, so the normal isotropic ratio of the product aldehyde is high, which can be higher than 15, and the alkane content in the obtained product is lower than 1%.

Description

A kind of phosphine-containing organic mixed polymer-metal heterogeneous catalyst and its preparation and application

technical field

The invention belongs to the field of heterogeneous catalysis and fine chemical industry, and specifically relates to a phosphine-containing organic mixed polymer-metal heterogeneous catalyst, a preparation method thereof, and an application thereof in the production of high isocyanide by hydroformylation of internal olefins.

Background technique

Olefin hydroformylation (Hydroformylation, also known as OXO-Synthesis) refers to the reaction of olefins and synthesis gas (CO/H ₂ ) under the catalysis of transition metal carbonyl complexes to generate aldehydes with one carbon higher than the raw material olefins. Homogeneous complexation catalytic process for industrial production. The continuous development of olefin hydroformylation is mainly due to the impetus of the petrochemical industry. The petroleum cracking process and the Fischer-Tropsch synthesis process produce a large amount of olefins, which provide cheap synthetic raw materials for the hydroformylation reaction and make it industrialized. At the same time, the product aldehyde of the olefin hydroformylation reaction is a very useful chemical intermediate, which can be used to synthesize carboxylic acids and corresponding esters, and fatty amines. The most important use is that it can be hydrogenated into Alcohol, alcohol itself can be widely used in fine chemical industry as organic solvent, plasticizer and surfactant.

Patent CN1319580A describes a variety of bidentate phosphite ligands with relatively large steric hindrance, and these ligands have high aldehyde normal Different ratios of selectivity. However, homogeneous catalysts are not easy to recover and ligand synthesis is difficult.

Patent CN1210514A reports the Rh complex catalyst for olefin hydroformylation reaction. The Rh complex uses a multi-dentate organic nitrogen compound as a ligand, and the ligand contains at least one tertiary nitrogen group that can be protonated in a weak acid , but the catalyst also faces the problem that it is not easy to recycle.

In the patent CN102911021A, the composite catalytic system composed of Rh complex, biphenyl skeleton or binaphthyl skeleton diphosphine ligand, and triphenylphosphine or phosphite triphenyl ester monophosphine ligand is used as a catalyst. The normal aldehyde has higher selectivity in the formylation reaction, which reduces the amount of expensive bisphosphine ligands, but the catalytic system is still homogeneous, and the catalyst cannot be reused.

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

In 2001, Holger Klein et al. (Angew.Chem.Int.Ed.2001,40,No.18) synthesized NAPHOS-type homogeneous ligands. Good selectivity was achieved in the formylation reaction (the positive-to-isotropic ratio of the product aldehyde was very high). However, the catalytic system is essentially a homogeneous reaction, the recovery of the catalyst is difficult, and the hydroformylation reaction of high-carbon olefins, including internal olefins, is very costly.

Billig et al. from UCC (Union Carbide Corporation) synthesized the Biphephos ligand, which has excellent performance in propylene hydroformylation reactions. Arno Behr and Christian Vogl et al. used the Biphephos ligand to further systematically study the ligand. After complexing with Rh, it catalyzes the hydroformyl reaction of internal olefins and terminal olefins (Journal of Molecular Catalysis A: Chemical, 2003, 206, 179-184; 2005, 232, 41-44; 2005, 226, 215–219), and the stereo of the product aldehyde The selectivity is good, and Arno Behr and Christian Vogl have also done some exploratory work on two-phase olefin hydroformylation. However, the problem of homogeneous catalyst heterogeneity has not been fundamentally solved, the catalyst deactivates quickly, and the recycling of the catalyst has not been realized.

The hydroformylation of internal olefins has always been a difficult and hot topic in research. Chemists have devoted a lot of effort to the synthesis of homogeneous multidentate ligands applied to the hydroformylation of internal olefins, but there is no specific target for The emergence of heterogeneous catalysts and processes for the hydroformylation of internal olefins.

Contents of the invention

In order to solve the above-mentioned problems, the object of the present invention is to provide a phosphine-containing organic mixed polymer-metal heterogeneous catalyst and its application in the production of high iso-rataldehyde by hydroformylation of internal olefins.

Technical scheme of the present invention is:

A phosphine-containing organic mixed polymer-metal heterogeneous catalyst, using one, two, or three of metal Rh, Co or Ir as an active component, and using a phosphine-containing organic mixed polymer as a carrier, the metal in the catalyst supports The loading is 0.01-10wt%. The phosphine-containing organic mixed polymer is formed by copolymerization of multidentate organic phosphine ligands containing olefinic groups and monodentate organic phosphine ligands containing olefinic groups. The active metal component is mixed with the mixed polymer carrier. The exposed P forms multiple coordination bonds, and the formed catalyst performs well in the process of producing high iso-rataldehyde by hydroformylation of internal olefins.

The alkene group is preferably a vinyl group, the multidentate organophosphine ligand containing an alkene group is a bidentate phosphite organophosphorus ligand containing a vinyl group, and the monodentate organophosphine ligand containing an alkene group is The body is a vinyl-containing triphenylphosphine ligand.

The organic mixed polymer carrier has a hierarchical pore structure with a specific surface area of 100-3000m ² /g, and contains macropores, mesopores and micropores at the same time, with a pore volume of 0.1-5.0cm ³ /g and a pore size distribution of 0.2 ~50.0nm.

In the heterogeneous catalyst, after mixing the multidentate organic phosphine ligand and the monodentate organic phosphine ligand, a solvothermal polymerization method is used to trigger the polymerization reaction of the olefin group in the organic phosphine ligand through a free radical initiator to form a The organic phosphine-containing polymer with hierarchical pore structure is used as the carrier. The precursor of the active component and the carrier are stirred in an organic solvent. The active component forms multiple coordination bonds with the exposed P in the organic phosphine-containing polymer carrier, evaporate After adding a volatile solvent, a coordination bond type heterogeneous catalyst is obtained.

The preparation method of heterogeneous catalyst is:

a) At 273 ~ 473K, under an inert gas atmosphere, in an organic solvent, add monodentate organic phosphine ligands and multidentate organic phosphine ligands, add or not add a crosslinking agent, and then add a free radical initiator, after mixing, Stir the mixture for 0.1 to 100 hours, and the preferred stirring time range is 0.1 to 50 hours;

b) Transfer the mixed solution prepared in step a) to a synthetic autoclave, and use solvothermal polymerization under an inert gas atmosphere at 273-473K, and leave it to stand for 1-100 hours for polymerization reaction to obtain a phosphine-containing organic compound Polymer;

c) removing the solvent from the mixed polymer obtained in step b) in a vacuum at room temperature to obtain an organic mixed polymer with a hierarchical porous structure containing exposed P, which is the carrier of the heterogeneous catalyst;

d) at 273-473K, under an inert gas atmosphere, in the solvent containing the precursor of the active component, add the organic mixed polymer carrier obtained in step c), and stir for 0.1-100 hours, preferably the stirring time range is 0.1-50 hours, Afterwards, the organic solvent was removed in vacuo to obtain a heterogeneous catalyst.

The organic solvent described in step a) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, methylene chloride or chloroform; the crosslinking agent is styrene, ethylene, propylene, dichloromethane One or more of vinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-triethynylbenzene; the free radical initiator is cyclohexanone peroxide , one or more of dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanonitrile.

The molar ratio of the monodentate organophosphine ligand and the multidentate organophosphine ligand described in step a) is 0.01:1 to 100:1, and when a crosslinking agent is added, the monodentate organophosphine ligand and the crosslinking The molar ratio of the agent is 0.01:1～10:1, and the molar ratio of the monodentate organic phosphine ligand to the free radical initiator is 300:1～10:1. The concentration range in organic solvent is 0.01-1000g/L.

The solvent described in step d) is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, methylene chloride or chloroform, and the active component is Rh, Co, Ir One, two or three, the precursors of Rh are Rh(CH ₃ COO) ₂ , RhH(CO)(PPh ₃ ) ₃ , Rh(CO) ₂₍ acac), RhCl ₃ ; the precursors of Co are Co(CH ₃ COO) ₂ , Co(CO) ₂ (acac), Co(acac) ₂ , CoCl ₂ ; the precursors of Ir are Ir(CO) ₃ (acac), Ir(CH ₃ COO) ₃ , Ir( acac) ₃ , IrCl ₄ . The loading amount of the metal in the catalyst ranges from 0.01 to 10 wt%.

The prepared P-containing organic mixed polymer carrier-loaded active metal catalyst is used in the hydroformylation reaction of internal olefins, with high catalytic activity and good product selectivity, and can be used in fixed bed, slurry bed, bubbling bed and trickle flow bed reaction process. The reaction temperature is 323-573K, the reaction pressure is 0.1-10.0MPa, the gas space velocity is 100-20000h ^-1 , and the liquid hourly space velocity is 0.01-10.0h ^-1 . The main components of the reaction raw material synthesis gas are H ₂ and CO, the volume content of (H ₂ +CO) is 20-100%, and the volume ratio of H ₂ /CO is 0.5-5.0. The raw material internal olefins mainly come from C ₄ -C ₂₀ olefins in processes such as petroleum catalytic cracking, Fischer-Tropsch synthesis, and refinery dry gas recovery. The double bond can be located at the 2nd to 10th position of the carbon chain. The raw material of this process and method is highly adaptable, and can be one or several kinds of C ₄ ~C ₂₀ internal olefins (including terminal olefins), the purity of the raw material is 20-100%, and the product is mainly one carbon atom more than the raw material olefin of normal aldehydes.

Reaction principle of the present invention:

The present invention introduces a vinyl group (Vinyl) group on the aromatic ring of a typical bisphosphine ligand such as Biphephos, that is, a polydentate organic phosphine ligand (Vinyl Biphephos) containing a vinyl group as a polymerization monomer, in an autoclave Using solvothermal polymerization, copolymerization with monodentate organic phosphine ligands such as tris (4-vinylphenyl) phosphine to form organic hybrid polymers with high surface area and hierarchical pore structure, because there are a large number of organic hybrid polymers in the skeleton Exposed P containing lone pairs of electrons can be used as a catalyst carrier to form multiple coordination bonds with the empty orbitals of active transition metal ions, thereby forming catalytic active sites. In the catalyst, the organic phosphine mixed polymer has dual functions of carrier and ligand, and the active metal component is highly dispersed in the carrier, forming multiple coordination bonds with high-concentration exposed P. The active metal components are highly dispersed in the organic phosphine mixed polymer carrier in the form of single atoms, which greatly improves the utilization efficiency of metals. Moreover, the active component is not easy to be lost, the catalyst has a long service life, and the multidentate phosphine ligand in the skeleton has a significant stereo effect, and the prepared catalyst can significantly improve the stereoselectivity of the product.

The catalyst organic mixed polymer carrier skeleton provided by the present invention contains P, and the organic mixed polymer has the dual functions of a ligand and a carrier; the active metal component can be dispersed in this large surface area multilevel In the pore structure organic hybrid carrier, the metal utilization efficiency is greatly improved. The monophosphine ligand structural unit in the carrier organophosphine mixture skeleton makes the mixture have a higher P concentration, and it is easy to form a double or multiple metal-P coordination bond with the active metal component, and the coordination bond has a strong The chemical bonding ability makes the active components not easy to lose.

The beneficial effects of the present invention are:

The multi-dentate and monodentate organic phosphine ligand structure units are contained in the framework of the heterogeneous catalyst described in the present invention, wherein the monodentate organic phosphine ligand makes the surface of the mixed polymer have higher exposed P, and the multidentate phosphine ligand It has a significant stereo effect, the active metal atoms or ions form multiple coordination bonds with the exposed P on the polymer, and the active components are not easy to lose. The active components of the catalyst are Rh, Co or Ir, and this type of catalyst has a high Stereoselectivity, the polymer has a high specific surface area hierarchical pore structure, and has the dual functions of a carrier and a ligand. The active metal component may be highly dispersed in the channel or on the surface of the organic phosphine mixture carrier in the form of a single atom, improving The utilization efficiency of metal components is improved.

This type of coordination bond type heterogeneous catalyst is suitable for reaction processes such as fixed bed, slurry bed, bubbling bed and trickle bed, and the process and method for producing corresponding aldehydes by hydroformylation of internal olefins provided by the present invention can be used Fixed bed, slurry bed, bubbling bed and trickle bed and other reaction processes, internal olefins are first isomerized into terminal olefins in the hydroformylation reaction, and then selectively generate normal aldehydes with higher added value, which can be Solve the long-standing problems of poor reactivity and selectivity and serious loss of metal components in the heterogeneous process of internal olefin hydroformylation.

The heterogeneous catalyst provided by the present invention has good performance in the hydroformylation reaction of internal olefins. Under the action of this type of catalyst, the internal olefins are first isomerized into terminal olefins, and then the hydroformylation reaction occurs selectively. The corresponding normal aldehyde is generated, so the normal isotropic ratio of the product aldehyde is high, which can be higher than 15, and the alkane content in the obtained product is lower than 1%. The heterogeneous catalyst has good stability, and the separation of the catalyst, the reactant and the product is simple and easy efficient. The production cost of normal aldehyde is greatly reduced, and a new industrial technology is provided for the hydroformylation reaction of internal olefins.

Description of drawings

In Figure 1, Figure A is a typical olefin-functionalized bisphosphine ligand, and Figure B is a schematic structural diagram of Vinyl Biphephos.

Figure 2 is a schematic diagram of Vinyl Biphephos polymerization technology route.

Figure 3 is a schematic diagram of typical monodentate organophosphine ligands and multidentate organophosphine ligands and cross-linking agents used in polymerization, where L1-L16 are monodentate organophosphine ligands, and L17-L19 are multidentate organic Phosphine ligands, L20 and L21 are crosslinkers.

Fig. 4 is the ¹ H spectrum of Vinyl Biphephos ligand.

Fig. 5 is the ¹³ C spectrum of Vinyl Biphephos ligand.

Fig. 6 is the ³¹ P spectrum of Vinyl Biphephos ligand.

Fig. 7 is a high resolution mass spectrum of Vinyl Biphephos ligand.

Fig. 8 is the thermogravimetric curve of the catalyst synthesized in Example ₁ under N atmosphere.

Detailed ways

The following examples illustrate the present invention better, but do not limit the scope of protection of the present invention.

Example 1

Under 298K and an inert gas protection atmosphere, 10.0 grams of Vinyl Biphephos monomers (accompanying drawing 1) were dissolved in 100.0 ml of tetrahydrofuran solvent, and 2.5 g of comonomer tris (4-vinylphenyl) phosphine (L1) was added simultaneously, Add 1.0 g of free radical initiator azobisisobutyronitrile to the above solution, and stir for 2 hours. The stirred solution was moved to an autoclave, and polymerized by solvothermal polymerization at 373K and an inert gas atmosphere for 24 hours. After the above polymerized solution is cooled to room temperature, the solvent is removed under vacuum at room temperature to obtain an organophosphine mixed polymer carrier copolymerized with Vinyl Biphephos and tris(4-vinylphenyl)phosphine organic monomer. Figure 2 is a schematic diagram of the technical route of Vinyl Biphephos organic mixed polymer carrier polymerization. Take by weighing 3.13 milligrams of tricarbonyl rhodium acetylacetonate and be dissolved in 10.0 ml of tetrahydrofuran solvent, add 1.0 gram of organic mixed polymer carriers obtained by copolymerization of Vinyl Biphephos and tris (4-vinylphenyl) phosphine, and place this mixture at 298 K and inert After stirring for 24 hours under a gas-protected atmosphere, the solvent was vacuum-evacuated at room temperature, and an excellent catalyst for the hydroformylation reaction of internal olefins was obtained.

Example 2

In Example 2, except taking 10.0 grams of comonomer tris (4-vinylphenyl) phosphine (L1), replacing 2.5 grams of comonomer tris (4-vinylphenyl) phosphine (L1), the remaining The catalyst synthesis process is the same as in Example 1.

Example 3

In Example 3, except that 0.1 gram of free radical initiator azobisisobutyronitrile was weighed instead of 1.0 gram of free radical initiator azobisisobutyronitrile, the rest of the catalyst synthesis process was the same as that of Example 1.

Example 4

In Example 4, except that 100.0 ml of THF solvent was replaced by 50.0 ml of THF solvent, the rest of the catalyst synthesis process was the same as that of Example 1.

Example 5

In Example 5, except that 100.0 ml of tetrahydrofuran solvent was replaced by 100.0 ml of dichloromethane solvent, the remaining catalyst synthesis process was the same as that of Example 1.

Example 6

In Example 6, except that the polymerization temperature of 393K is used instead of 373K, the catalyst synthesis process is the same as in Example 1.

Example 7

In Example 7, except that the polymerization time of 12 hours was replaced by 24 hours, the rest of the catalyst synthesis process was the same as that of Example 1.

Example 8

In Example 8, except that 10.0 grams of L20 was added as a crosslinking agent, the rest of the catalyst synthesis process was the same as in Example 1.

Example 9

In Example 9, except that 1.0 g of styrene was added as a crosslinking agent, the rest of the catalyst synthesis process was the same as in Example 1.

Example 10

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

Example 11

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

Example 12

Put 0.5 g of the catalyst prepared above into a fixed-bed reactor, and put quartz sand at both ends. The micro feed pump pumps 2-octene, the flow rate is 0.1ml/min, the mass flow meter controls the space velocity of the synthesis gas (H ₂ :CO=1:1) to 1000h ^-1 , and the hydrogen formation is carried out under the conditions of 373K and 1MPa Acylation reaction. The reaction was collected in a collection pot cooled in an ice bath. The obtained liquid product was analyzed by HP-7890N gas chromatography equipped with HP-5 capillary column and FID detector, and n-propanol was used as internal standard. The tail gas from the collection tank was analyzed online by HP-7890N gas chromatograph equipped with Porapak-QS column and TCD detector. The reaction results are listed in Table 1.

Example 13

0.5 g of the catalyst prepared in Example 1 was loaded into a slurry bed reactor with a capacity of 50 ml, and 30 ml of hexanal was added as a slurry liquid, and the reaction gas mixture (H ₂ :CO:C ₃ H ₆ =1: 1:1), the hydroformylation reaction was carried out at 393K, 1.0MPa, the space velocity of the reaction mixture gas was 2000h ^-1 and the stirring rate was 750 rpm. The reaction is absorbed and collected through a collection tank equipped with 60ml of cooled deionized water, and the reaction product and slurry liquid entrained with the tail gas are all dissolved in the water of the collection tank. Others are the same as in Example 12, and the data are listed in Table 1.

The different catalysts described in Example 12 were prepared according to the steps of Examples 1-11, and the catalyst of Example 13 was prepared according to the steps of Example 1.

Synthesized catalyst specific surface area and 2-octene reaction data in the embodiment 1-13 of table 1

*The experimental conditions are 100℃, 1MPa, 2-octene flow rate is 0.1ml/min, synthesis gas (CO:H ₂ =1:1) space velocity is 1000h ^-1 , and all metals are considered to be active sites in TOF calculation . ** indicates that the reaction temperature is 230°C. The active component of Example 10 is Co, and the active component of Example 11 is Ir. The data in Example 13 are slurry bed reaction data for propylene.

Claims (9)

1. A phosphine-containing organic mixed polymer-metal heterogeneous catalyst is characterized in that: in the heterogeneous catalyst, one, two, or three of metal Rh, Co or Ir are used as active components, and The phosphine organic mixed polymer is used as the carrier, and the phosphine-containing organic mixed polymer is formed by copolymerization of multi-dentate organic phosphine ligands containing olefinic groups and monodentate organic phosphine ligands containing olefinic groups. The metal loading range in the catalyst is 0.01~ 10wt%; the described polydentate organophosphine ligand containing alkene group is: The monodentate organophosphine ligand containing alkene group is: One of. 2. The catalyst according to claim 1, characterized in that: the organic mixed polymer carrier has a hierarchical porous structure with a specific surface area of 100-3000m ² /g, and contains macropores, mesopores and micropores at the same time, The pore volume is 0.1-5.0 cm ³ /g, and the pore size distribution is 0.2-50.0 nm. 3. according to the described catalyst of claim 1, it is characterized in that: described heterogeneous catalyst is after multi-dentate organophosphine ligand and monodentate organophosphine ligand are mixed, adopts solvothermal polymerization method, through radical initiator Initiate the polymerization reaction of the olefin group in the organic phosphine ligand to generate a phosphine-containing organic mixture with a hierarchical porous structure as a carrier. The precursor of the active component and the carrier are stirred in an organic solvent, and the active component and the phosphine-containing organic mixture The exposed P in the polymer carrier forms multiple coordination bonds, and after evaporating the volatile solvent, a heterogeneous catalyst of the coordination bond type is obtained. 4. a preparation method of the arbitrary described catalyst of claim 1-3, is characterized in that: a) At 273 ~ 473K, under an inert gas atmosphere, in an organic solvent, add monodentate organic phosphine ligands and multidentate organic phosphine ligands, add or not add a crosslinking agent, and then add a free radical initiator, after mixing, stirring the mixture for 0.1 to 100 hours; b) Transfer the mixed solution prepared in step a) to a synthetic autoclave, and use solvothermal polymerization under an inert gas atmosphere at 273-473K, and leave it to stand for 1-100 hours for polymerization reaction to obtain a phosphine-containing organic compound Polymer; c) removing the solvent from the mixed polymer obtained in step b) in a vacuum at room temperature to obtain an organic mixed polymer with a hierarchical porous structure containing exposed P, which is the carrier of the heterogeneous catalyst; d) at 273-473K, under an inert gas atmosphere, in the solvent containing the precursor of the active component, add the organic mixed polymer carrier obtained in step c), and stir for 0.1-100 hours, and then remove the organic solvent in a vacuum to obtain heterogeneous catalyst. 5. according to the described preparation method of claim 4, it is characterized in that: the organic solvent described in step a) is one or more than two in benzene, toluene, THF, methyl alcohol, ethanol, methylene chloride or chloroform ; The crosslinking agent is one or both of styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-triethynylbenzene More than one species; the free radical initiator is one or two of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanonitrile above. 6. The preparation method according to claim 4, characterized in that: the molar ratio of the monodentate organophosphine ligand and the multidentate organophosphine ligand described in step a) is 0.01:1 to 100:1. When the linking agent is added, the molar ratio of the monodentate organic phosphine ligand to the crosslinking agent is 0.01:1 to 10:1, and the molar ratio of the monodentate organic phosphine ligand to the free radical initiator is 300:1 to 10: 1. The concentration range of the monodentate organic phosphine ligand in the organic solvent is 0.01-1000g/L before polymerizing into an organic mixed polymer. 7. according to the described preparation method of claim 4, it is characterized in that: the solvent described in step d) is one or both in water, benzene, toluene, THF, methanol, ethanol, methylene chloride or chloroform Above, the active component is one or more of Rh, Co, Ir, wherein the precursor of Rh is Rh(CH ₃ COO) ₂ , RhH(CO)(PPh ₃ ) ₃ , Rh(CO ) ₂ (acac), RhCl ₃ ; the precursor of Co is Co(CH ₃ COO) ₂ , Co(CO) ₂ (acac), Co(acac) ₂ , CoCl ₂ ; the precursor of Ir is Ir(CO) ₃ (acac), Ir(CH ₃ COO) ₃ , Ir(acac) ₃ , IrCl ₄ , the loading amount of the metal in the catalyst ranges from 0.01 to 10 wt%. 8. The preparation method according to claim 4, characterized in that: the stirring time in steps a) and d) ranges from 0.1 to 50 hours. 9. According to the application of the heterogeneous catalyst described in any one of claims 1-3 in the production of high isotropic aldehyde by hydroformylation of internal olefins, it is characterized in that: the hydroformylation reaction of internal olefins, the temperature of reaction is 323～573K, the reaction pressure is 0.1～10.0MPa, the gas space velocity is 100～20000h ^-1 , the liquid hourly space velocity is 0.01～10.0h ^-1 , the main components of the reaction raw material synthesis gas are H ₂ and CO, (H ₂ +CO) volume content is 20-100%, H ₂ /CO volume ratio is 0.5-5.0, the raw material internal olefins are C ₄ -C ₂₀ olefins, the double bond is located on the 2nd to 10th positions of the carbon chain, the internal olefin raw materials The purity is 20-100%, and the product is mainly normal aldehyde with one carbon atom more than the raw material olefin.