CN117299221A - Multiphase diphosphine ligand catalyst, preparation method and application - Google Patents
Multiphase diphosphine ligand catalyst, preparation method and application Download PDFInfo
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- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003446 ligand Substances 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 claims abstract description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- -1 diphenylphosphino Chemical group 0.000 claims abstract description 23
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 14
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005086 pumping Methods 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of catalyst preparation, and discloses a multiphase diphosphine ligand catalyst and a preparation method thereof, wherein (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene is polymerized by a solvothermal method to form a P-containing ligand polymer with a multistage pore structure; and (3) adding a proper amount of rhodium dicarbonyl acetylacetonate into the tetrahydrofuran solution, stirring and dissolving, adding the P ligand-containing polymer with the hierarchical pore structure prepared in the step (I), stirring, and vacuum pumping the solvent at room temperature to obtain the multiphase diphosphine ligand catalyst with the hierarchical pore structure. The invention prepares the (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene diphosphine ligand into a multi-level pore structure and loads rhodium dicarbonyl acetylacetonate to prepare a heterogeneous catalyst system so as to improve the reaction efficiency and reduce the occurrence of side reactions.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a multiphase diphosphine ligand catalyst and a preparation method thereof.
Background
At present, the hydroformylation reaction is olefin and synthesisThe reaction of the gas to produce aldehydes one carbon higher than the feed olefins. Whereas allyl alcohol hydroformylation is a well known and industrially practiced process. Allyl alcohol and synthesis gas (CO+H) 2 ) Reacting in the presence of a catalyst to form 4-hydroxybutyraldehyde. The choice of catalyst plays a critical role in the reaction. In the prior publication No. CN114149312A, rhodium dicarbonyl acetylacetonate and 2, 3-0-isopropylidene-2, 3-dihydroxy-1, 4-bis [ bis (3, 5-dimethylphenyl) phosphino are disclosed]Butane biphosphine ligand catalytic system, belonging to solid homogeneous catalyst system; the catalyst system has small steric hindrance and high reaction activity, but is difficult to separate and has serious catalyst loss.
Through the above analysis, the problems and defects existing in the prior art are as follows:
the existing catalyst for the reaction of allyl alcohol and synthesis gas is difficult to separate from a reaction system, and the catalyst loss is serious.
Disclosure of Invention
In order to overcome the problems in the related art, the invention provides a heterogeneous diphosphine ligand catalyst and a preparation method thereof.
The technical scheme of the invention is as follows:
a preparation method of the heterogeneous diphosphine ligand catalyst comprises the following steps:
step one, preparing a polymer with a hierarchical pore structure and P ligand: polymerizing (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene by a solvothermal method to form a P ligand-containing polymer with a multistage pore structure;
step two, preparing a heterogeneous diphosphine ligand catalyst: and (3) adding a proper amount of rhodium dicarbonyl acetylacetonate into the tetrahydrofuran solution, stirring and dissolving, adding the P ligand-containing polymer with the hierarchical pore structure prepared in the step (I), stirring, and vacuum pumping the solvent at room temperature to obtain the multiphase diphosphine ligand catalyst with the hierarchical pore structure.
In one embodiment, in step one, the specific steps for preparing the P ligand-containing polymer of the hierarchical pore structure include:
(1) Dissolving a proper amount of 1R,4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene in a tetrahydrofuran solution;
(2) Adding 0.5g of azodiisobutyronitrile initiator into the solution, stirring for 2 hours, continuing to react for 24 hours, and pumping away the solvent under vacuum condition after the reaction solution is cooled to room temperature to obtain the P ligand-containing polymer with a multistage pore structure.
In one embodiment, the implementation conditions of step (1) are: temperature 298K and nitrogen blanket.
In one embodiment, the implementation conditions of step (2) are: the temperature was raised to 373K under nitrogen.
In one example, in step (1), 15g of (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene are dissolved in 100ml of tetrahydrofuran solution.
In one embodiment, in step two, the heterogeneous diphosphine ligand catalyst is prepared under the following conditions: temperature 298K and nitrogen blanket.
In one example, in step two, 13 mg of rhodium dicarbonyl acetylacetonate was added to a three-necked flask of 100ml of THF, and the amount of the P-ligand-containing polymer having a hierarchical pore structure added was 1.0g, and the stirring time was 24 hours.
In one embodiment, in step one, the (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene has the formula:
the CAS number of the (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene is: 71042-54-1.
It is another object of the present invention to provide a heterogeneous diphosphine ligand catalyst prepared using the method of preparing the heterogeneous diphosphine ligand catalyst.
It is another object of the present invention to provide the use of a heterogeneous diphosphine ligand catalyst in the reaction of allyl alcohol with synthesis gas to produce 4-hydroxybutyraldehyde.
By combining all the technical schemes, the invention has the advantages and positive effects that:
the invention prepares the (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene diphosphine ligand into a multi-level pore structure and loads rhodium dicarbonyl acetylacetonate to prepare a heterogeneous catalyst system so as to improve the reaction efficiency and reduce the occurrence of side reactions.
The loss of the active noble metal of the catalyst is negligible; the catalyst and the reaction system have almost no separation cost; no solvation process; a large amount of low-grade heat in the hydroformylation reaction is utilized efficiently.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure of the invention as claimed.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 is a flow chart of a method for preparing a heterogeneous diphosphine ligand catalyst provided by an embodiment of the invention;
FIG. 2 is a flowchart showing the steps for preparing a P ligand-containing polymer having a hierarchical pore structure according to an embodiment of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
As shown in fig. 1, the preparation method of the heterogeneous diphosphine ligand catalyst provided by the embodiment of the invention comprises the following steps:
s101, preparing a polymer with a hierarchical pore structure and P ligand: polymerizing (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene by a solvothermal method to form a P ligand-containing polymer with a multistage pore structure;
s102, preparing a heterogeneous diphosphine ligand catalyst: and (3) adding a proper amount of rhodium dicarbonyl acetylacetonate into the tetrahydrofuran solution, stirring and dissolving, adding the P ligand-containing polymer with the hierarchical pore structure prepared in the step (S101), stirring, and vacuum pumping the solvent at room temperature to obtain the multiphase diphosphine ligand catalyst with the hierarchical pore structure.
As shown in fig. 2, in step S101 in the embodiment of the present invention, the specific steps for preparing the P ligand-containing polymer with a hierarchical pore structure include:
s201, dissolving a proper amount of 1R,4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene in tetrahydrofuran solution;
s202, adding 0.5g of azodiisobutyronitrile initiator into the solution, stirring for 2 hours, continuing to react for 24 hours, and pumping away the solvent under vacuum condition after the reaction solution is cooled to room temperature to obtain the P ligand-containing polymer with a multistage pore structure.
In step S101 of the embodiment of the present invention, the structural formula of the (1 r,4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene is:
the CAS number of the (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene is: 71042-54-1.
The specific implementation mode of the preparation method of the heterogeneous diphosphine ligand catalyst in the embodiment of the invention comprises the following steps:
(1) Preparing a P-containing ligand polymer with a hierarchical pore structure:
15g of (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene are dissolved in 100ml of THF under 298K and nitrogen gas, 0.5g of azobisisobutyronitrile initiator is added to the above solution and stirred for 2h. The temperature was raised to 373K and the reaction was continued under nitrogen for 24h. After the reaction solution is cooled to room temperature (298K), the solvent is pumped away under the vacuum condition, and the P-containing ligand polymer with a multistage pore structure is formed by the solvothermal polymerization of (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene.
(2) Preparing a heterogeneous diphosphine ligand catalyst:
under 298K and nitrogen protection, 13 mg of rhodium dicarbonyl acetylacetonate is taken and added into a three-neck flask of 100ml of THF, stirred and dissolved, 1.0g of multi-stage pore structure P-containing ligand polymer is added, and after stirring for 24 hours, the solvent is pumped away in vacuum at room temperature, thus obtaining the multi-phase P-containing ligand polymer catalyst with multi-stage pore structure.
Example 1
Rhodium dicarbonyl acetylacetonate and 2, 3-0-isopropylidene-2, 3-dihydroxy-1, 4-bis [ bis (3, 5-dimethylphenyl) phosphino ] butane diphosphine ligand (mass ratio of 13:1000) are added into a fixed bed reactor, allyl alcohol and synthesis gas (CO: H2=1:1) with the molar ratio of 1:1.5 are introduced for reaction at 353K and 1.5MPa, and the generated 4-hydroxybutanal is collected in a cold trap collection tank. The liquid product was analyzed using HP-789N gas chromatography equipped with an HP-5 capillary column and an FID detector, using ethanol as an internal standard. The reaction results are shown in Table 1.
Example 2
Rhodium dicarbonyl acetylacetonate and an organic ligand polymer with a hierarchical pore structure (the mass ratio is 13:1000) are added into a fixed bed reactor, allyl alcohol and synthesis gas (CO: H2=1:1) with the molar ratio of 1:1.5 are introduced, the reaction is carried out at 353K and 1.5MPa, and the generated 4-hydroxybutanal is collected in a cold trap collecting tank. The liquid product was analyzed using HP-789N gas chromatography equipped with an HP-5 capillary column and an FID detector, using ethanol as an internal standard. The reaction results are shown in Table 1.
Example 3
Rhodium dicarbonyl acetylacetonate and (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene polymer (mass ratio: 13:1000) are added into a fixed bed reactor, allyl alcohol and synthesis gas (CO: H2=1:1) in a molar ratio of 1:1.5 are introduced for reaction at 353K and 1.5MPa, and the generated 4-hydroxybutanal is collected in a cold trap collection tank. The liquid product was analyzed using HP-789N gas chromatography equipped with an HP-5 capillary column and an FID detector, using ethanol as an internal standard. The reaction results are shown in Table 1.
TABLE 1 comparison of reaction results of allyl alcohol and synthesis gas with different catalysts
Examples | Allyl alcohol conversion (%) | 4-hydroxybutyraldehyde Selectivity (%) |
1 | 87.25 | 73.9 |
2 | 92.33 | 93.2 |
3 | 94.2 | 95.64 |
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: it is possible to modify the technical solution described in the foregoing embodiments or to make equivalent substitutions for some or all of the technical features thereof, and these modifications or substitutions should be covered in the scope of the present invention.
Claims (10)
1. A method for preparing a heterogeneous diphosphine ligand catalyst, the method comprising:
step one, preparing a polymer with a hierarchical pore structure and P ligand: polymerizing (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene by a solvothermal method to form a P ligand-containing polymer with a multistage pore structure;
step two, preparing a heterogeneous diphosphine ligand catalyst: and (3) adding a proper amount of rhodium dicarbonyl acetylacetonate into the tetrahydrofuran solution, stirring and dissolving, adding the P ligand-containing polymer with the hierarchical pore structure prepared in the step (I), stirring, and vacuum pumping the solvent at room temperature to obtain the multiphase diphosphine ligand catalyst with the hierarchical pore structure.
2. The method for preparing a heterogeneous biphospitalized ligand catalyst according to claim 1, wherein in step one, the specific steps for preparing the P-ligand-containing polymer having a hierarchical pore structure comprise:
(1) Dissolving a proper amount of 1R,4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene in a tetrahydrofuran solution;
(2) Adding 0.5g of azodiisobutyronitrile initiator into the solution, stirring for 2 hours, continuing to react for 24 hours, and pumping away the solvent under vacuum condition after the reaction solution is cooled to room temperature to obtain the P ligand-containing polymer with a multistage pore structure.
3. The process for preparing a heterogeneous biphospholgand catalyst as claimed in claim 2, wherein step (1) is carried out under the following conditions: temperature 298K and nitrogen blanket.
4. The process for preparing a heterogeneous biphospholgand catalyst as claimed in claim 2, wherein step (2) is carried out under the following conditions: the temperature was raised to 373K under nitrogen.
5. The method for producing a heterogeneous diphosphine ligand catalyst according to claim 2, wherein in step (1), 15g of (1 r,4s,5s,6 s) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene is dissolved in 100ml of tetrahydrofuran solution.
6. The method for preparing the heterogeneous diphosphine ligand catalyst according to claim 1, wherein in the second step, the preparation of the heterogeneous diphosphine ligand catalyst is performed under the following conditions: temperature 298K and nitrogen blanket.
7. The method for preparing a heterogeneous diphosphine ligand catalyst according to claim 1, wherein in the second step, 13 mg of rhodium dicarbonyl acetylacetonate is added into a three-neck flask of 100ml of THF, the addition amount of the P ligand-containing polymer with the hierarchical pore structure is 1.0g, and the stirring time is 24 hours.
8. The method for preparing a heterogeneous diphosphine ligand catalyst of claim 1, wherein in step one, the structural formula of (1 r,4s,5s,6 s) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene is:
the CAS number of the (1R, 4S,5S, 6S) -5, 6-bis (diphenylphosphino) bicyclo [2, 1] hept-2-ene is: 71042-54-1.
9. A heterogeneous diphosphine ligand catalyst, characterized in that the heterogeneous diphosphine ligand catalyst is prepared by the preparation method of the heterogeneous diphosphine ligand catalyst according to any one of claims 1 to 8.
10. Use of the heterogeneous diphosphine ligand catalyst of claim 9 in the reaction of allyl alcohol with synthesis gas to produce 4-hydroxybutyraldehyde.
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