Phosphine-containing polymer with rigid skeleton structure and preparation method and application thereof

Abstract

The present invention discloses a phosphine-containing polymer with a rigid backbone structure, its preparation method, and its application. The repeating structural units in the phosphine-containing polymer have the following structure: wherein the dotted lines represent bond connection positions. The phosphine-containing polymer prepared by the present invention has a rigid backbone structure, eliminating the swelling effect of traditional flexible polymers, making it suitable for post-processing and molding. The prepared supported rhodium catalyst exhibits high activity and stability in the hydroformylation reaction of olefins.

Description

Technical Field

[0001] The present invention belongs to the field of polymer technology, and in particular relates to a phosphine-containing polymer with a rigid skeleton structure and a preparation method and application thereof. Background Art

[0002] The aldehyde compounds produced by hydroformylation are widely used in the synthesis of fine chemicals such as plasticizers, surfactants, pharmaceuticals, pesticides, and flavorings. As one of the largest homogeneous reactions currently industrialized, nearly 20 million tons of aldehydes and alcohols are produced annually using this method. Taking the hydroformylation of propylene to 1,4-octanol as an example, by the end of 2018, global 1,4-octanol production capacity had reached 16.5 million tons / year, of which domestic production capacity had exceeded 5.1 million tons / year. The catalysts used in hydroformylation reactions are primarily cobalt and rhodium. Compared to cobalt catalysts, rhodium catalysts can operate at lower synthesis gas pressures and reaction temperatures, and their reactivity can be hundreds of times greater than that of cobalt. However, homogeneous rhodium catalyst systems still have many shortcomings, such as the complex synthesis of the rhodium-phosphine complex, its susceptibility to air oxidation, and its insufficient thermal stability. In homogeneous reactions, the separation and recovery of the catalyst requires high-temperature distillation, which can easily decompose the rhodium-phosphine complex, leading to decreased stability. This makes the catalyst particularly unsuitable for the hydroformylation of long-chain olefins (C ≥ 6) with high boiling points (Petroleum Chemistry, 2015, 55, 587-603). Due to the lack of a suitable rhodium catalyst and the need to reduce catalyst costs, the hydroformylation of long-chain olefins in industry still uses inefficient cobalt catalysts (Johnson Matthey Technol. Rev., 2017, 61, 246-256).

[0003] Since heterogeneous catalysis offers the advantage of easy separation of catalysts and reactants, converting homogeneous reactions into heterogeneous phases has long been a research priority in industrial catalysis. Research on heterogeneous rhodium catalysts has primarily focused on molecular catalysts, nanoparticle catalysts, and the more recently developed single-atom catalysts. Supports used for rhodium metal support primarily include inorganic oxides, MOFs, carbon materials, and organic polymers. For example, rhodium complex catalysts supported by porous silicon materials (CN101642719B; J. Catal., 2005, 232, 108-116; J. Porous Mater., 2018, 25, 303-320; Green Chem., 2009, 11, 1146-1154), supported nano rhodium particle catalysts (Nano Res., 2014, 7, 1364-1369; Appl. Catal. A-Gen., 2016, 527, 53-59) and metal oxide-supported single-atom rhodium catalysts (Angew Chem. Int. Ed., 2016, 55, 16054-16058; Nat. Commun., 2016, 7, 14036) are used. Such catalysts have problems such as poor stability, low metal utilization and difficulty in preparation, making their industrial application difficult.

[0004] In recent years, researchers have developed a series of porous organic polymers containing phosphine ligands. These materials are generated by solvent thermal reaction using vinyl-functionalized aryl phosphine as monomers. The loaded rhodium catalyst easily forms a single-atom rhodium active center and exhibits high activity in heterogeneous hydroformylation reactions. It is not only easy to separate the catalyst from the reaction system, but also has good reaction stability (e.g., CN104667976A). By regulating the polymerization monomers, the chemical selectivity and regioselectivity of the hydroformylation reaction product are adjustable (e.g., CN104667977A; CN104710289A). Based on the above advantages, this technology has achieved 50,000-ton industrial applications in less than ten years of research. In specific studies, it was found that organic polymers with such flexible skeleton structures have a swelling effect (J.Am.Chem.Soc.2015, 137, 5204-5209), and the catalyst after swelling no longer has mechanical strength, resulting in limited catalyst application processes. Because of this, this type of catalyst is currently only used in the industry to produce propionaldehyde from gaseous ethylene and cannot be used for high-boiling-point olefins. Summary of the Invention

[0005] The main purpose of the present invention is to provide a phosphine-containing polymer with a rigid skeleton structure to solve the technical defects of the existing polymer, such as easy swelling leading to poor mechanical strength of the catalyst.

[0006] Another object of the present invention is to provide a preparation method and application of a phosphine-containing polymer with a rigid skeleton structure to overcome the deficiencies of the prior art.

[0007] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0008] An embodiment of the present invention provides a phosphine-containing polymer having a rigid skeleton structure, wherein the repeating structural unit in the phosphine-containing polymer has a structure as shown in formula (I):

[0009]

[0010] Among them, the dotted lines represent the bond connection positions;

[0011] Furthermore, the specific surface area of ​​the phosphine-containing polymer is 120 to 260 m 2 / g, pore size is 1~90nm.

[0012] An embodiment of the present invention further provides a method for preparing the aforementioned phosphine-containing polymer having a rigid skeleton structure, which comprises: preparing the phosphine-containing polymer having a rigid skeleton structure by at least a solvent thermal method and / or a ball milling method.

[0013] Furthermore, the solvothermal method specifically includes: in a protective atmosphere, reacting a first mixed reaction system comprising 4,4',4"-tritylphosphine, symmetrical indacene-1,3,5,7(2H,6H)-tetraketone and an acid at 80-130° C. for 24-96 hours to obtain the phosphine-containing polymer having a rigid skeleton structure.

[0014] Furthermore, the ball milling method specifically includes: in a protective atmosphere, ball milling a second mixed reaction system containing 4,4',4"-tribenzaldehyde phosphine, symmetrical indacene-1,3,5,7(2H,6H)-tetraketone, magnesium oxide and zirconium oxide balls at room temperature for 2 hours to obtain the phosphine-containing polymer with a rigid skeleton structure.

[0015] The embodiments of the present invention also provide the use of the phosphine-containing polymer having a rigid skeleton structure in the preparation of a supported rhodium catalyst or in the hydroformylation reaction of olefins.

[0016] The present invention also provides a method for preparing a supported rhodium catalyst, which comprises: reacting a third mixed reaction system comprising a rhodium source, a phosphine-containing polymer and a solvent to prepare a supported rhodium catalyst; wherein the phosphine-containing polymer is the aforementioned phosphine-containing polymer having a rigid skeleton structure.

[0017] An embodiment of the present invention further provides a method for catalyzing olefins to synthesize aldehydes, comprising:

[0018] Providing a supported rhodium catalyst prepared by the above method;

[0019] In the presence of the supported rhodium catalyst, the olefin compound undergoes a hydroformylation reaction to prepare the aldehyde compound.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The synthesis method of the phosphine-containing polymer with a rigid skeleton structure provided by the present invention is simple and easy to operate, with high yield and innovative polymerization method. The polymer has a rigid skeleton structure, which eliminates the swelling effect of traditional flexible polymers and can therefore be used for post-processing and molding;

[0022] (2) The supported rhodium catalyst prepared by the present invention exhibits high activity and stability in the hydroformylation reaction of olefins. The processed and shaped rhodium catalyst can be used in a fixed-bed reactor, which has a simple process flow, reduced equipment investment cost, and continuous operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 1 is the infrared spectrum of the phosphine-containing polymer in Example 1 of the present invention and the supported rhodium catalyst prepared using the phosphine-containing polymer in Example 1 before and after use;

[0025] Figure 2 The phosphine-containing polymer in Example 1 of the present invention and the supported rhodium catalyst prepared with the phosphine-containing polymer in Example 1 before and after use 31 P solid-state NMR spectrum. DETAILED DESCRIPTION

[0026] In view of the shortcomings of the prior art, the inventors of this case, after long-term research and extensive practice, have proposed the technical solution of the present invention. The technical solution of the present invention will be clearly and completely described below. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making any creative effort shall fall within the scope of protection of the present invention.

[0027] Specifically, as one aspect of the technical solution of the present invention, it relates to a phosphine-containing polymer having a rigid skeleton structure, wherein the repeating structural unit in the phosphine-containing polymer has a structure as shown in formula (I):

[0028]

[0029] The dashed lines represent the bond connection locations.

[0030] Furthermore, the specific surface area of ​​the phosphine-containing polymer is 120 to 260 m 2 / g, pore size is 1~90nm.

[0031] Specifically, the phosphine-containing polymer with a rigid skeleton structure in the present invention comprises a network porous skeleton and a rigid large π-conjugated structure, and has no swelling effect in a solvent.

[0032] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned phosphine-containing polymer having a rigid skeleton structure, which comprises: preparing the phosphine-containing polymer having a rigid skeleton structure by at least a solvent thermal method and / or a ball milling method.

[0033] In some more specific embodiments, the solvothermal method specifically comprises: reacting a first mixed reaction system comprising 4,4',4"-tritylphosphine, symmetrical indacene-1,3,5,7(2H,6H)-tetraketone and an acid at 80-130°C for 24-96 hours in a protective atmosphere to obtain the phosphine-containing polymer having a rigid skeleton structure.

[0034] Furthermore, the acid includes acetic acid and / or trifluoroacetic acid, but is not limited thereto.

[0035] Furthermore, the concentration of 4,4',4"-tribenzaldehyde phosphine in the first mixed reaction system is 0.001 to 0.1 mol / L, preferably 0.005 to 0.5 mol / L.

[0036] Furthermore, the molar ratio of the symmetrical indacene-1,3,5,7(2H,6H)-tetraone to 4,4',4"-tritylphosphine is 1 to 2:1, preferably 1.2 to 1.8:1.

[0037] Furthermore, the preparation method further comprises: after the reaction is completed, filtering, washing and drying the obtained mixture.

[0038] Specifically, the solvothermal method comprises: reacting a mixed solution consisting of 4,4',4"-tritylphosphine, symmetrical indacene-1,3,5,7(2H,6H)-tetraone and an acid at 80-130°C for 24-96 hours under nitrogen protection, filtering, washing with water, ethanol and dichloromethane respectively, and then vacuum drying to obtain a phosphine-containing polymer with a rigid skeleton structure.

[0039] In some more specific embodiments, the ball milling method specifically comprises: in a protective atmosphere, ball milling a second mixed reaction system comprising 4,4',4"-tribenzaldehyde phosphine, symmetrical indacene-1,3,5,7(2H,6H)-tetraketone, magnesium oxide and zirconium oxide balls at room temperature for 2 hours to obtain the phosphine-containing polymer having a rigid skeleton structure.

[0040] Furthermore, the content of 4,4',4"-tribenzaldehyde phosphine in the second mixed reaction system is 5 to 50 wt%, preferably 10 to 30 wt%.

[0041] Furthermore, the content of symmetric indacene-1,3,5,7(2H,6H)-tetraone in the second mixed reaction system is 7.5 to 75 wt%, preferably 15 to 45 wt%.

[0042] Specifically, the ball milling method includes placing a mixed system consisting of 4,4',4"-tritylphosphine, symmetrical indacene-1,3,5,7(2H,6H)-tetraone, magnesium oxide powder and zirconium oxide balls into a stainless steel tank, ball milling the mixture at room temperature for 2 hours under nitrogen protection, washing the mixture with dilute hydrochloric acid, water, N,N-dimethylformamide, ethanol and dichloromethane, and then vacuum drying the mixture to obtain a phosphine-containing polymer with a rigid skeleton structure.

[0043] Another aspect of the embodiments of the present invention further provides use of the aforementioned phosphine-containing polymer having a rigid skeleton structure in the preparation of a supported rhodium catalyst or in the hydroformylation reaction of olefins.

[0044] For example, the hydroformylation reaction of olefins includes a reaction of catalyzing olefins to synthesize aldehydes, but is not limited thereto.

[0045] Another aspect of the embodiments of the present invention further provides a method for preparing a supported rhodium catalyst, comprising: reacting a third mixed reaction system comprising a rhodium source, a phosphine-containing polymer, and a solvent to prepare a supported rhodium catalyst;

[0046] Wherein, the phosphine-containing polymer adopts the aforementioned phosphine-containing polymer with a rigid skeleton structure.

[0047] Furthermore, the rhodium source includes rhodium dicarbonyl acetylacetonate, but is not limited thereto.

[0048] Furthermore, the solvent includes toluene, but is not limited thereto.

[0049] Another aspect of the present invention provides a method for catalyzing olefins to synthesize aldehydes, comprising:

[0050] Providing a supported rhodium catalyst prepared by the above method;

[0051] In the presence of the supported rhodium catalyst, the olefin compound undergoes a hydroformylation reaction to prepare the aldehyde compound.

[0052] In some more specific embodiments, the method specifically includes: reacting a fourth mixed reaction system comprising the supported rhodium catalyst, an olefin compound and toluene at 70 to 140° C. for 2 to 40 hours in a synthetic atmosphere to obtain the aldehyde compound.

[0053] Specifically, the method comprises: in a kettle reactor, allowing a supported rhodium catalyst to undergo a hydroformylation reaction with an olefin compound in a synthetic atmosphere and a toluene solvent at 70 to 140° C. for 2 to 40 hours to obtain an aldehyde compound.

[0054] Furthermore, the reaction also includes recovering and reusing the loaded rhodium catalyst after the reaction is completed.

[0055] Furthermore, the recovery method is vacuum filtration.

[0056] Furthermore, the reuse method is the same as the first use step.

[0057] In some more specific embodiments, the reaction specifically comprises: in a synthetic atmosphere, continuously feeding a solution containing an olefin compound into a reaction device provided with the supported rhodium catalyst, at a reaction pressure of 1 to 6 MPa, a temperature of 50 to 90° C., and a liquid hourly space velocity of 0.6 to 12 h -1 , gas space velocity is 500~4000h -1 The aldehyde compound is prepared by continuous reaction under the conditions of

[0058] Specifically, the reaction comprises: processing the supported rhodium catalyst into 30-60 mesh granules by tableting, and then loading the granules into a fixed bed reactor; introducing synthesis gas and setting the reaction pressure to 1-6 MPa; using a high-pressure feed pump to charge a mixture of olefin compounds and toluene into the reactor; and setting the reaction temperature to 50-90°C and the liquid hourly space velocity to 0.6-12 h -1 , gas space velocity is 500~4000h -1 , and the liquid product is discharged from the discharge port at regular intervals.

[0059] Furthermore, the synthesis atmosphere is a mixed atmosphere of H2 and CO.

[0060] Furthermore, the volume ratio of H2 to CO in the synthesis atmosphere is 1:1.

[0061] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments. This embodiment is implemented on the premise of the technical solution of the invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0062] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0063] Example 1

[0064] 1.73 g of 4,4',4"-tritylphosphine and 1.61 g of symmetric indacene-1,3,5,7(2H,6H)-tetraone were added sequentially to 1000 mL of acetic acid. The mixed solution was reacted at 120°C under nitrogen for 72 hours, during which a precipitate gradually formed. The reaction mixture was filtered, washed with water, ethanol, and dichloromethane, respectively, and then dried under vacuum. In this example, the yield of a phosphine-containing polymer with a rigid skeleton structure was approximately 86%.

[0065] The infrared analysis chart of the phosphine-containing polymer with a rigid skeleton structure prepared in this example is shown in Figure 1. 31 P solid NMR images are shown in Figure 2 shown.

[0066] Example 2

[0067] 1.73 g of 4,4',4"-tritylphosphine and 1.61 g of symmetric indacene-1,3,5,7(2H,6H)-tetraone were added sequentially to 400 mL of trifluoroacetic acid. The mixed solution was reacted at 80°C under nitrogen for 48 hours, during which a precipitate gradually formed. The reaction mixture was filtered, washed with water, ethanol, and dichloromethane, respectively, and then dried under vacuum. In this example, a phosphine-containing polymer with a rigid skeleton structure was obtained in an approximately 82% yield.

[0068] Example 3

[0069] The preparation method of this example is basically the same as that of Example 1, except that the amount of acetic acid in Example 1 is increased to 2000 mL and the reaction time is extended to 96 h. The yield of the phosphine-containing polymer with a rigid skeleton structure obtained in this example is about 89%.

[0070] Example 4

[0071] The preparation method of this example is basically the same as that of Example 2, except that the amount of trifluoroacetic acid in Example 2 is increased to 800 mL, and the reaction temperature is raised to 100° C. The yield of the phosphine-containing polymer with a rigid skeleton structure obtained in this example is about 91%.

[0072] Example 5

[0073] 3.46 g of 4,4',4"-tritylphosphine, 3.22 g of symmetric indacene-1,3,5,7(2H,6H)-tetraone, and 1 g of magnesium oxide powder were mixed separately and placed in a 250 mL stainless steel pot along with zirconium oxide pellets. The mixture was ball-milled at room temperature under nitrogen for 2 h. The powder was removed and rinsed several times with 0.5% hydrochloric acid, then washed successively with N,N-dimethylformamide, ethanol, and dichloromethane, and dried under vacuum. In this example, a phosphine-containing polymer with a rigid backbone structure was obtained in a yield of approximately 40%.

[0074] Example 6

[0075] The preparation method of this example is basically the same as that of Example 3, except that the amount of magnesium oxide powder in Example 3 is increased to 2 g. The yield of the phosphine-containing polymer with a rigid skeleton structure obtained in this example is about 56%.

[0076] Example 7

[0077] The preparation method of the loaded rhodium catalyst of the present embodiment is as follows:

[0078] 26 mg of acetylacetonato dicarbonyl rhodium was dissolved in 30 mL of toluene, and 1 g of the prepared phosphine-containing polymer with a rigid skeleton structure was added. The mixed system was stirred at room temperature for 20 hours and then filtered. After washing several times with a large amount of toluene, the filter cake was dried in vacuum to obtain a supported rhodium catalyst.

[0079] Olefin hydroformylation

[0080] 1. Tank Reactor

[0081] The inventors used the phosphine-containing polymers with rigid backbone structures of Examples 1-6, respectively, and the method of Example 7 to obtain supported rhodium catalysts for olefin hydroformylation. The specific steps were as follows: the supported rhodium catalyst, toluene, and olefin were added to a reactor. After four replacements with synthesis gas, the reactor was filled with synthesis gas at different pressures (a mixture of H₂ and CO at a volume ratio of 1:1). The reaction was then heated and allowed to proceed. After cooling, the reaction was separated by filtration, and the filtrate was analyzed by GC (results shown in Table 1).

[0082] Table 1: Results of supported rhodium catalyst in a tank reactor

[0083]

[0084]

[0085] Reaction conditions: 15 mL kettle, 1-octene = 1.18 g, toluene = 1 mL, S / C = 5000.

[0086] To verify the stability of the supported rhodium catalyst, a 100 mL reactor was used for a catalyst reuse experiment. After the reaction, the supported rhodium catalyst was filtered under reduced pressure, washed with toluene, and then reloaded into the reactor. A total of six reactions were performed. The catalyst activity and reusability were both good. The reaction results are shown in Table 2. It can be seen that the catalyst reaction activity is higher when a larger reactor volume is used. This is because a larger reactor size is more conducive to sufficient mixing of the materials.

[0087] Table 2: Reusability of supported rhodium catalysts

[0088]

[0089] Reaction conditions: 100 mL Parr kettle, 1-octene = 11.8 g, toluene = 10 mL, T = 100° C., P = 5-6 MPa, t = 6 h, S / C = 5000.

[0090] The infrared spectra of the supported rhodium catalyst prepared with the phosphine-containing polymer in Example 1 before and after use are as follows: Figure 1 As shown; the supported rhodium catalyst prepared with the phosphine-containing polymer in Example 1 before and after use 31 P solid NMR images are shown in Figure 2 shown.

[0091] From the infrared and 31 It can be seen from the P solid NMR image that the structure of the supported rhodium catalyst does not change before and after the reaction, indicating that the properties of the polymer support and catalyst are stable.

[0092] 2. Fixed Bed Reactor

[0093] The supported rhodium catalyst was processed into 30-60 mesh granules by tableting and then loaded into a fixed bed reactor. Synthesis gas was introduced and the reaction pressure was set to 1-6 MPa. A mixture of 1-octene and toluene (1:9) was charged into the reactor using a high-pressure feed pump. The reaction temperature was set to 50-90°C and the liquid hourly space velocity was set to 0.6-12 h -1 , gas space velocity is 500~4000h -1 Liquid products were periodically discharged from the discharge port and analyzed by GC (results shown in Table 3). Compared to a tank reactor, the residence time of the material in the catalyst bed is shorter, resulting in a significantly higher normal-to-isotope ratio (l / b) of the aldehyde products. This indicates that fixed-bed reactors are more conducive to obtaining high selectivity for linear aldehydes.

[0094] Table 2: Results of supported rhodium catalyst in fixed bed reactor

[0095]

[0096] In order to verify the stability of the catalyst, a long-term test was further carried out in a fixed bed reactor. -1 , the gas space velocity is 1000h -1 The continuous experiment lasted for 360 hours under the conditions of 1% NH and 1% NH, and the reaction activity and product selectivity were maintained, indicating that the catalyst has good stability.

[0097] Comparative Example 1

[0098] The inventors of this case used patent CN103288995A to prepare a triphenylphosphine-containing polymer and further employed the method of Example 7 of this case to prepare a supported rhodium catalyst. They then conducted a hydroformylation reaction using 1-octene in a fixed-bed reactor. While the conversion rate was similar to that of the present invention, the normal-to-isotope ratio of the aldehyde product was significantly lower. Furthermore, due to the high swelling properties of the control sample, the catalyst lost its shape after the reaction and exhibited poor mechanical strength. This suggests that the catalyst prepared using the control example is not suitable for large-scale fixed-bed reactions.

[0099] Example 8

[0100] 1.73 g of 4,4',4"-tritylphosphine and 1.61 g of symmetric indacene-1,3,5,7(2H,6H)-tetraone were added sequentially to 1000 mL of acetic acid. The mixed solution was reacted at 80°C under nitrogen for 96 hours, during which a precipitate gradually formed. The reaction mixture was filtered, washed with water, ethanol, and dichloromethane, respectively, and then dried under vacuum to obtain a phosphine-containing polymer with a rigid skeleton structure.

[0101] Example 9

[0102] 1.73 g of 4,4',4"-tritylphosphine and 1.61 g of symmetric indacene-1,3,5,7(2H,6H)-tetraone were added sequentially to 1000 mL of trifluoroacetic acid. The mixed solution was reacted at 130°C under nitrogen for 24 hours, during which a precipitate gradually formed. The reaction mixture was filtered, washed with water, ethanol, and dichloromethane, respectively, and then vacuum-dried to obtain a phosphine-containing polymer with a rigid skeleton structure.

[0103] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments using other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0104] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical variations made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the scope of protection of the present invention.

Claims

1. Use of a phosphine-containing polymer having a rigid skeleton structure in the preparation of a supported rhodium catalyst or in the hydroformylation reaction of an olefin; wherein the repeating structural unit in the phosphine-containing polymer has a structure as shown in formula (I): in, Dashed lines represent bond connection locations.

2. The use according to claim 1, characterized in that: The hydroformylation reaction of olefins includes a catalytic reaction of synthesizing aldehydes from olefins.

3. The use according to claim 1, characterized in that: The specific surface area of ​​the phosphine-containing polymer is 120 to 260 m 2 / g, pore size is 1~90nm.

4. The use according to claim 1, characterized in that The method for preparing the phosphine-containing polymer with a rigid skeleton structure comprises: preparing the phosphine-containing polymer with a rigid skeleton structure by at least a solvent thermal method and / or a ball milling method.

5. The use according to claim 4, characterized in that The solvothermal method specifically includes: in a protective atmosphere, reacting a first mixed reaction system comprising 4,4',4"-tritylphosphine, symmetrical indacene-1,3,5,7(2H,6H)-tetraketone and an acid at 80-130° C. for 24-96 hours to obtain the phosphine-containing polymer having a rigid skeleton structure.

6. The use according to claim 5, characterized in that: The acid includes acetic acid and / or trifluoroacetic acid.

7. The use according to claim 5, characterized in that: The concentration of 4,4',4"-tribenzaldehyde phosphine in the first mixed reaction system is 0.001-0.1 mol / L.

8. The use according to claim 5, characterized in that: The concentration of 4,4',4"-tribenzaldehyde phosphine in the first mixed reaction system is 0.005-0.5 mol / L.

9. The use according to claim 5, characterized in that: The molar ratio of the symmetrical indacene-1,3,5,7(2H,6H)-tetraketone to 4,4',4"-tritylbenzaldehyde phosphine is 1-2:

1.

10. The use according to claim 9, characterized in that: The molar ratio of the symmetrical indacene-1,3,5,7(2H,6H)-tetraketone to 4,4',4"-tritylbenzaldehyde phosphine is 1.2-1.8:

1.

11. The use according to claim 5, characterized in that The method for preparing the phosphine-containing polymer with a rigid skeleton structure further comprises: filtering, washing, and drying the obtained mixture after the reaction is completed.

12. The use according to claim 4, characterized in that The ball milling method specifically includes: in a protective atmosphere, subjecting a second mixed reaction system comprising 4,4',4"-tritylphosphine, symmetrical indacene-1,3,5,7(2H,6H)-tetraketone, magnesium oxide and zirconium oxide balls to ball milling at room temperature for 2 hours to obtain the phosphine-containing polymer having a rigid skeleton structure.

13. The use according to claim 12, characterized in that: The content of 4,4',4"-tribenzaldehyde phosphine in the second mixed reaction system is 5 to 50 wt%.

14. The use according to claim 13, characterized in that: The content of 4,4',4"-tribenzaldehyde phosphine in the second mixed reaction system is 10-30 wt%.

15. The use according to claim 12, characterized in that: The content of sym-indacene-1,3,5,7(2H,6H)-tetraone in the second mixed reaction system is 7.5-75 wt %.

16. The use according to claim 15, characterized in that: The content of sym-indacene-1,3,5,7(2H,6H)-tetraone in the second mixed reaction system is 15 to 45 wt %.

17. A method for preparing a supported rhodium catalyst, characterized in that: include: allowing a third mixed reaction system comprising a rhodium source, a phosphine-containing polymer, and a solvent to react to prepare a supported rhodium catalyst; The phosphine-containing polymer is a phosphine-containing polymer with a rigid skeleton structure; the repeating structural unit in the phosphine-containing polymer has a structure as shown in formula (I): The dashed lines represent the bond connections.

18. The preparation method according to claim 17, characterized in that: The rhodium source includes rhodium dicarbonyl acetylacetonate.

19. The preparation method according to claim 17, characterized in that: The solvent includes toluene.

20. A method for catalyzing the synthesis of aldehydes from olefins, characterized in that: include: Providing a supported rhodium catalyst prepared by the method according to any one of claims 17 to 19; In the presence of the supported rhodium catalyst, the olefin compound undergoes a hydroformylation reaction to prepare the aldehyde compound.

21. The method according to claim 20, characterized in that Specifically include: In a synthetic atmosphere, a fourth mixed reaction system comprising the supported rhodium catalyst, the olefin compound and toluene is reacted at 70-140° C. for 2-40 hours to obtain the aldehyde compound.

22. The method according to claim 21, characterized in that: The synthesis atmosphere is a mixed atmosphere of H2 and CO.

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