Phosphorus-containing porous organic polymer supported nickel catalyst and preparation method thereof

Abstract

The invention relates to the technical field of catalysts, and particularly discloses a phosphorus-containing porous organic polymer supported nickel catalyst which is prepared from a Ni precursor and a phosphorus-containing porous organic polymer, the loading amount mass fraction of Ni in the catalyst is 0.1-10%, and the phosphorus-containing porous organic polymer is a random copolymer and has a structural general formula I; the invention also provides a preparation method and application thereof. After the porous organic polymer containing the phosphorus ligand provided by the invention and transition metal salt form a catalyst, the phosphorous acid diester compound can be efficiently catalyzed and synthesized, the phosphorous acid diester compound can be recycled after the reaction, and the performance cannot be obviously reduced in the cyclic catalysis process.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and in particular relates to a phosphorus-containing porous organic polymer-supported nickel catalyst and a preparation method thereof. Background Art

[0002] In the past decade, porous organic polymers have been widely used in the fields of photoelectric conversion, gas adsorption and separation, catalysis, energy storage and conversion due to their high specific surface area, controllable pore structure, good chemical and thermal stability, and easy surface functionalization. They are an emerging material with great development potential. Among porous materials, scientists first began to study inorganic porous materials such as activated carbon, zeolite, and porous silica. These materials have a large specific surface area and high porosity, so they are widely used as catalytic materials and adsorption and separation materials. However, they also have disadvantages such as single synthesis conditions, difficulty in functionalization, and poor preparation controllability, which limits the application of these materials to a certain extent. Polymers can be used as loading substrates to solve this problem. Porous materials have been used in catalytic applications for a long time. This is because porous organic framework materials generally have their own special properties, such as high specific surface area, which can provide more catalytic sites for catalytic reactions. On the other hand, porous organic frameworks are insoluble in general solvents, so they play an important role in the recovery and recycling of metals. Secondly, porous organic frameworks are easy to modify and can accommodate a variety of metals, functional groups or metal coordination sites, which enriches the diversity of catalytic reactions. In the above context, in order to meet the continuous improvement of requirements for organic porous framework materials and the continuous understanding of their structure, it is of great significance to design and develop functional porous organic framework materials. Summary of the invention

[0003] The first object of the present invention is to provide a phosphorus-containing porous organic polymer supported nickel catalyst, which can not only efficiently catalyze the synthesis of phosphite diester compounds, but also be recycled and reused after the reaction, and the performance does not decrease during the cyclic catalytic process.

[0004] The second object of the present invention is to provide a method for preparing the above catalyst.

[0005] The third object of the present invention is to provide the use of the above catalyst.

[0006] The purpose of the present invention is specifically achieved through the following technical solutions:

[0007] A phosphorus-containing porous organic polymer-supported nickel catalyst, wherein the catalyst is prepared from a Ni precursor and a phosphorus-containing porous organic polymer, wherein the mass fraction of Ni loading in the catalyst is 0.1%-10%; the phosphorus-containing porous organic polymer is a random copolymer having the following general structural formula I:

[0008]

[0009] In the general structural formula I, a is a methylene group with a molar content of 0-5; m is the molar content of the phosphorus-containing polymer monomer, n is the molar content of the comonomer, and m:n is 1:0-100. However, the subscripts m and n do not represent the linking order of the monomers. The linking order of the monomers may not be fixed, and the polymer is a random polymer; R is

[0010] Monomer unit.

[0011] Preferably, the Ni precursor is selected from one or more of Ni(acac)2, NiCl2, Ni(PPh3)2Cl2, Ni(dppp)Cl2, Ni(dppf)Cl2, Ni(OTf)2, Ni(BINAP)Cl2, Ni(COD)2, Ni(OAc)2, preferably NiCl2; m:n is 1:1-20.

[0012] The preparation method of the phosphorus-containing porous organic polymer-supported nickel catalyst comprises the following steps: placing a Ni precursor and a phosphorus-containing porous organic polymer in a solvent under the protection of an inert gas, stirring at 0-200° C., so that the Ni precursor is anchored on the phosphorus-containing porous organic polymer by coordination, and then removing the solvent to obtain the catalyst;

[0013] The phosphorus-containing porous organic polymer has the following structural formula I:

[0014]

[0015] In the general structural formula I, a is a methylene group with a molar content of 0 to 5; m is the molar content of the phosphorus-containing polymer monomer; n is the molar content of the comonomer; m:n is 1:0 to 100; R is Monomer unit.

[0016] Preferably, the Ni precursor is selected from one or more of Ni(acac)2, NiCl2, Ni(PPh3)2Cl2, Ni(dppp)Cl2, Ni(dppf)Cl2, Ni(OTf)2, Ni(BINAP)Cl2, Ni(COD)2, and Ni(OAc)2; the mass fraction of Ni loading is 0.1%-10% based on the weight of the final catalyst obtained and calculated according to the amount of elemental Ni; the solvent is selected from n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, benzene, and toluene; the stirring temperature is 25-100°C; the stirring time is 12-48h; and the inert gas is argon or nitrogen.

[0017] Further preferably, m:n is 1:1-20; the Ni precursor is NiCl2; based on the weight of the final catalyst obtained, calculated according to the amount of elemental Ni, the mass fraction of Ni loading is 0.1%-1%; the stirring time is 24-36h; the solvent is tetrahydrofuran or toluene; and the inert gas is argon.

[0018] Furthermore, the preparation method of the polymer of the general structural formula I is: under the protection of an inert gas, vinyl-functionalized phosphorus-containing polymer monomer The comonomer based on the substituent R is dissolved in tetrahydrofuran, a free radical initiator azobisisobutyronitrile is added, and the mixture is stirred for reaction for 24-48 hours to obtain a polymer of the general structural formula I;

[0019] The comonomer based on the substituent R is

[0020]

[0021] Preferably, in the preparation method of the polymer of the general structural formula I, the molar ratio of the phosphorus-containing polymer monomer to the comonomer based on the substituent R is 1:0-100; the molar amount of azobisisobutyronitrile is 0.1%-5% of the molar amount of vinyl in the raw material; the stirring reaction temperature is 60-150°C; and the inert gas is argon or nitrogen.

[0022] Further preferably, in the method for preparing the polymer of the general structural formula I, the molar ratio of the phosphorus-containing polymer monomer to the comonomer based on the substituent R is 1:1-20; the temperature of the stirring reaction is 80-100° C.; and the inert gas is argon.

[0023] Furthermore, the preparation method of the phosphorus-containing polymer monomer is as follows:

[0024]

[0025] Step 1: phosphorus trichloride was added dropwise to tetrahydrofuran containing (4-vinylphenyl)magnesium bromide under stirring at 0°C, the temperature was raised to room temperature, the reaction was stirred overnight, quenched, extracted with ethyl acetate, the solvent was removed under reduced pressure, and compound 1 was separated by column chromatography, the eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1;

[0026] Step 2: Compound 1, dibromoalkane and acetonitrile were added to a reactor, and the mixture was stirred under reflux at 90°C for 24 hours. After the solvent was removed under reduced pressure, methanol and 6M KOH were added, and the mixture was stirred under reflux for 24 hours. The temperature was lowered, the solvent was removed under reduced pressure, and compound 2 was separated by column chromatography. The eluent was a mixture of dichloromethane and methanol in a volume ratio of 50:1.

[0027] Step 3: Under the protection of inert gas, compound 2 is added into the reactor, toluene is added to dissolve it, trichlorosilane is added dropwise, and the reaction is refluxed and stirred at 110°C for 12 hours, and then 2M NaOH is added to quench, ethyl acetate is extracted, the solvent is removed under reduced pressure, and compound 3 is separated by column chromatography. The eluent is a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1, and a vinyl-functionalized phosphorus-containing polymer monomer can be obtained.

[0028] The application of the phosphorus-containing porous organic polymer-supported nickel catalyst in catalytic synthesis of phosphite diester compounds.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] The porous organic polymer-supported nickel catalyst containing phosphorus ligands provided by the present invention is used for the efficient catalytic synthesis of phosphorous acid diester compounds, has mild reaction conditions, and can achieve a yield of up to 94%, is suitable for large-scale production, has practical value, can be recycled and reused after the reaction, does not degrade in performance during the cyclic catalytic process, can reduce production costs, and adds a new type of catalyst to heterogeneous catalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The structural unit structure of the phosphorus-containing porous organic polymer-supported nickel catalyst A in Example 1;

[0032] Figure 2 The vinyl functionalized phosphorus-containing polymer compound 3 was prepared in deuterated chloroform. 1 H spectrum;

[0033] Figure 3 The vinyl functionalized phosphorus-containing polymer compound 3 was prepared in deuterated chloroform. 13 C spectrum;

[0034] Figure 4 The vinyl functionalized phosphorus-containing polymer compound 3 was prepared in deuterated chloroform. 31 P spectrum;

[0035] Figure 5 The tri(4-vinylphenyl)phosphine comonomer L3 in deuterated chloroform 1 H spectrum;

[0036] Figure 6 The tri(4-vinylphenyl)phosphine comonomer L3 in deuterated chloroform 13 C spectrum;

[0037] Figure 7 The tri(4-vinylphenyl)phosphine comonomer L3 in deuterated chloroform 31 P spectrum;

[0038] Figure 8is a preparation route diagram of the phosphorus-containing porous organic polymer catalyst A in Example 1;

[0039] Fig. 9 This is the XRD characterization diagram of the phosphorus-containing porous organic polymer catalyst A in Example 1

[0040] Fig.10 is the FT-IR characterization diagram of the phosphorus-containing porous organic polymer catalyst A in Example 1;

[0041] Fig.11 is a BET characterization diagram of the phosphorus-containing porous organic polymer catalyst A in Example 1;

[0042] Fig.12 is a pore size distribution diagram of the phosphorus-containing porous organic polymer catalyst A in Example 1;

[0043] Fig.13 is a SEM characterization image of the phosphorus-containing porous organic polymer catalyst A in Example 1;

[0044] Fig.14 This is the TEM characterization image of the phosphorus-containing porous organic polymer catalyst A in Example 1. DETAILED DESCRIPTION

[0045] The preferred embodiments of the present invention are described below. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0046] Unless otherwise specified, the raw materials in the examples of the present invention were purchased through commercial channels, such as Anage, Bidex and other reagent companies, and the raw materials did not need to be further purified.

[0047] The preparation methods of some products in the examples are as follows:

[0048] 1. Vinyl-functionalized phosphorus-containing polymer monomers The preparation method is as follows:

[0049]

[0050] Step 1: under stirring at 0°C, 20.0 mmol of phosphorus trichloride was added dropwise to 40 ml of tetrahydrofuran containing 80.0 mmol of (4-vinylphenyl)magnesium bromide, and the mixture was heated to room temperature and stirred to react overnight. After quenching, the mixture was extracted with ethyl acetate, the solvent was removed under reduced pressure, and compound 1 was separated by column chromatography, wherein the eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1;

[0051] Step 2: 10.0 mmol of compound 1, 20.0 mmol of dibromoalkane and 20 ml of acetonitrile were added to a reactor, refluxed and stirred at 90°C for 24 h, the solvent was removed under reduced pressure, 10 ml of methanol and 6M KOH were added, refluxed and stirred for 24 h, the temperature was lowered, the solvent was removed under reduced pressure, and compound 2 was separated by column chromatography, the eluent was a mixture of dichloromethane and methanol in a volume ratio of 50:1;

[0052] Step 3: Under the protection of inert gas, 1.0 mmol of compound 2 was added into the reactor, toluene was added to dissolve it, 24.0 mmol of trichlorosilane was added dropwise, and the reaction was refluxed and stirred at 110°C for 12 hours, and then 2M NaOH was added to quench, ethyl acetate was extracted, the solvent was removed under reduced pressure, and compound 3 was separated by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1, and a vinyl-functionalized phosphorus-containing polymer monomer was obtained.

[0053] 2. Polymers of general structural formula I The preparation method is as follows:

[0054] Under inert gas protection, vinyl functionalized phosphorus-containing polymer monomers are polymerized The comonomer based on the substituent R is dissolved in tetrahydrofuran, and a free radical initiator azobisisobutyronitrile is added, and the reaction is stirred for 24-48 hours to obtain a polymer of the general structural formula I. The general reaction formula is as follows:

[0055]

[0056] The molar ratio of the phosphorus-containing polymer monomer to the comonomer based on the substituent R is 1:0-100, preferably 1:1-20; the molar amount of azobisisobutyronitrile is 0.1%-5% of the molar amount of vinyl in the raw material; the stirring reaction temperature is 60-150°C, preferably 80-100°C; the inert gas is argon or nitrogen, preferably argon; the comonomer based on the substituent R is

[0057]

[0058] In the general structural formula I, a is a methylene group with a molar content of 0 to 5; m is the molar content of the phosphorus-containing polymer monomer; n is the molar content of the comonomer; m:n is 1:0-100, preferably 1:1-20; however, the subscripts m and n do not represent the linking order of the monomers, and the linking order of the monomers may not be fixed, which is a random polymer; R is Monomer unit.

[0059] 3. The preparation method of phosphorus-containing porous organic polymer supported nickel catalyst is as follows:

[0060] Under the protection of inert gas, a Ni precursor and a phosphorus-containing porous organic polymer (polymer of structural formula I) are placed in a solvent and stirred at 0-200° C. to allow the Ni precursor to be anchored on the phosphorus-containing porous organic polymer by coordination, and then the solvent is removed to obtain a phosphorus-containing porous organic polymer-loaded nickel catalyst.

[0061] The Ni precursor is selected from one or more of Ni(acac)2, NiCl2, Ni(PPh3)2Cl2, Ni(dppp)Cl2, Ni(dppf)Cl2, Ni(OTf)2, Ni(BINAP)Cl2, Ni(COD)2, and Ni(OAc)2, preferably NiCl2; the mass fraction of Ni loading is 0.1%-10%, preferably 0.1%-1%, based on the weight of the final catalyst obtained and calculated according to the amount of elemental Ni; the solvent is selected from n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, benzene, and toluene, preferably tetrahydrofuran or toluene, preferably tetrahydrofuran or toluene; the stirring temperature is preferably 25-100°C; the stirring time is 12-48h, preferably 24-36h; the inert gas is argon or nitrogen, preferably argon.

[0062] Example 1

[0063] At room temperature and inert gas argon protection atmosphere, 0.9 g of vinyl functionalized phosphorus-containing polymer monomer (i.e., compound 3) and 5.92 g of comonomer L3 were mixed and dissolved in 120 ml tetrahydrofuran, 0.16 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 with stirring and continued to stir and react, and the polymerization was carried out by solvent thermal polymerization at 100°C and nitrogen protection atmosphere for 24 hours, and the above polymerized solution was cooled to room temperature, and the solvent was vacuumed off at room temperature to obtain a phosphorus-containing organic polymer carrier. 62.8 mg of nickel chloride was weighed and dissolved in 100.0 ml of tetrahydrofuran solvent, 1.0 g of the phosphorus-containing organic polymer carrier obtained by copolymerization was added, the mixture was stirred at 25°C and inert gas argon protection atmosphere for 24 hours, and then the solvent was vacuumed off at room temperature to obtain a multiphase phosphorus-containing porous organic polymer supported nickel catalyst A.

[0064] Example 2

[0065] In Example 2, except that 5.92 g of L1 comonomer was used instead of 5.92 g of L3 comonomer, the rest of the implementation process was the same as that of Example 1. The obtained phosphorus-containing porous organic polymer in-situ encapsulated nickel catalytic material was recorded as Catalyst B.

[0066] Example 3

[0067] In Example 3, except that 5.92 g of L2 comonomer was used instead of 5.92 g of L3 comonomer, the rest of the implementation process was the same as that of Example 1. The obtained phosphorus-containing porous organic polymer in-situ encapsulated nickel catalytic material was recorded as Catalyst C.

[0068] according to Fig. 9 XRD characterization diagram and Fig.13 It can be seen from the SEM characterization diagram that the phosphorus-containing porous organic polymer of structural formula I is a random copolymer, and the pores contain micropores and mesopores, which is more conducive to the catalytic reaction.

[0069] Example 4

[0070] Taking Catalyst A in Example 1 as an example, the reusability of the phosphorus-containing porous organic polymer in situ encapsulated nickel catalytic material in the catalytic synthesis of diphenylethyl phosphite (diphenylethyl phosphite belongs to a phosphite diester compound, and phosphite diesters [(RO)2P(O)H] are a type of major intermediate used in fine and industrial organophosphorus chemistry) in the reaction is illustrated.

[0071] In a 10 mL reaction tube, 30 mg of the catalyst A prepared above was added, and 0.0176 g (0.2 mmol) of sodium hypophosphite, 0.122 g (1.0 mmol) of phenylethyl alcohol, 74 uL (0.6 mmol) of trimethylacetyl chloride and 3.0 mL of acetonitrile were added. After sealing, the temperature was raised to 120 ° C and the reaction was carried out for 12 hours to obtain diphenylethyl phosphite. After the reaction was completed, the reaction tube was cooled to room temperature, the solid catalyst was separated by centrifugation and washed three times with methanol and distilled water respectively, and the dried catalyst was used for recycling. Triphenylphosphine was added to the reaction solution as an internal standard, and the nuclear magnetic yield was used for analysis. The reaction data of the catalyst reuse are shown in Table 1. As can be seen from Table 1, the catalytic material prepared by the present invention can be reused five times, and the catalytic activity can be well maintained.

[0072] Table 1 Reusability of catalyst A in Example 1 in the synthesis of diphenyl ethyl phosphite

[0073]

[0074]

[0075] Example 5-18

[0076] In Examples 5-18, except that 1.0 mmol of different alcohol substrates were used instead of 1.0 mmol of phenylethanol, the rest of the implementation process was the same as that of Example 4. The reaction results of different alcohol substrates are shown in Table 2. As can be seen from Table 2, the catalyst prepared by the present invention can be applied to the reaction of different alcohols and exhibits excellent catalytic activity.

[0077] Table 2 Catalytic performance of catalyst A of Example 1 in different alcohol substrates

[0078]

[0079]

[0080] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention is described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A phosphorus-containing porous organic polymer supported nickel catalyst, characterized in that: The catalyst is prepared from a Ni precursor and a phosphorus-containing porous organic polymer, wherein the Ni loading mass fraction in the catalyst is 0.1%-10%; the phosphorus-containing porous organic polymer is a random copolymer having the following structural formula I: In the general structural formula I, a is a methylene group with a molar content of 0 to 5; m is the molar content of the phosphorus-containing polymer monomer; n is the molar content of the comonomer; m:n is 1:0 to 100; R is Monomer unit.

2. The phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 1, characterized in that: The Ni precursor is selected from one or more of Ni(acac)2, NiCl2, Ni(PPh3)2Cl2, Ni(dppp)Cl2, Ni(dppf)Cl2, Ni(OTf)2, Ni(BINAP)Cl2, Ni(COD)2, and Ni(OAc)2, preferably NiCl2; m:n is 1:1-20.

3. The method for preparing the phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 1 or 2, characterized in that: Under the protection of inert gas, a Ni precursor and a phosphorus-containing porous organic polymer are placed in a solvent, stirred at 0-200° C., so that the Ni precursor is anchored on the phosphorus-containing porous organic polymer by coordination, and then the solvent is removed to obtain the catalyst; The phosphorus-containing porous organic polymer has the following structural formula I: In the general structural formula I, a is a methylene group with a molar content of 0 to 5; m is the molar content of the phosphorus-containing polymer monomer; n is the molar content of the comonomer; m:n is 1:0 to 100; R is Monomer unit.

4. The method for preparing a phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 3, characterized in that: The Ni precursor is selected from one or more of Ni(acac)2, NiCl2, Ni(PPh3)2Cl2, Ni(dppp)Cl2, Ni(dppf)Cl2, Ni(OTf)2, Ni(BINAP)Cl2, Ni(COD)2, and Ni(OAc)2; the mass fraction of Ni loading is 0.1%-10% based on the weight of the final catalyst obtained and calculated according to the amount of elemental Ni; the solvent is selected from n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, benzene, and toluene; the stirring temperature is 25-100°C; the stirring time is 12-48h; and the inert gas is argon or nitrogen.

5. The method for preparing a phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 4, characterized in that: m:n is 1:1-20; the Ni precursor is NiCl2; based on the weight of the final catalyst obtained, calculated according to the amount of elemental Ni, the mass fraction of Ni loading is 0.1%-1%; the stirring time is 24-36h; the solvent is tetrahydrofuran or toluene; and the inert gas is argon.

6. The method for preparing a phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 3, characterized in that: The preparation method of the polymer of the general structural formula I is as follows: under the protection of an inert gas, a vinyl-functionalized phosphorus-containing polymer monomer is reacted with The comonomer based on the substituent R is dissolved in tetrahydrofuran, a free radical initiator azobisisobutyronitrile is added, and the mixture is stirred for reaction for 24-48 hours to obtain a polymer of the general structural formula I; The comonomer based on the substituent R is 7. The method for preparing a phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 6, characterized in that: In the preparation method of the polymer of the general structural formula I, the molar ratio of the phosphorus-containing polymer monomer to the comonomer based on the substituent R is 1:0-100; the molar amount of the azobisisobutyronitrile is 0.1%-5% of the molar amount of vinyl in the raw material; the temperature of the stirring reaction is 60-150° C.; and the inert gas is argon or nitrogen.

8. The method for preparing a phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 7, characterized in that: In the preparation method of the polymer of the general structural formula I, the molar ratio of the phosphorus-containing polymer monomer to the comonomer based on the substituent R is 1:1-20; the temperature of the stirring reaction is 80-100° C.; and the inert gas is argon.

9. The method for preparing a phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 6, characterized in that: The preparation method of the phosphorus-containing polymer monomer is as follows: Step 1: phosphorus trichloride was added dropwise to tetrahydrofuran containing (4-vinylphenyl)magnesium bromide under stirring at 0°C, the temperature was raised to room temperature, the reaction was stirred overnight, quenched, extracted with ethyl acetate, the solvent was removed under reduced pressure, and compound 1 was separated by column chromatography, the eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1; Step 2: Compound 1, dibromoalkane and acetonitrile were added to a reactor, and the mixture was stirred under reflux at 90°C for 24 hours. After the solvent was removed under reduced pressure, methanol and 6M KOH were added, and the mixture was stirred under reflux for 24 hours. The temperature was lowered, the solvent was removed under reduced pressure, and compound 2 was separated by column chromatography. The eluent was a mixture of dichloromethane and methanol in a volume ratio of 50:

1. Step 3: Under the protection of inert gas, compound 2 is added into the reactor, toluene is added to dissolve it, trichlorosilane is added dropwise, and the reaction is refluxed and stirred at 110°C for 12 hours, and then 2M NaOH is added to quench, ethyl acetate is extracted, the solvent is removed under reduced pressure, and compound 3 is separated by column chromatography. The eluent is a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1, and a vinyl-functionalized phosphorus-containing polymer monomer can be obtained.

10. Use of the phosphorus-containing porous organic polymer-supported nickel catalyst according to claim 1 in catalytic synthesis of phosphite diester compounds.

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