Ionic liquid polymer catalyst, its preparation method and application

Abstract

The application discloses an ionic liquid polymer catalyst and a preparation method and application thereof, and relates to the field of ionic liquid polymer catalysts. The catalyst is obtained through polymerization reaction of a vinyl functionalized triphenylphosphine ligand, a vinyl functionalized triphenylphosphine ionic liquid and a metal source; wherein the vinyl functionalized triphenylphosphine ionic liquid is obtained from the vinyl functionalized triphenylphosphine ligand. The ionic liquid polymer catalyst has more excellent catalytic performance and better substrate universality, the preparation method is simple, flue gas can be directly used as a CO2 source, and the CO2 does not need to be purified, so that energy is effectively saved and the environment is protected; meanwhile, the cycloaddition reaction condition is mild, green and pollution-free; the yield of the product cyclic carbonate is as high as 99%, and the ionic liquid polymer catalyst shows good prospects for solving the problems of reactivity, good universality, difficulty in recycling of the catalyst, serious loss of active metals and ligands and other problems in a multiphase cycloaddition reaction.

Description

Technical Field

[0001] This invention belongs to the field of cycloaddition reaction catalytic materials technology, specifically relating to an ionic liquid polymer catalyst, its preparation method, and its application. Background Technology

[0002] Cyclic carbonates are an important chemical raw material with advantages such as high polarity, high boiling point, high dipole moment, low volatility, low toxicity, good solubility, and biodegradability. They can be widely used in the preparation of cosmetics, lubricants, lithium battery electrolytes, and the synthesis of fine organic intermediates.

[0003] In industrial manufacturing, CO2 is considered a substitute for toxic carbonylation feedstocks (such as CO and phosgene) due to its abundant reserves, low cost, easy availability, and renewability. How to use it as a reactant to synthesize high-value-added cyclic carbonates has attracted widespread attention from scholars. However, the CO2 currently used in this reaction is still high-purity CO2 obtained from high-concentration and low-concentration (flue gas) waste gas through a series of desulfurization, deoxygenation, and dehydration steps. The CO2 preparation process in distillation requires significant human, material, and financial resources. Therefore, directly using low-concentration waste gas (flue gas) as the CO2 source to prepare cyclic carbonates through the cycloaddition of epoxides has extremely high industrial application value.

[0004] Currently, catalysts used for the cycloaddition reactions of CO2 and epoxides mainly include alkali metal salts, metal complexes, molecular sieves, ionic liquids, and homogeneous zinc / phosphine complexes. Among them, zinc / phosphine complexes stand out due to their unique functional designability and excellent CO2 adsorption capacity. However, the recycling of expensive phosphine ligands is a significant and unavoidable challenge. Therefore, there is an urgent need to design and develop a new type of highly efficient heterogeneous catalytic system that can improve the activity of cycloaddition reactions while enabling the effective recovery and reuse of metal and phosphine ligands.

[0005] It should be noted that the information disclosed in the background section above is only used to enhance the understanding of the background of this disclosure, and therefore may include information that does not constitute prior art known to those skilled in the art. Summary of the Invention

[0006] The purpose of this invention is to provide an ionic liquid polymer catalyst, its preparation method, and its application. This ionic liquid polymer catalyst has superior catalytic performance and better substrate versatility. The preparation method is simple, and it can directly utilize flue gas as a CO2 source without the need for CO2 purification, effectively saving energy and protecting the environment.

[0007] To achieve the above objectives, the present invention provides an ionic liquid polymer catalyst, which is obtained by polymerization of a vinyl-functionalized triphenylphosphine ligand with a chemical structure as shown in Formula I or II, a vinyl-functionalized triphenylphosphine ionic liquid, and a metal source; wherein the vinyl-functionalized triphenylphosphine ionic liquid is obtained by a vinyl-functionalized triphenylphosphine ligand with a chemical structure as shown in Formula I or II.

[0008]

[0009] Formula I

[0010]

[0011] Formula II

[0012] In formula I or II, R1 to R3 are selected from vinyl groups.

[0013] This invention encapsulates a metal active component within a polymer backbone based on a vinyl-functionalized triphenylphosphine ionic liquid, with the metal active component forming a coordination configuration with a phosphine ligand. This catalyst can be used in epoxide cycloaddition reactions using flue gas as a carbonyl source.

[0014] Preferably, the chemical structural formula of the vinyl-functionalized triphenylphosphine ionic liquid is shown in Formula III or IV:

[0015]

[0016] Formula III

[0017]

[0018] Formula IV;

[0019] Or / and, the substitution positions of R1~R3 ​​are each independently adjacent or opposite.

[0020] Preferably, the structural formula of the vinyl-functionalized triphenylphosphine ligand is selected from any one of the following:

[0021] , or ;

[0022] Or / and, the structural formula of the vinyl-functionalized triphenylphosphine ionic liquid is selected from any of the following:

[0023] ,

[0024] or ;

[0025] Or / and, the metal source is selected from any one or more of zinc, magnesium, copper, manganese, nickel, iron and cobalt sources.

[0026] Preferably, the zinc source is selected from any one or more of zinc chloride, zinc iodide, zinc bromide, zinc hydroxide, zinc acetate, basic zinc carbonate, zinc powder, zinc nitrate hexahydrate, and zinc nitride; the magnesium source is selected from any one or more of magnesium nitrate hexahydrate, magnesium carbonate, magnesium silicate, magnesium chloride hexahydrate, and magnesium stearate; the copper source is selected from any one or more of copper nitrate trihydrate, cuprous chloride, copper bromide, copper acetate, copper powder, and copper glycine; and the manganese source is selected from manganese chloride tetrahydrate and manganese powder. The metal source is selected from any one or more of manganese nitrate solution, manganese acetate tetrahydrate, and manganese powder; the nickel source is selected from any one or more of nickel chloride hexahydrate, nickel acetylacetone, nickel acetate, triphenylphosphine nickel, and nickel powder; the iron source is selected from any one or more of ferric chloride hexahydrate, ferrous bromide, ferrous chloride tetrahydrate, ferric acetate, ferric nitrate nonahydrate, and iron powder; the cobalt source is selected from any one or more of cobalt chloride hexahydrate, cobalt nitrate hexahydrate, cobalt acetate, cobalt octacarbonyl, and cobalt chloride. All of these metal sources can provide active metals for the preparation of ionic liquid polymer catalysts.

[0027] A second objective of this invention is to provide a method for preparing the aforementioned ionic liquid polymer catalyst, the method comprising: in an inert gas atmosphere, polymerizing a vinyl-functionalized triphenylphosphine ligand with a chemical structure as shown in Formula I or II, a vinyl-functionalized triphenylphosphine ionic liquid, and a metal-derived organic solvent at 60-100°C under the action of a free radical initiator.

[0028] Preferably, the organic solvent is selected from any one or more of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, n-hexane, toluene, anisole, dichloromethane, and chloroform, all of which can be used in the preparation method of the ionic liquid polymer catalyst; or / and, the free radical initiator is selected from any one or more of azobisisobutyronitrile, ammonium persulfate, potassium persulfate, benzoyl peroxide, and methyl ethyl ketone peroxide, all of which can be used in the preparation method of the ionic liquid polymer catalyst; or / and, the polymerization reaction time is 1~72h; or / and, the molar ratio of the vinyl-functionalized triphenylphosphine ligand, the vinyl-functionalized triphenylphosphine ionic liquid, and the metal source is 2:0.72:1.

[0029] Preferably, the preparation method of the vinyl-functionalized triphenylphosphine ionic liquid comprises: dissolving a vinyl-functionalized triphenylphosphine ligand, p-dihalobenzyl and p-tert-butylcatechol in anhydrous dichloromethane solution under an inert gas atmosphere, and stirring the reaction at 40°C; after the reaction is completed, washing with methyl tert-butyl ether and drying to obtain the vinyl-functionalized triphenylphosphine ionic liquid.

[0030] A third objective of this invention is to provide the application of the aforementioned ionic liquid polymer catalyst in the preparation of cyclic carbonates from flue gas rings and epoxy compounds via cycloaddition reactions.

[0031] Preferably, the cycloaddition reaction is carried out at a pressure of 0.5~4.0 MPa, a temperature of 40~150℃, and the reaction solvent is selected from any one or more of n-hexane, dioxane, acetonitrile, tetrahydrofuran, cyclohexane and dichloromethane, with a reaction time of 4~20 h; or / and the CO2 content in the flue gas is 15%~25%.

[0032] More preferably, the cycloaddition reaction is carried out at a pressure of 3-4.0 MPa, a temperature of 110-150°C, and the reaction solvent is selected from any one or more of n-hexane and acetonitrile, with a reaction time of 4-20 h.

[0033] Preferably, the epoxy compound has the following structural formula:

[0034]

[0035] In the formula, R4 to R5 are each independently selected from H, halogenated or unsubstituted alkanes or alkenes with carbon chain lengths of C1 to C6, -(CH2)OR6, substituted or unsubstituted phenyl or benzyl or phenoxy or benzyloxy; wherein R6 is selected from alkanes or alkenes with 1 to 8 carbons, or alkanes with carbon chain lengths of 1 to 3 substituted with alkoxysilane at the end.

[0036] Preferably, the epoxy compound has the following structural formula:

[0037] , , , , , , , , , , , , , , , , , , , , , .

[0038] The ionic liquid polymer catalyst, its preparation method, and its application of the present invention have the following advantages:

[0039] The ionic liquid polymer catalyst of this invention uses a vinyl-functionalized triphenylphosphine ligand as a monomer. The phosphine ligand is subjected to free radical polymerization with an active metal and a vinyl-functionalized triphenylphosphine ionic liquid, thereby embedding the metal in the ionic liquid polymer in one step. The prepared ionic liquid catalyst belongs to the polymer heterogeneous catalyst category. The abundant but dispersed phosphine ligands within the catalyst mesopores enhance the coordination of the copolymer catalyst, prevent the loss of active metal, significantly improve the catalyst's stability, and exhibit excellent reusability.

[0040] The ionic liquid catalyst prepared by this invention has excellent reaction performance (activity, chemoselectivity, substrate universality and catalyst reusability), and can effectively convert aromatic and aliphatic epoxides with different functional groups into cyclic carbonates through cycloaddition reactions with flue gas, with a yield of up to 99%.

[0041] Furthermore, compared with existing catalytic systems, the ionic liquid polymer catalyst prepared in this invention exhibits superior catalytic performance and better substrate versatility, and the preparation method is simple. Moreover, it can directly utilize flue gas as a CO2 source, eliminating the need for CO2 purification, effectively saving energy and protecting the environment. Simultaneously, it provides mild cycloaddition reaction conditions, resulting in a green and pollution-free process. The yield of the product, cyclic carbonate, reaches as high as 99%, demonstrating promising prospects for solving the challenges of reactivity, versatility, difficulty in catalyst recycling, and severe loss of active metals and ligands in heterogeneous cycloaddition reactions. Attached Figure Description

[0042] Figure 1 The images show the XRD (A) and XPS (B~D) characterization diagrams of catalyst A prepared in Example 1 of this invention.

[0043] Figure 2 The image shows the BET characterization of catalyst A prepared in Example 1 of this invention; A: Type IV adsorption isotherm; B: pore structure characterization.

[0044] Figure 3 The images show SEM (A) and TEM (B) characterizations of catalyst A prepared in Example 1 of this invention.

[0045] Figure 4The images show the HR-TEM characterization (A) and EDX maps (B~F) of catalyst A prepared in Example 1 of this invention. Detailed Implementation

[0046] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0047] It should be noted that: for conditions not specifically specified in the examples, standard conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0048] In this invention, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are used only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0049] The features mentioned in this invention can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification, provided that there is no contradiction in the combination of these features. Each feature disclosed in the specification can be replaced by any alternative feature that provides the same, equivalent, or similar purpose. Therefore, unless otherwise specified, the disclosed features are merely general examples of equivalent or similar features.

[0050] Example 1

[0051] An ionic liquid polymer catalyst, the preparation method of which and its application include:

[0052]

[0053]

[0054] Under argon protection, trivinylphenylphosphine (2.1 mmol), p-dibromobenzyl (1 mmol), and 4–5 mg of p-tert-butylcatechol were dissolved in anhydrous dichloromethane (20 mL). The mixture was stirred at 40 °C for 4 hours, then washed with methyl tert-butyl ether and dried to obtain a white solid A.

[0055] Under argon protection, the above-mentioned white solid A (0.36 mmol), trivinylphenylphosphine (1 mmol), zinc bromide (0.5 mmol), and 18 mg of the free radical initiator azobisisobutyronitrile were weighed and dissolved in anhydrous N,N-dimethylformamide (8 mL) solution. After stirring at 100 °C for 24 hours, the solution was washed with methyl tert-butyl ether and drained at room temperature to obtain catalyst Zn@PIP-1, denoted as catalyst A.

[0056] The applications of catalyst A are as follows:

[0057] Add 40 mg of the catalyst prepared in each of the above examples to a 100 mL reactor, add propylene oxide (2.5 mmol) and 4 mL of n-hexane, seal the reactor, replace the air in the system with flue gas three times, pressurize to a pressure of 3 MPa, and then heat to 110 °C and react for 12 h.

[0058] Example 2

[0059] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0060] Magnesium nitrate (0.5 mmol) was used instead of zinc bromide (0.5 mmol), and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as Catalyst B.

[0061] Example 3

[0062] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0063] Copper nitrate (0.5 mmol) was used instead of zinc bromide (0.5 mmol), and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as catalyst C.

[0064] Example 4

[0065] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0066] Manganese nitrate (0.5 mmol) was used instead of zinc bromide (0.5 mmol), and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as catalyst D.

[0067] Example 5

[0068] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0069] Nickel nitrate (0.5 mmol) was used instead of zinc bromide (0.5 mmol), and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as catalyst E.

[0070] Example 6

[0071] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0072] Ferric nitrate (0.5 mmol) was used instead of zinc bromide (0.5 mmol), and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as catalyst F.

[0073] Example 7

[0074] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0075] Cobalt nitrate (0.5 mmol) was used instead of zinc bromide (0.5 mmol), and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as catalyst G.

[0076] Example 8

[0077] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0078] Formula II was used instead of Formula I, and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as catalyst H.

[0079]

[0080] Formula II

[0081] Example 9

[0082] The application of the ionic liquid polymer catalyst in Example 1 differs in that:

[0083] Replace 3 MPa with 0.5 MPa pressure, otherwise the same as in Example 1.

[0084] Example 10

[0085] The application of the ionic liquid polymer catalyst in Example 1 differs in that:

[0086] Replace 3 MPa with 4 MPa pressure, otherwise the same as in Example 1.

[0087] Example 11

[0088] The application of the ionic liquid polymer catalyst in Example 1 differs in that:

[0089] Acetonitrile was used instead of hexane as the reaction solvent, and the rest was the same as in Example 1.

[0090] Example 12

[0091] The application of the ionic liquid polymer catalyst in Example 1 differs in that:

[0092] The reaction time was 4 hours instead of 12 hours, and the rest was the same as in Example 1.

[0093] Comparative Example 1

[0094] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0095] The polymerization reaction temperature was 10°C, and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as Catalyst I.

[0096] Comparative Example 2

[0097] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0098] The polymerization reaction temperature was 200°C, and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as catalyst J.

[0099] Comparative Example 3

[0100] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0101] Ethanol was used as the polymerization solvent instead of N,N-dimethylformamide, and the rest was the same as in Example 1. The resulting ionic liquid polymer catalyst was denoted as catalyst K.

[0102] Comparative Example 4

[0103] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0104] Hydrogen peroxide was used as the free radical initiator instead of azobisisobutyronitrile, and the rest was the same as in Example 1. The resulting ionic liquid polymer catalytic material was denoted as catalyst L.

[0105] Comparative Example 5

[0106] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0107] The molar ratio of the vinyl-functionalized triphenylphosphine ligand, the vinyl-functionalized triphenylphosphine ionic liquid, and the metal source is 1:0:1, and the rest is the same as in Example 1. The resulting ionic liquid polymer catalytic material is denoted as catalyst M.

[0108] Comparative Example 6

[0109] An ionic liquid polymer catalyst, whose preparation method and application are basically the same as those in Example 1, with the difference being:

[0110] The molar ratio of the vinyl-functionalized triphenylphosphine ligand, the vinyl-functionalized triphenylphosphine ionic liquid, and the metal source is 100:100:1, and the rest is the same as in Example 1. The resulting ionic liquid polymer catalytic material is denoted as catalyst N.

[0111] Experimental Example 1: Structural Characterization

[0112] 1. XRD and XPS characterization

[0113] See Figure 1 The XRD pattern of catalyst A in Example 1 shows that at 2θ = 15°... ◦ ~23 ◦ A broad diffraction peak was observed at 2θ = 15°. Similarly, PIP-1 prepared using the same method without the addition of a metal salt also showed a peak at 2θ = 15°. ◦ ~23 ◦ A broad diffraction peak was observed, indicating the presence of disordered connections and amorphous structure between aromatic benzene rings in this organic framework material.

[0114] See Figure 1 XPS spectra from B to D indicate the presence of P and Zn elements on catalyst A in Example 1.

[0115] 2. BET characterization

[0116] The structural characteristics of catalyst A in Example 1 were evaluated at 77 K using a nitrogen adsorption isotherm; the results are shown in [reference needed]. Figure 2 .

[0117] The results showed a reversible type IV adsorption isotherm, indicating the presence of a hierarchical porous structure. According to quenched solid density functional theory (QSDFT), the pore size is mainly distributed in the range of 0.5–2.272 nm, which is beneficial for the encapsulation of Zn species and the diffusion of substances during the reaction.

[0118] 3. SEM and TEM characterization

[0119] See Figure 3 SEM images of sample A in Example 1 show that catalyst A mainly exhibits an amorphous packing structure. (See also...) Figure 3TEM images (B) show that catalyst A in Example 1 has a large number of irregularly distributed pores on its surface. These rough surfaces and distinct pore layers not only increase the contact area between reactants and catalytically active sites, but also facilitate the diffusion of reactants and products.

[0120] 3. Characterization using HR-TEM and EDX maps

[0121] See Figure 4 HR-TEM shows that in catalyst A of Example 1, Zn exists in the form of single atoms and is highly dispersed in the polymer.

[0122] See Figure 4 The B~F EDX images show that C, P, Br and Zn elements are uniformly distributed on catalyst A in Example 1.

[0123] Performance Evaluation of Experiment Example 2

[0124] 1. Catalytic performance

[0125] The catalysts prepared in Examples 1-8 and Comparative Examples 1-6 were used in the cycloaddition reaction of flue gas and propylene oxide to illustrate the catalytic performance of different catalysts in the cycloaddition reaction of propylene oxide with flue gas as the carbonyl source, as detailed below:

[0126] Add 40 mg of the catalyst prepared in each of the above examples to a 100 mL reactor, add propylene oxide (2.5 mmol) and 4 mL of n-hexane, seal the reactor, replace the air in the system with flue gas three times, pressurize to a pressure of 3 MPa, and then heat to 110 °C and react for 12 h.

[0127] After the reaction was completed, the reactor was cooled to room temperature, and biphenyl was added as an internal standard. The reaction solution was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector. The catalytic performance data of different catalysts are shown in Table 1.

[0128] Table 1 Catalytic performance of different catalysts in Examples 1-8 and Comparative Examples 1-6

[0129]

[0130] As shown in Table 1, the catalyst of the present invention has good catalytic performance for the cycloaddition reaction of epoxides with flue gas as the carbonyl source.

[0131] 2. Cyclic stability

[0132] Taking catalyst A prepared in Example 1 as an example, the reusability of the ionic liquid polymer catalyst in the catalytic cycloaddition reaction of propylene oxide is illustrated as follows:

[0133] Add 40 mg of the catalyst prepared above to a 100 mL reactor, along with 2.5 mmol of propylene oxide and 4 mL of n-hexane. After sealing, replace the air in the system three times with flue gas until the pressure reaches 3 MPa. Then, heat the system to 110 °C and react for 12 h.

[0134] After the reaction was completed, the reactor was cooled to room temperature, the solid catalyst was separated by centrifugation and washed three times with methyl tert-butyl ether, and then dried in a vacuum drying oven at 60°C for 12 h. The dried catalyst was then recycled.

[0135] Biphenyl was added to the reaction solution as an internal standard, and the reaction was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector. Reaction data for catalyst reuse are shown in Table 2.

[0136] Table 2. Reusability of Catalyst A in Example 1

[0137]

[0138] As can be seen from Table 2, the catalyst prepared by this invention can be reused at least five times, and its catalytic activity can still be maintained at a high level.

[0139] 3. Substrate adaptability

[0140] Taking catalyst A prepared in Example 1 as an example, the catalytic performance of the ionic liquid polymer catalyst in catalyzing different epoxide reactions is illustrated. Except for replacing 2.5 mmol of propylene oxide with 2.5 mmol of different epoxide substrates, the reaction process was the same as the propylene oxide reaction in the catalytic performance experiment. The structures are shown in Table 3 below.

[0141] Table 3 Catalytic performance of catalyst A in different olefin hydroformylation reactions in Example 1

[0142]

[0143] As can be seen from Table 3, the catalytic materials prepared in this invention exhibit excellent catalytic activity and good applicability when applied to different epoxide cycloaddition reactions with flue gas as the carbonyl source.

[0144] Although the present invention has been described in detail through the preferred embodiments above, it should be understood that the above description should not be considered as a limitation of the present invention. Various modifications and substitutions to the present invention will be apparent to those skilled in the art after reading the above description. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. An ionic liquid polymer catalyst characterized in that, The catalyst is obtained by polymerization of a vinyl-functionalized triphenylphosphine ligand with a chemical structure as shown in formula I or II, a vinyl-functionalized triphenylphosphine-based ionic liquid and a metal source; Formula I; Formula II; In formula I or II, R1~R3 are selected from vinyl; The structural formula of the vinyl-functionalized triphenylphosphine ionic liquid is selected from any one of the following: , or ; The metal source is selected from any one or two or more of a zinc source, a magnesium source, a manganese source, an iron source and a cobalt source.

2. The ionic liquid polymer catalyst of claim 1, wherein, The structural formula of the vinyl-functionalized triphenylphosphine ligand is selected from any one of the following: , or .

3. The ionic liquid polymer catalyst of claim 2, wherein, The zinc source is selected from any one or two or more of zinc chloride, zinc iodide, zinc bromide, zinc hydroxide, zinc acetate, basic zinc carbonate, zinc powder, zinc nitrate hexahydrate and zinc nitride. The magnesium source is selected from any one or two or more of magnesium nitrate hexahydrate, magnesium carbonate, magnesium silicate, magnesium chloride hexahydrate and magnesium stearate. The manganese source is selected from any one or two or more of manganese chloride tetrahydrate, manganese powder, manganese nitrate solution and manganese acetate tetrahydrate. The iron source is selected from any one or two or more of iron chloride hexahydrate, ferrous bromide, ferrous chloride tetrahydrate, iron acetate, iron nitrate nonahydrate and iron powder. The cobalt source is selected from any one or two or more of cobalt chloride hexahydrate, cobalt nitrate hexahydrate, cobalt acetate, dicobalt octacarbonyl and cobalt chloride.

4. The method for preparing the ionic liquid polymer catalyst according to any one of claims 1 to 3, characterized in that, The method comprises: Under an inert gas atmosphere, the vinyl-functionalized triphenylphosphine ligand with a chemical structure as shown in formula I or II, the vinyl-functionalized triphenylphosphine-based ionic liquid and the metal source are subjected to polymerization in an organic solvent at 60~100℃ under the action of a free radical initiator.

5. The preparation method according to claim 4, characterized in that, The organic solvent is selected from any one or two or more of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, n-hexane, toluene, anisole, dichloromethane and chloroform. Or / and, the free radical initiator is selected from any one or two or more of azobisisobutyronitrile, ammonium persulfate, potassium persulfate, benzoyl peroxide and methyl ethyl ketone peroxide. Or / and, the polymerization time is 1~72h. Or / and, the molar ratio of the vinyl-functionalized triphenylphosphine ligand, the vinyl-functionalized triphenylphosphine-based ionic liquid and the metal source is 2:0.72:

1.

6. The preparation method according to claim 4, characterized in that, The preparation method of the vinyl-functionalized triphenylphosphine-based ionic liquid comprises: Under an inert gas atmosphere, the vinyl-functionalized triphenylphosphine ligand, p-dihalobenzyl and p-tert-butylcatechol are dissolved in anhydrous dichloromethane solution and stirred at 40℃ for reaction; After the reaction is completed, methyl tert-butyl ether is used for washing and drying to obtain the vinyl-functionalized triphenylphosphine-based ionic liquid.

7. Use of the ionic liquid polymer catalyst according to any one of claims 1~3 in catalyzing the preparation of cyclic carbonates from flue gas and epoxide through a cycloaddition reaction.

8. Use according to claim 7, characterized in that, The cycloaddition reaction is carried out at a reaction pressure of 0.5~4.0 MPa, a temperature of 40~150℃, a reaction solvent selected from any one or two or more of n-hexane, dioxane, acetonitrile, tetrahydrofuran, cyclohexane and dichloromethane, and a reaction time of 4~20h. Or / and, the CO2 content in the flue gas is 15%~25%.

9. Use according to claim 7, characterized in that, The structural formula of the epoxy compound is as follows: ; wherein R4-R5 are each independently selected from H, halogen or unsubstituted alkyl or alkenyl of carbon chain length 1-6, -(CH2)OR6, substituted or unsubstituted phenyl or benzyl or phenoxy or benzyloxy; wherein R6 is selected from alkyl or alkenyl of carbon number 1-8, or alkyl of carbon chain length 1-3 substituted at the end with alkoxy silicon.

Images