Imidazole type anion exchange resin, preparation method and application thereof, and method for reaction of carbon dioxide and epoxy compound

Abstract

The invention relates to the field of ion exchange resin, and discloses imidazole type anion exchange resin, a preparation method and application thereof, and a method for reacting carbon dioxide with an epoxy compound. The anion exchange resin comprises a resin matrix # imgabs 0 # and an imidazole group connected with the resin matrix # imgabs 1 # through an alkylene group, wherein the resin matrix # imgabs2 is a hydrogenated styrene-dienylbenzene copolymer, the styrene-dienylbenzene copolymer contains a styrene structural unit as shown in a formula (1) and a dienylbenzene structural unit as shown in a formula (2), and in the formula (1) # imgabs3, R11 is alkyl or hydrogen, and R12 is alkyl or hydrogen; in the formula (2), n is an integer between 0 and 2. The imidazole type anion exchange resin provided by the invention has excellent thermal stability.

Description

Technical Field

[0001] The present invention relates to the technical field of ion exchange resins, and particularly relates to an imidazole-based anion exchange resin, a preparation method and application thereof, and a method for reacting carbon dioxide with an epoxide. Background Art

[0002] The new energy industry is an emerging industry that the country focuses on developing. At the same time, the development of new energy vehicles has made the application of power batteries more and more important. As important components of power battery electrolytes, alkylene carbonate solvents such as ethylene carbonate and propylene carbonate have an increasing demand year by year. In addition, alkylene carbonates also have important uses in industries such as printing, polymer manufacturing, and textiles.

[0003] Currently, the mainstream production method of alkylene carbonate is to use alkylene oxide and carbon dioxide to prepare under the action of a homogeneous catalytic system. The homogeneous system has problems such as difficult separation of the catalyst, catalyst residue, and high cost of solid-liquid waste treatment. Therefore, higher requirements are put forward for the greenness and economy of the production process of alkylene carbonate.

[0004] Compared with the homogeneous catalytic system, the heterogeneous catalytic system does not have problems such as difficult separation of the catalyst product and catalyst residue. The currently developed heterogeneous catalytic systems include oxides, MOFs, carbon materials, ionic liquids, etc. Such as MgO-Al2O3 metal compounds, bifunctional porous metal-organic framework material UiO-67-IL, imidazole-based ionic liquid catalyst supported on chitosan, hydroxyl imidazole-based ionic liquid supported on ion exchange resin, zinc halide catalyst supported on ion exchange resin, etc. Among them, more research has been done on catalysts supported on ion exchange resins.

[0005] Zhang et al. reported a hydroxyl imidazole-based ionic liquid PS-HEIMBR supported on ion exchange resin (Catalysis Today 2009, 148, 361–367). When this catalyst is applied to the epoxide / CO2 system, high requirements are placed on the particle size of the catalyst particles. When the catalyst particles are 100 μm, after reacting at 120 °C and 2.5 MPa for 4 hours, the conversion rate of propylene oxide and the selectivity of propylene carbonate can reach 99%, showing high catalytic efficiency. However, 1 mm catalyst particles without grinding treatment can only convert 87% of propylene oxide under the same conditions. And bromoethanol is required during the preparation of this catalyst, which increases the production cost of the catalyst and is not conducive to industrial application.

[0006] CN105503608A discloses a halogen-type composite hydroxyimidazole resin catalyst. When preparing the catalyst, nanomaterials such as carbon nanotubes and hydroxyhalides are added to improve the material properties. Under the action of this catalyst, ethylene oxide is treated at 120 °C and 2.0 MPa for 3 hours, and the conversion rate of ethylene oxide can reach 98.6%, and the selectivity of ethylene carbonate can reach 99.7%. However, reagents such as nanomaterials and hydroxyhalides used in the preparation also increase the production cost of the catalyst, and the repeatability of the catalyst is not good, and the performance will decline after 5 repeated uses.

[0007] Xia et al. reported a system with chitosan loaded with zinc halide as the main catalyst and 1-butyl-3-methylimidazolium bromide as the co-catalyst in Appl. Catal. A 2005, 279: 125 - 129. Under the conditions of 110 °C and 1.5 MPa, after reacting propylene oxide and CO2 for 1 hour, the selectivity of propylene carbonate can reach over 99%, and the yield can reach 95%. After adjusting the process parameters, the highest yield of propylene carbonate can reach 97%. However, due to the insufficient stability and strength of the catalytic system, after 5 repeated uses, the yield of propylene carbonate decreases from 95% to 87%, which is not conducive to industrial scale-up production.

[0008] It can be seen that although heterogeneous catalytic systems, including ion exchange resin catalysts, have many advantages, there are still some deficiencies. How to improve the performance of the catalyst and develop a heterogeneous catalytic system with high thermal stability is still a research hotspot for catalysts in the reaction of epoxides and carbon dioxide. Summary of the Invention

[0009] The object of the present invention is to overcome the problem of poor thermal stability of ion exchange resin catalysts in the prior art, and to provide an imidazole-type anion exchange resin, its preparation method and application, and a method for the reaction of carbon dioxide and epoxides. This imidazole-type anion exchange resin has high thermal properties, and when used in the reaction of carbon dioxide and epoxides, the activity of the catalyst is good.

[0010] To achieve the above object, in the first aspect of the invention, an imidazole-type anion exchange resin is provided, and the anion exchange resin includes: a resin matrix and an imidazole group connected to the resin matrix through an alkylene group ; the resin matrix is a hydrogenated styrene-dienylbenzene copolymer, and the styrene-dienylbenzene copolymer contains a styrene structural unit represented by formula (1) and a dienylbenzene structural unit represented by formula (2).

[0011]

[0012] In formula (1), R11 is an alkyl group or hydrogen, and R12 is an alkyl group or hydrogen; in formula (2), n is an integer between 0 and 2.

[0013] The second aspect of the present invention provides a preparation method of the imidazole-based anion exchange resin described in the present invention. The preparation method includes:

[0014] S1 In the presence of a hydrogenation catalyst, a hydrogenation solvent, and hydrogen, the halomethyl microspheres represented by formula (A) are subjected to a hydrogenation reaction to obtain hydrogenated halogenated spheres;

[0015] S2 The hydrogenated halogenated spheres are subjected to imidazolization and anion exchange;

[0016]

[0017] Wherein, It contains a styrene-based structural unit represented by formula (A1) and a divinylbenzene structural unit represented by formula (A2),

[0018]

[0019] In formula (A1), the definitions of R11 and R12 are the same as those of R11 and R12 in formula (1); in formula (A2), the definition of n is the same as that of n in formula (1); Y is a halogen.

[0020] The third aspect of the present invention provides an application of the imidazole-based anion exchange resin described in the present invention in the catalytic addition reaction of carbon dioxide and epoxide.

[0021] The fourth aspect of the present invention provides a method for reacting carbon dioxide and epoxide. The method includes: using the imidazole-based anion exchange resin described in the present invention as a catalyst, and in the presence of this catalyst, carbon dioxide and epoxide are subjected to a catalytic addition reaction.

[0022] Through the above technical solutions, the imidazole-based anion exchange resin provided by the present invention has excellent thermal stability. When the imidazole-based anion exchange resin in the present invention is used as a catalyst in the catalytic addition reaction of carbon dioxide and epoxide, for example, in the reaction of carbon dioxide and epoxide, it not only has excellent catalytic performance but also has excellent thermal stability. Description of the Drawings

[0023] Figure 1 It is the TGA diagram of the imidazole-based anion exchange resin in Example 1;

[0024] Figure 2 It is the FTIR diagram of the imidazole-based anion exchange resin in Example 1. Detailed Embodiments

[0025] The endpoints and any values in the ranges disclosed herein are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0026] The first aspect of the present invention provides an imidazole-based anion exchange resin, and the anion exchange resin includes: a resin matrix and an imidazole group connected to the resin matrix through an alkylene group ; wherein, the resin matrix is a hydrogenated styrene-divinylbenzene copolymer, and the styrene-divinylbenzene copolymer contains a styrene structural unit represented by formula (1) and a divinylbenzene structural unit represented by formula (2),

[0027]

[0028] In formula (1), R11 is an alkyl group or hydrogen, and R12 is an alkyl group or hydrogen; in formula (2), n is an integer between 0 and 2.

[0029] In the present invention, it can be understood that the hydrogenated styrene-divinylbenzene copolymer refers to a polymer compound containing the resin matrix of the present invention under the action of hydrogenation, part or all of the original unsaturated bonds in the resin matrix become saturated bonds, and the resin matrix may contain hydrogenated styrene structural units and may also contain hydrogenated divinylbenzene structural units The resin matrix in the present invention is a hydrogenated styrene-divinylbenzene copolymer, so that the imidazole-based anion exchange resin has excellent thermal stability, and when it is used in the reaction of carbon dioxide and epoxide, it also has excellent catalytic activity.

[0030] According to the present invention, the connecting group "alkylene group" between the imidazole group and the resin matrix can be methylene, ethylene, propylene, etc., and preferably methylene.

[0031] According to the present invention, in some preferred embodiments, the degree of hydrogenation of the anion exchange resin is 1% - 100%, for example, 1%, 10%, 15%, 20%, 30%, 45%, 60%, 65%, 75%, 85%, 90%, 95%, 99%, 100%, or a range composed of any two of the above values. The anion exchange resin under the foregoing embodiments has excellent catalyst activity and target product selectivity in the reaction of carbon dioxide with epoxides, and can maintain excellent catalytic activity even after long-term use.

[0032] According to the present invention, in some more preferred embodiments, the degree of hydrogenation of the anion exchange resin is 10% - 90%, preferably 15% - 70%. The anion exchange resin under the foregoing embodiments has more excellent catalyst activity and target product selectivity in the reaction of carbon dioxide with epoxides, and can maintain excellent catalytic activity even after long-term use.

[0033] The degree of hydrogenation in the present invention is obtained by elemental analysis of an imidazole-type anion exchange resin containing a non-hydrogenated (0%) styrene-divinylbenzene copolymer, an imidazole-type anion exchange resin containing a fully hydrogenated (100%) styrene-divinylbenzene copolymer, and an imidazole-type anion exchange resin after actual hydrogenation treatment.

[0034] According to the present invention, in some embodiments, the resin matrix has a crosslinking degree of 2% - 20%, for example, 2%, 5%, 7%, 9%, 10%, 12%, 14%, 15%, 20%, or a range composed of any two of the above values, preferably 4% - 10%. The anion exchange resin under the foregoing embodiments has excellent catalyst activity in the reaction of carbon dioxide with epoxides, and can maintain excellent catalytic activity even after long-term use.

[0035] According to the present invention, in some embodiments, in formula (1), R11 is a C1 - C6 alkyl group or hydrogen, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl or hydrogen. The anion exchange resin under the foregoing embodiments has excellent catalyst activity in the reaction of carbon dioxide with epoxides, and can maintain excellent catalytic activity even after long-term use.

[0036] According to the present invention, in some embodiments, in formula (1), R12 is a C1 - C4 alkyl group or hydrogen, for example, methyl, ethyl, propyl, butyl or hydrogen. The anion exchange resin under the foregoing embodiments has excellent catalyst activity in the reaction of carbon dioxide with epoxides, and can maintain excellent catalytic activity even after long-term use.

[0037] In the present invention, the C1-C6 alkyl group and the C1-C4 alkyl group can be straight-chain alkyl groups satisfying the corresponding number of carbon atoms, or can be branched-chain alkyl groups.

[0038] According to the present invention, in some embodiments, in formula (2), n is 0 or 1. When the anion exchange resin under the foregoing embodiments is used in the reaction of carbon dioxide with an epoxide, it has excellent catalytic activity, and can maintain excellent catalytic activity even after long-term use.

[0039] According to the present invention, in some embodiments, the anion exchange resin has the structure shown in formula (I).

[0040]

[0041] In formula (I), N is a nitrogen atom; R1 is selected from alkylene groups, R2 is selected from hydroxyl groups, carboxyl groups, amino groups or hydrogen, and X - is an anion.

[0042] According to the present invention, in some preferred embodiments, in formula (I), R1 is selected from C1-C6 alkylene groups, such as methylene, ethylene, propylene, butylene, pentylene or hexylene.

[0043] According to the present invention, in some preferred embodiments, in formula (I), X - is selected from halogen anions and / or organic acid root anions.

[0044] According to the present invention, the halogen anions that can be listed include Br - and Cl - etc.; the organic acid root ions that can be listed include oxalate, carbonate, acetate, etc., and halogen anions are preferred.

[0045] The second aspect of the present invention provides a preparation method of the imidazole-based anion exchange resin described in the present invention, and the preparation method includes:

[0046] S1 In the presence of a hydrogenation catalyst, a hydrogenation solvent and hydrogen, subject the halomethyl microspheres shown in formula (A) to a hydrogenation reaction to obtain hydrogenated halogen spheres;

[0047] S2 Subject the hydrogenated halogen spheres to imidazolization and anion exchange;

[0048]

[0049] Among them, contains a styrene-based structural unit shown in formula (A1) and a divinylbenzene structural unit shown in formula (A2).

[0050]

[0051] In formula (A1), the definitions of R11 and R12 are the same as those of R11 and R12 in formula (1); in formula (A2), the definition of n is the same as that of n in formula (2); Y is a halogen.

[0052] In the present invention, the imidazole-based anion exchange resin prepared by the preparation method of the present invention has good thermal stability. When it is used as a catalyst in the reaction of carbon dioxide with epoxides, it has excellent catalytic activity and target product selectivity, and can maintain excellent catalytic activity even after long-term use.

[0053] According to the present invention, in some embodiments, the conditions of the hydrogenation reaction include: the hydrogenation temperature is 90 - 180 °C, such as 90 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, or a range composed of any two of the above values, preferably 100 - 140 °C. The anion exchange resin prepared by the foregoing embodiment has better thermal stability and catalytic activity.

[0054] According to the present invention, in some embodiments, the conditions of the hydrogenation reaction include: the hydrogenation pressure is 1.0 - 8.0 MPa, such as 1.0 MPa, 2.0 MPa, 4.0 MPa, 6.0 MPa, 8.0 MPa, or a range composed of any two of the above values. The anion exchange resin prepared by the foregoing embodiment has better thermal stability and catalytic activity.

[0055] According to the present invention, in some embodiments, the conditions of the hydrogenation reaction include: the hydrogenation time is 3 - 24 hours, such as 3 hours, 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 18 hours, 24 hours, or a range composed of any two of the above values, preferably 5 - 24 hours, more preferably 5 - 10 hours. The anion exchange resin prepared by the foregoing embodiment has better thermal stability and catalytic activity.

[0056] According to the present invention, as long as the object of the present invention can be achieved, the specific type of the hydrogenation catalyst is not particularly limited. In some embodiments, the hydrogenation catalyst contains one or more active components of Ru, Pd, Pt, and Ni, and optionally one or more promoters of Cr, Cu, and Fe.

[0057] In the present invention, "optionally" means that the promoter may or may not be contained.

[0058] The catalyst described in the present invention can be a homogeneous hydrogenation catalyst or a heterogeneous hydrogenation catalyst.

[0059] According to the present invention, the hydrogenation catalysts that can be enumerated include Pt-based catalysts (such as 5 wt% Pt / C catalyst), Ni-based catalysts (such as KMK-2110, KMK-3110, KMK-5110, etc.), and Pd-based catalysts (such as Pd / C 500 type, GH555).

[0060] According to the present invention, in some embodiments, the hydrogenation solvent is selected from one or more of methanol, absolute ethanol, tetrahydrofuran, acetone, methyl ethyl ketone, toluene, ethyl acetate, benzene, and butyl acetate. By adopting the foregoing embodiments, the hydrogenation process can proceed more smoothly.

[0061] According to the present invention, the halogenomethyl microspheres can be obtained commercially or prepared by self-making. Preferably, the method for self-making includes: polymerizing a styrene compound and a divinylbenzene and then performing halogenomethylation. Specifically, it can be understood that the structure of the styrene compound is as shown in formula (A11), and the structure of the divinylbenzene is as shown in formula (A21).

[0062]

[0063] In formula (A11), the definitions of R11 and R12 are the same as those of R11 and R12 in formula (A1); the definitions of R11, R12, and n are the same as those of n in formula (A2).

[0064] According to the present invention, as long as the object of the present invention can be achieved, the type of polymerization is not particularly limited. Suspension polymerization is preferred. Specifically, the method for preparing the halogenomethyl microspheres includes: mixing a styrene compound, a divinylbenzene, and a radical initiator, then adding an aqueous solution containing a dispersant (such as a 0.5-2.0 w% PVA aqueous solution), and then performing a suspension polymerization reaction. Preferably, the conditions for the suspension polymerization reaction include: reacting with stirring at 65-75 °C for 1-3 h, reacting at 78-85 °C for 2-5 h, and reacting at 90-98 °C for 3-6 h to obtain a small spherical product. Stop stirring and age the small spheres at 90-98 °C for 1-4 h, and then perform post-treatment after suspension polymerization to obtain a styrene-based ion exchange resin; preferably, the amount of the dispersant used is 0.5-4 wt% of the mass of the styrene compound; preferably, the amount of water used is 150-300 wt% of the mass of the styrene compound; preferably, the amount of the radical initiator used is 1-5 wt% of the mass of the styrene compound; the radical initiators that can be enumerated include benzoyl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, etc.; preferably, the method for post-treatment after suspension polymerization includes: rinsing with ethanol and then continuing to rinse with water, and drying; wherein, the styrene-based ion exchange resin is subjected to halogenomethylation to obtain the halogenomethyl microspheres.

[0065] According to the present invention, preferably, the method for halomethylation includes: in the presence of a Lewis acid catalyst, a styrene-based ion exchange resin reacts with a halomethylating reagent for halomethylation reaction, and then purification and separation are carried out; preferably, the Lewis acid catalyst is selected from at least one of ZnCl2, AlCl3, TiCl4, SbF5, and ZrCl4; preferably, the dosage of the Lewis acid catalyst is 5-20 wt% of the mass of the styrene-based ion exchange resin; preferably, the conditions of the halomethylating reagent include: the reaction temperature is 50-60 °C, and the reaction time is 5-15 hours; preferably, the method for purification and separation includes: filtering out the halogenated mother liquor after the halomethylation reaction, then washing with methanol, and finally drying.

[0066] According to the present invention, the dosages of the styrene-based compound and the divinylbenzene can be selected according to the crosslinking degree required for the final imidazole-based anion exchange resin, that is, the crosslinking degree referred to in the present invention = mass of crosslinking agent / (mass of monomer + mass of crosslinking agent) * 100%; wherein the crosslinking agent is divinylbenzene and the monomer is a styrene-based compound.

[0067] According to the present invention, the crosslinking degree of the halomethyl microspheres is 2%-20%, preferably 4%-10%.

[0068] According to the present invention, as long as the object of the present invention can be achieved, the particle size of the halomethyl microspheres is not particularly limited. In some embodiments, the particle size of the halomethyl microspheres is 0.4-1.2 mm.

[0069] According to the present invention, in some embodiments, the method for imidazolization includes: in the presence of an imidazolization solvent, a hydrogenated halogen sphere reacts with an imidazolization reagent for imidazolization reaction. By adopting the foregoing embodiments, the prepared anion exchange resin has excellent catalytic activity when used in the reaction of carbon dioxide with an epoxide, and can maintain excellent catalytic activity even after long-term use.

[0070] According to the present invention, in some preferred embodiments, the imidazolization reagent is selected from N-alkylimidazoles, or N-alkylimidazole derivatives in which one hydrogen on the terminal carbon of N-alkylimidazole is substituted by a hydroxyl group, a carboxyl group, or an amino group; preferably, the alkyl group in the N-alkylimidazole is a straight-chain or branched-chain alkyl group having 1-6 carbon atoms. By adopting the foregoing embodiments, the prepared anion exchange resin has more excellent catalytic activity when used in the reaction of carbon dioxide with an epoxide.

[0071] According to the present invention, the selected imidazolization solvent only needs to be conducive to the progress of the imidazolization reaction. In some embodiments, the imidazolization solvent is at least one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and tetrahydrofuran.

[0072] According to the present invention, the conditions for the imidazolization reaction include: the reaction temperature is 50 - 100 °C; the reaction time is 10 - 48 hours.

[0073] According to the present invention, after the imidazolization, the reaction system still contains the imidazolization solvent. The solid substance can be obtained by filtration, washing, and drying as the hydrogen halide sphere. Among them, in order to further remove the imidazolization solvent during washing, it can be washed successively with deionized water and methanol.

[0074] According to the present invention, the anion exchange is to obtain an anion - containing ion - exchange resin through exchange. In some embodiments, the method of anion exchange includes: in the presence of a salt solution containing X - anions, the solid substance obtained by imidazolization is subjected to an anion - exchange reaction, where X - is selected from halogen anions and / or organic acid root anions.

[0075] According to the present invention, as long as the object of the present invention can be achieved, the conditions for the anion - exchange reaction are not particularly limited, and it is preferably carried out with stirring at room temperature.

[0076] According to the present invention, in some embodiments, the salt solution of X - anions is a metal salt solution containing X - ions; among them, the metal salt solution containing X - ions refers to a solution obtained by mixing a metal salt containing X - ions with water, and the concentration of the metal salt solution is not particularly limited, and is preferably 0.05 - 1.0 mol / L.

[0077] According to the present invention, as long as the anion - exchange resin of the present invention can be obtained through the anion - exchange reaction, the dosage of the salt solution containing X - anions and the solid substance (hydrogen halide sphere) obtained by imidazolization is not particularly limited, and it is preferably the solid substance obtained by imidazolization: the salt solution containing X - anions = 1 g:(10 - 30) mL.

[0078] According to the present invention, the reaction system after the anion - exchange reaction still contains water. In order to obtain the anion - exchange resin of the present invention, filtration, water washing, and drying can be carried out after the anion - exchange reaction; among them, the end point of the preferred water washing is that the pH of the washing liquid is 7, and the drying can be atmospheric drying or vacuum drying, and vacuum drying is preferred.

[0079] The third aspect of the present invention provides the application of the imidazole - type anion - exchange resin of the present invention in the catalytic addition reaction of carbon dioxide and epoxides.

[0080] In the present invention, the imidazole-based anion exchange resin of the present invention is used in the catalytic addition reaction of carbon dioxide and epoxide, and has excellent catalytic activity and stability.

[0081] The fourth aspect of the present invention provides a method for reacting carbon dioxide with an epoxide, the method comprising: using the imidazole-based anion exchange resin described in the present invention as a catalyst, and in the presence of the catalyst, carbon dioxide and the epoxide undergo a catalytic addition reaction.

[0082] In the present invention, when the imidazole-based anion exchange resin of the present invention is used as a catalyst in the catalytic addition reaction of carbon dioxide and epoxide, the catalyst not only has good catalytic activity, but also can maintain excellent catalytic activity during long-term use.

[0083] According to the present invention, in some preferred embodiments, the epoxide has the structure shown in formula (X),

[0084]

[0085] wherein, in formula (X), R4, R5, R6, and R7 are each independently selected from hydrogen, C1-C6 alkyl, or C6-C 10 aryl.

[0086] According to the present invention, in some preferred embodiments, in formula (X), R4, R5, R6, and R7 are each independently selected from hydrogen, methyl, ethyl, propyl, butyl, or phenyl.

[0087] According to the present invention, as long as the object of the present invention can be achieved, the amount of the catalyst is not particularly limited. In some preferred embodiments, the mass ratio of the catalyst to the epoxide is (0.001-1):1.

[0088] According to the present invention, as long as the object of the present invention can be achieved, the conditions of the catalytic addition reaction are not particularly limited at present. In some preferred embodiments, the conditions of the catalytic addition reaction include: the reaction temperature is 60-180 °C, preferably 80-130 °C.

[0089] According to the present invention, in some preferred embodiments, the conditions of the catalytic addition reaction include: the reaction pressure is 0.25-10.0 MPa, preferably 1.0-3.5 MPa.

[0090] According to the present invention, in some preferred embodiments, the conditions of the catalytic addition reaction include: the reaction time is 1-8 hours, preferably 2-5 hours.

[0091] The present invention will be described in detail below by way of examples.

[0092] Example 1

[0093] Preparation of chloromethyl microspheres A: In a 500 ml three-necked flask, add 150 g of styrene, 11.5 g of divinylbenzene, and 3 g of benzoyl peroxide, stir evenly, then add 300 g of 1.0 w% PVA aqueous solution. Then, carry out a stirring reaction at 70 °C for 3 h, at 80 °C for 3 h, and at 95 °C for 4 h to obtain a spherical product. Stop stirring and age the microspheres at 95 °C for 2 h. After the product is washed with ethanol and then with water, it is dried to obtain styrene-based ion exchange resin A; in a 500 mL three-necked flask, add 50 g of styrene-based ion exchange resin A and 200 mL of chloromethyl methyl ether, let it stand at room temperature for 2 hours, then add 8 g of zinc chloride as a catalyst and start stirring, gradually heat up to 60 °C and react for 10 hours. After the reaction is completed, cool it to room temperature, filter out the chlorination mother liquor, wash it with methanol, and dry it to obtain chloromethyl microspheres A (particle size 0.4 - 1.2 mm);

[0094] Hydrogenation reaction: In a 200 ml autoclave, add 50 g of chloromethyl microspheres A (the crosslinking degree of the resin matrix is 7%), 2.0 g of Pt-based catalyst (5 wt% Pt / C catalyst), and 100 ml of absolute ethanol, stir evenly; then carry out a hydrogenation reaction at 100 °C and 4.0 Mpa for 5 hours. After the reaction is completed, filter, wash with ethanol, and dry to obtain hydrogenated chlorinated microspheres A;

[0095] Imidazolization reaction: In a 500 mL three-necked flask, add 50 g of hydrogenated chlorinated microspheres A, 100 ml of N-methylimidazole, and 200 mL of acetonitrile, react under reflux for 18 hours, cool to room temperature, filter, wash successively with deionized water and methanol, and then dry in vacuum at 60 °C for 12 hours to obtain hydrogenated imidazole microspheres A; Ion exchange reaction: In a 1000 mL three-necked flask, add 50 g of hydrogenated imidazole microspheres A and 500 mL of deionized aqueous solution of NaBr with a concentration of 0.4 mol / L, stir at room temperature for 10 hours for ion exchange reaction; then wash with deionized water until the washing solution pH = 7, and obtain imidazole-type anion exchange resin after vacuum drying, denoted as Cat-A.

[0096] The TGA of Cat-A is as Figure 1 shown; The FTIR of Cat-A is as Figure 2 shown, and the elemental (C, H, N) analysis data of Cat-A are shown in Table 1.

[0097] The hydrogenation degree of Cat-A is 15%.

[0098] Table 1

[0099] C H N 56.76 5.75 9.73

[0100] Example 2

[0101] Preparation of chloromethyl microspheres B: In a 500 ml three-necked flask, add 150 g of styrene, 15 g of divinylbenzene, and 4 g of benzoyl peroxide, stir evenly, then add 300 g of 1.0 w% PVA aqueous solution. Then, carry out a stirring reaction at 70 °C for 3 h, at 80 °C for 3 h, and at 95 °C for 5 h to obtain a spherical product. Stop stirring, keep the temperature at 95 °C to age the microspheres for 3 h. Then, wash the product with ethanol and continue to wash with water, and dry to obtain styrene-based ion exchange resin B. In a 500 mL three-necked flask, add 50 g of styrene-based ion exchange resin B and 200 mL of chloromethyl methyl ether, let it stand at room temperature for 2 hours, then add 8 g of zinc chloride as a catalyst and start stirring, gradually heat up to 60 °C and react for 10 hours. After the reaction is completed, cool to room temperature, filter out the chlorination mother liquor, wash with methanol, and dry to obtain chloromethyl microspheres B (particle size 0.4 - 1.2 mm).

[0102] Hydrogenation reaction: In a 200 ml flask, add 50 g of chloromethyl microspheres (the cross-linking degree of the resin matrix is 9%), 3.5 g of Ni-based catalyst (KMK - 2110), and 150 ml of acetone, stir evenly; then carry out a hydrogenation reaction at 120 °C and a pressure of 6.0 Mpa for 8 hours. After the reaction is completed, filter, wash with ethanol, and dry to obtain hydrogenated chlorinated microspheres B.

[0103] Imidazolization reaction: In a 500 mL three-necked flask, add 50 g of hydrogenated chlorinated microspheres B, 100 ml of N-ethylimidazole, and 200 mL of N,N-dimethylformamide, react at 100 °C for 15 hours, cool to room temperature, filter, wash successively with deionized water and methanol, and then dry in vacuum at 60 °C for 12 hours to obtain hydrogenated imidazole microspheres B.

[0104] Ion exchange reaction: In a 1000 mL three-necked flask, add 50 g of hydrogenated imidazole microspheres B and 500 mL of deionized aqueous solution of NaBr with a concentration of 0.5 mol / L, stir at room temperature for an ion exchange reaction for 24 hours; then wash with deionized water until the pH of the washing liquid is 7, and dry in vacuum to obtain a catalyst, denoted as Cat-B.

[0105] The hydrogenation degree of Cat-B is 45%.

[0106] Example 3

[0107] Preparation of chloromethyl microsphere C: In a 500 ml three-necked flask, add 150 g of styrene, 3 g of diallyl phenyl, and 4 g of benzoyl peroxide, stir evenly, then add 300 g of 1.0 w% PVA aqueous solution. Then, react with stirring at 70 °C for 3 h, at 80 °C for 5 h, and at 95 °C for 3 h to obtain a spherical product. Stop stirring and age the spheres at 95 °C for 2 h. Then, wash the product with ethanol and continue to wash with water, and dry to obtain styrene-based ion exchange resin C. In a 500 mL three-necked flask, add 50 g of styrene-based ion exchange resin C and 200 mL of chloromethyl ether, let stand at room temperature for 2 h, then add 8 g of zinc chloride as a catalyst and start stirring, gradually heat up to 60 °C and react for 10 h. After the reaction, cool to room temperature, filter out the chlorination mother liquor, wash with methanol, and dry to obtain chloromethyl microsphere C (particle size 0.4 - 1.2 mm).

[0108] Hydrogenation reaction: In a 200 ml autoclave, add 50 g of chloromethyl microsphere C (resin matrix crosslinking degree 2%), 2.0 g of Pd-based catalyst (Pd / C 500 type), and 100 ml of tetrahydrofuran, stir evenly; then carry out the hydrogenation reaction at 140 °C and 2.0 Mpa pressure for 6 h. After the reaction, filter, wash with ethanol, and dry to obtain hydrogenated chlorosphere C.

[0109] Imidazolization reaction: In a 500 mL three-necked flask, add 40 g of hydrogenated chlorosphere C, 100 ml of N-propyl imidazole, and 200 mL of deionized water, react at 100 °C for 18 h, cool to room temperature, filter, wash successively with deionized water and methanol, and then dry in vacuum at 60 °C for 12 h to obtain hydrogenated imidazole sphere C.

[0110] Ion exchange reaction: In a 1000 mL three-necked flask, add 30 g of hydrogenated imidazole sphere C and 500 mL of deionized aqueous solution of NaBr with a concentration of 0.5 mol / L, stir at room temperature for the ion exchange reaction for 24 h; then wash with deionized water until the washing liquid pH = 7, and dry in vacuum to obtain the catalyst, denoted as Cat-C.

[0111] The hydrogenation degree of Cat-C is 25%.

[0112] Example 4

[0113] Preparation of chloromethyl microsphere D: In a 500 ml three-necked flask, add 150 g of styrene, 24.5 g of divinylbenzene, and 3 g of benzoyl peroxide, stir evenly, then add 300 g of 1.0 w% PVA aqueous solution. Then, carry out stirring reaction at 70 °C for 3 h, at 80 °C for 4 h, and at 95 °C for 4 h to obtain a spherical product. Stop stirring, keep the temperature at 95 °C to age the microspheres for 2 h. After the product is rinsed with ethanol and then with water, and dried to obtain styrene-based ion exchange resin D; In a 500 mL three-necked flask, add 50 g of styrene-based ion exchange resin D and 200 mL of chloromethyl methyl ether, let it stand at room temperature for 2 hours, then add 8 g of zinc chloride as a catalyst and start stirring, gradually raise the temperature to 60 °C and react for 10 hours. After the reaction, cool to room temperature, filter out the chlorination mother liquor, wash with methanol, and dry to obtain chloromethyl microsphere D (particle size is 0.4 - 1.2 mm);

[0114] Hydrogenation reaction: In a 200 ml autoclave, add 50 g of chloromethyl microsphere D (the crosslinking degree of the resin matrix is 14%), 2.5 g of Ni-based catalyst (KMK - 3110), and 100 ml of absolute ethanol, stir evenly; then carry out hydrogenation reaction at 100 °C and 4.0 Mpa pressure for 10 hours. After the reaction, filter, wash with ethanol, and dry to obtain hydrogenated chlorosphere D;

[0115] Imidazolization reaction: In a 500 mL three-necked flask, add 30 g of hydrogenated chlorosphere D, 60 ml of N-methylimidazole, and 200 mL of N,N-dimethylformamide, react at 100 °C for 24 hours, cool to room temperature, filter, wash successively with deionized water and methanol, and then dry in vacuum at 60 °C for 12 hours to obtain hydrogenated imidazole sphere D;

[0116] Ion exchange reaction: In a 1000 mL three-necked flask, add 30 g of hydrogenated imidazole sphere D and 500 mL of deionized aqueous solution of NaBr with a concentration of 0.4 mol / L, stir at room temperature for ion exchange reaction for 24 hours; then wash with deionized water until the pH of the washing liquid is 7, and dry in vacuum to obtain the catalyst, denoted as Cat-D.

[0117] The hydrogenation degree of Cat-D is 65%.

[0118] Example 5

[0119] Hydrogenation reaction: In a 200 ml autoclave, add 50 g of chloromethyl microsphere A in Example 1 (the crosslinking degree of the resin matrix is 7%), 3.0 g of Ni-based catalyst (KMK - 5110), and 100 ml of absolute ethanol, stir evenly; then carry out hydrogenation reaction at 100 °C and 4.0 Mpa pressure for 15 hours. After the reaction, filter, wash with ethanol, and dry to obtain hydrogenated chlorosphere E;

[0120] The chloroethylated resin E was subjected to imidization reaction and ion exchange reaction according to the method of Example 1 to finally obtain an imidazolium-based anion exchange resin, denoted as Cat-E.

[0121] The hydrogenation degree of Cat-E was 99%.

[0122] Example 6

[0123] Hydrogenation reaction: In a 200 ml autoclave, 50 g of chloromethylated microspheres (the crosslinking degree of the resin matrix was 7%) and 2.5 g of a Pd-based catalyst (GH555) were added, and 100 ml of absolute ethanol was added and stirred evenly; then the hydrogenation reaction was carried out at 100 °C and a pressure of 4.0 MPa for 3 hours. After the reaction, filtration was carried out, washed with ethanol, and dried to obtain hydrogenated chloroethylated resin F;

[0124] The hydrogenated chloroethylated resin E was subjected to imidization reaction and ion exchange reaction according to the method of Example 1 to finally obtain an imidazolium-based anion exchange resin, denoted as Cat-F.

[0125] The hydrogenation degree of Cat-F was 1%.

[0126] Comparative Example 1

[0127] In a 500 mL three-necked flask, 40 g of the chloromethylated microspheres A in Example 1, 100 ml of N-methylimidazole and 200 mL of N,N-dimethylformamide were added, and the reaction was carried out at 100 °C for 6 hours, cooled to room temperature, filtered, washed successively with deionized water and methanol, and then dried in vacuo at 60 °C for 12 hours to obtain imidazole microspheres G;

[0128] In a 1000 mL three-necked flask, 50 g of imidazole microspheres G and 500 mL of a deionized aqueous solution of NaBr with a concentration of 0.8 mol / L were added, and the ion exchange reaction was carried out with stirring at room temperature for 24 hours; then washed with deionized water until the pH of the washing solution was 7, and dried in vacuo to obtain an imidazolium-based anion exchange resin, denoted as Cat-G.

[0129] Example 7

[0130] The imidazolium-based anion exchange resin prepared in Example 1 was used as a catalyst for the addition reaction of epoxides and carbon dioxide. The experimental conditions were as follows: Under the protection of high-purity nitrogen, 30.0 g of ethylene oxide and 3.0 g of the catalyst Cat-A were added to a 150 ml autoclave, and the gas was fully replaced with 1.0 MPa CO2. CO2 was charged to maintain the reaction pressure at 3.0 MPa, and the temperature was raised to 140 °C. After reacting for 1 hour, the catalyst was filtered off, and the conversion rate C of ethylene oxide was measured EO was 98.5%, and the selectivity S of ethylene carbonate EC was 99.4%.

[0131] Examples 8-16

[0132] The types of catalysts, temperature, and pressure were changed, and other reaction conditions were the same as those in Example 7. The addition reaction of ethylene oxide and carbon dioxide was carried out, and the reaction results are shown in Table 2.

[0133] Table 2

[0134] Example Catalyst Pressure / MPa Temperature / °C Time / h <![CDATA[C EO , %]]> <![CDATA[S EG ,%]]> 8 Cat-B 3.0 140 1 98.9 99.1 9 Cat-C 3.0 140 1 98.5 99.1 10 Cat-D 3.0 140 2 98.3 99.3 11 Cat-E 3.0 140 1 97.1 99.2 12 Cat-F 3.0 140 1 95.3 99.1 13 Cat-A 3.0 100 2 95.4 99.4 14 Cat-A 3.0 140 2 99.9 99.3 15 Cat-A 5.0 120 2 98.6 99.3 16 Cat-G 3.0 120 2 94.5 98.9

[0135] Example 17

[0136] The catalyst Cat-A used in Example 7 was filtered, washed, and dried, and then the reaction of ethylene oxide and carbon dioxide was catalyzed again according to the reaction steps and conditions in Example 14 to obtain the results of the catalyst recycled 2 times, as shown in Table 3. By analogy, catalytic reactions with the number of cycles of 3 to 5 times were carried out respectively, and the results are shown in Table 3.

[0137] Table 3

[0138] Number of cycles <![CDATA[C EO %]]> <![CDATA[S EC %]]> 2 99.9 99.4 3 99.9 99.3 4 99.8 99.2 5 99.9 99.3

[0139] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. An imidazole-based anion exchange resin, characterized in that, The anion exchange resin comprises: a resin matrix and an imidazole group connected to the resin matrix through an alkylene group ; Among them, the resin matrix is a hydrogenated styrene-dienylbenzene copolymer, and the styrene-dienylbenzene copolymer contains a styrene structural unit represented by formula (1) and a dienylbenzene structural unit represented by formula (2). In formula (1), R11 is an alkyl or hydrogen, and R12 is an alkyl or hydrogen; in formula (2), n is an integer between 0 and 2.

2. The anion exchange resin according to claim 1, wherein the degree of hydrogenation of the anion exchange resin is 1%-100%, preferably 10%-90%, and more preferably 15%-70%.

3. The anion exchange resin according to claim 1 or 2, wherein The resin matrix has a crosslinking degree of 2% - 20%, preferably 4% - 10%; and / or in formula (1), R11 is a C1-C6 alkyl or hydrogen; and / or in formula (1), R12 is a C1-C4 alkyl or hydrogen; and / or in formula (2), n is 0 or 1.

4. The anion exchange resin according to any one of claims 1-3, wherein the anion exchange resin has the structure shown in formula (I), In formula (I), N is a nitrogen atom; R1 is selected from alkylene groups, R2 is selected from hydroxyl, carboxyl, amino or hydrogen, and X - is an anion; preferably, R1 is selected from C1-C6 alkylene; and / or X - Selected from halogen anions and / or organic acid anions.

5. The preparation method of the imidazole-based anion exchange resin according to any one of claims 1-4, characterized in that, the preparation method comprises: S1 In the presence of a hydrogenation catalyst, a hydrogenation solvent and hydrogen, subjecting the halomethyl microspheres shown in formula (A) to a hydrogenation reaction to obtain hydrogenated halogen spheres; S2 subjecting the hydrogenated halogen spheres to imidazolization and anion exchange; Among them, containing a styrene structural unit represented by formula (A1) and a divinylbenzene structural unit represented by formula (A2), In formula (A1), the definitions of R11 and R12 are the same as those of R11 and R12 described in any one of claims 1-4; in formula (A2), the definition of n is the same as that of n described in any one of claims 1-4; Y is a halogen.

6. The preparation method according to claim 5, wherein the conditions of the hydrogenation reaction include: the hydrogenation temperature is 90-180°C; and / or the hydrogenation pressure is 1.0-8.0 MP; and / or the hydrogenation time is 3-24 hours; and / or the hydrogenation catalyst contains one or more active components of Ru, Pd, Pt and Ni, and optionally one or more promoters of Cr, Cu and Fe; and / or the hydrogenation solvent is selected from one or more of methanol, absolute ethanol, tetrahydrofuran, acetone, methyl ethyl ketone, toluene, ethyl acetate, benzene and butyl acetate.

7. The preparation method according to claim 5 or 6, wherein the halomethyl microspheres are obtained by polymerizing a styrene compound and divinylbenzene followed by halomethylation, and preferably the polymerization is suspension polymerization; and / or the crosslinking degree of the halomethyl microspheres is 2%-20%, preferably 4%-10%; and / or the particle size of the halomethyl microspheres is 0.4-1.2 mm.

8. The preparation method according to any one of claims 5-7, wherein the method of imidazolization comprises: in the presence of an imidazolization solvent, subjecting the hydrogenated halogen spheres to an imidazolization reaction with an imidazolization reagent; preferably, the imidazolization reagent is selected from N-alkylimidazoles, or N-alkylimidazole derivatives in which one hydrogen on the terminal carbon of N-alkylimidazole is substituted by a hydroxyl, carboxyl or amino group; preferably the alkyl in N-alkylimidazole is a C1-C6 straight-chain or branched-chain alkyl; and / or the imidazolization solvent is at least one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide and tetrahydrofuran; and / or the conditions of the imidazolization reaction include: the reaction temperature is 50-100°C; and / or the reaction time is 10-48 hours; and / or The method for anion exchange includes: in the presence of a salt solution containing X - anions, performing an anion exchange reaction on the solid substance obtained by imidazolization, where X - is selected from halogen anions and / or organic acid root anions, preferably the salt solution of the X - anions is a metal salt solution containing X - ions.

9. Use of the imidazole-based anion exchange resin according to any one of claims 1-4 in the catalytic addition reaction of carbon dioxide and epoxide.

10. A method for the reaction of carbon dioxide with an epoxide, characterized in that, The method comprises: using the imidazole-based anion exchange resin according to any one of claims 1-4 as a catalyst, and in the presence of the catalyst, carrying out a catalytic addition reaction of carbon dioxide and epoxide; Preferably, the epoxide has the structure shown by formula (X), Among them, in formula (X), R4, R5, R6, and R7 are each independently selected from hydrogen, C1-C6 alkyl, or C6-C 10 aryl, preferably each independently selected from hydrogen, methyl, ethyl, propyl, butyl, or phenyl; and / or The mass ratio of the catalyst to the epoxide is (0.001-1):1; and / or The conditions of the catalytic addition reaction include: The reaction temperature is 60-180°C, preferably 80-130°C; and / or The reaction pressure is 0.25-10.0 MPa, preferably 1.0-3.5 MPa; and / or The reaction time is 1-8 hours, preferably 2-5 hours.

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