Quaternary ammonium type anion exchange resin, preparation method and application thereof, and method for catalyzing hydration reaction of epoxy-containing compound

Abstract

The invention relates to the field of ion exchange resin, and discloses quaternary ammonium type anion exchange resin, a preparation method and application thereof, and a catalytic hydration reaction method of an epoxy-containing compound. The anion exchange resin comprises a resin matrix # imgabs 0 # and a quaternary ammonium group connected with the resin matrix # imgabs 1 # through an alkylene group; wherein the resin matrix # imgabs2 is a hydrogenated styrene-dienylbenzene copolymer, and the styrene-dienylbenzene copolymer contains a styrene structural unit as shown in a formula (1), a dienylbenzene structural unit as shown in a formula (2), a # imgabs3 # formula (1) and a # imgabs4 # formula (2); in the formula (1), R11 is alkyl or hydrogen, and R12 is alkyl or hydrogen; in the formula (2), n is an integer between 0 and 2. The quaternary ammonium type anion exchange resin provided by the invention has excellent swelling resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of ion exchange resins, and particularly relates to a quaternary ammonium type anion exchange resin, a preparation method and application thereof, and a method for catalytic hydration reaction of an epoxy compound-containing substance. Background Art

[0002] Oxygen-containing compounds can be prepared into corresponding vicinal diols after hydration, which are important organic chemical raw materials. For example, ethylene glycol can be prepared by the hydration of ethylene oxide. The hydration reaction can be divided into non-catalytic hydration and catalytic hydration. In terms of catalytic hydration, ion exchange resins are currently the most widely studied catalysts for EO catalytic hydration.

[0003] Ion exchange resins are a class of high molecular compounds with ion exchange groups, which can utilize the ion exchange function to achieve separation and purification, so as to achieve the purposes of concentration, separation, purification, and purification. Among them, the structure of strong base anion exchange resins contains quaternary ammonium groups, which are obtained by reacting the chloromethyl groups on chloromethylated polystyrene chains with tertiary amines. Limited by the structure of the quaternary ammonium itself, strong base anion exchange resins are prone to Hofmann degradation reactions when heated, resulting in the detachment of the quaternary ammonium groups in the resin structure and the conversion of strong base groups into weak base groups, thereby causing the inactivation of strong base anion exchange resins. Therefore, the use temperature of strong base ion exchange resins containing quaternary ammonium groups is usually relatively low, generally limited to below 60°C.

[0004] The use performance of ion exchange resin catalysts can be improved by changing the R group linked to the quaternary ammonium nitrogen atom, changing the electronic effect of the benzene ring (introducing electron-withdrawing or electron-donating groups), changing the spacer between the benzene ring and the quaternary ammonium group, or introducing nano-additives and other methods.

[0005] Mitsubishi Corporation of Japan developed a class of ion exchange resins with relatively high heat resistance through the copolymerization of functional monomers of styrene and divinylbenzene. There is a hydrocarbon group or an alkoxymethylene chain connected between the benzene ring and the quaternary ammonium nitrogen atom of the resin (Masaomi Tomii, Hirohisa Kubota, Polymer Processing (Japan) [J], 1999, 48(2): 57-63). The quaternary ammonium groups in the resin are relatively stable when heated and can be used for a long time at 90°C. However, the selectivity of ethylene glycol is only 89%. At the same time, the functional monomer is synthesized by the Grignard reaction, with a long route, harsh operating conditions, low yield, difficult separation and purification of the functional monomer, and low purity, which affects the use performance of the final resin catalyst.

[0006] Chen Qun et al. (Ion Exchange and Adsorption, 2009, 25(6): 534-541) studied the preparation of strongly basic anion exchange resins with long carbon chain spacer arms by functionalizing styrene-divinylbenzene copolymer white balls as the resin matrix. The resin has good thermal stability and shows good catalytic performance in the catalytic hydration of ethylene oxide. By optimizing the process, under the conditions of temperature 90 °C, pressure 1.8 MPa, space velocity 0.17 h-1, and water ratio 6.4:1, the conversion rate of ethylene oxide can reach 98.0%, and the selectivity of ethylene glycol reaches about 95.0%. However, this technology does not fundamentally solve the swelling problem of the resin catalyst.

[0007] ZL201010261758.2 and ZL201310515574.8 disclose a series of composite ion exchange resins prepared by suspension polymerization and functionalization reactions using carbon nanomaterials or graphene as nano additives to improve the performance of the resin for ethylene oxide hydration. Under the conditions of water ratio 10:1, pressure 1.2 MPa, and temperature 90-102 °C, the EO conversion rate and EG selectivity are better than those of conventional resins; ZL20150604401.2 discloses a method for improving the temperature resistance of ion exchange resins by changing the group connected to the quaternary ammonium nitrogen atom. By reacting 1,6-dicyanoguanidinohexane with the resin skeleton in one step and further reacting with octadecyl bromide, an exchange resin with double long chains is synthesized, improving the thermal stability of the resin.

[0008] Currently, for ion exchange resin catalysts used in the hydration reaction of epoxides, how to improve the performance of the catalyst remains a research hotspot for ion exchange resin catalysts. Summary of the Invention

[0009] The purpose of the present invention is to overcome the problem of poor swelling resistance of existing ion exchange resins, and to provide a quaternary ammonium type anion exchange resin, its preparation method and application, and a method for catalytic hydration reaction of epoxide-containing compounds. The quaternary ammonium type anion exchange resin has excellent swelling resistance, and when used in catalytic hydration reaction, it also has excellent catalytic activity.

[0010] To achieve the above purpose, in the first aspect of the present invention, a quaternary ammonium type anion exchange resin is provided, which includes: a resin matrix and a quaternary ammonium group connected to the resin matrix through an alkylene group The resin matrix is a hydrogenated styrene-based-divinylbenzene copolymer, and the styrene-based-divinylbenzene copolymer contains a styrene-based structural unit shown in formula (1) and a divinylbenzene structural unit shown in formula (2). 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.

[0011] The second aspect of the present invention provides a preparation method of the quaternary ammonium type anion exchange resin described in the present invention, and the preparation method includes:

[0012] S1 In the presence of a hydrogenation catalyst, a hydrogenation solvent and hydrogen, subject the halo-methyl microspheres represented by formula (A) to a hydrogenation reaction to obtain hydrogenated halo-spheres;

[0013] S2 Quaternize and anion-exchange the hydrogenated halo-spheres;

[0014]

[0015] Among them, It contains a styrene-based structural unit represented by formula (A1) and a divinylbenzene structural unit represented by formula (A2),

[0016]

[0017] 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.

[0018] The third aspect of the present invention provides the application of the quaternary ammonium type anion exchange resin described in the present invention in a catalytic hydration reaction.

[0019] The fourth aspect of the present invention provides a method for a catalytic hydration reaction of an epoxy compound-containing material, and the method includes: using the quaternary ammonium type anion exchange resin described in the present invention as a catalyst, and in the presence of this catalyst, subject the epoxy compound-containing material and water to a catalytic hydration reaction.

[0020] Through the above technical solutions, the quaternary ammonium type anion exchange resin provided by the present invention has excellent swelling resistance. When the quaternary ammonium type anion exchange resin in the present invention is used as a catalyst in the catalytic hydration reaction of an epoxy compound, such as in the catalytic hydration reaction of an epoxy compound-containing material and water, it not only has excellent catalytic performance, but also has excellent swelling resistance, that is, it has excellent service performance. Description of the Drawings

[0021] Figure 1 It is the TGA diagram of the quaternary ammonium type anion exchange resin in Example 1;

[0022] Figure 2 It is the FTIR diagram of the quaternary ammonium type anion exchange resin in Example 1. Detailed Embodiments

[0023] The endpoints and any values disclosed in this text 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 in this text.

[0024] The first aspect of the present invention provides a quaternary ammonium type anion exchange resin, and the anion exchange resin includes: a resin matrix and a quaternary ammonium group connected to the resin matrix through an alkylene group ;

[0025] 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),

[0026]

[0027] 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.

[0028] The quaternary ammonium type anion exchange resin containing a hydrogenated styrene-dienylbenzene copolymer in the present invention has excellent swelling resistance, and when it is used in a hydration reaction, it also has excellent catalyst activity.

[0029] According to the present invention, the linking group "alkylene group" between the quaternary ammonium group and the resin matrix can be methylene, ethylene, propylene, etc., and preferably methylene.

[0030] According to a preferred embodiment of the present invention, the anion exchange resin has a structure represented by formula (I),

[0031]

[0032] In formula (I), R1, R2, and R3 are each independently an alkyl group, and X - is an anion;

[0033] According to a preferred embodiment of the present invention, in formula (I), X - is selected from one or more of bicarbonate ion, hydroxide ion, bisulfite ion, formate ion, acetate ion, and citrate ion.

[0034] According to a particularly preferred embodiment of the present invention, in formula (I), R1, R2, and R3 are each independently C1-C10 alkyl group.

[0035] In the present invention, C1-C 10 alkyl group refers to an alkyl group containing 1-10 carbon atoms, which can be a straight-chain alkyl group or a branched-chain alkyl group, preferably a C1-C4 alkyl group.

[0036] According to a preferred embodiment of the present invention, the crosslinking degree of the resin matrix is 2%-20%, preferably 4%-10%. The quaternary ammonium type anion exchange resin under the foregoing embodiment has more excellent heat resistance, and when it is used in the catalytic hydration reaction, it can still maintain excellent catalytic activity after long-term use.

[0037] According to a preferred embodiment of the present invention, in formula (1), R11 is a C1-C6 alkyl group or hydrogen, such as methyl, ethyl, propyl, butyl, pentyl, hexyl or hydrogen. The quaternary ammonium type anion exchange resin under the foregoing embodiment has more excellent swelling resistance, and when it is used in the catalytic hydration reaction, it has excellent catalytic activity.

[0038] According to a preferred embodiment of the present invention, in formula (1), R12 is a C1-C4 alkyl group or hydrogen. The quaternary ammonium type anion exchange resin under the foregoing embodiment has more excellent swelling resistance, and when it is used in the catalytic hydration reaction, it has excellent catalytic activity.

[0039] In the present invention, the C1-C6 alkyl group and the C1-C4 alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group that satisfies the corresponding number of carbon atoms.

[0040] According to a preferred embodiment of the present invention, in formula (2), n is 0 or 1. The quaternary ammonium type anion exchange resin under the foregoing embodiment has more excellent swelling resistance, and when it is used in the catalytic hydration reaction, it has excellent catalytic activity.

[0041] According to a preferred embodiment of the present invention, the hydrogenation degree of the anion exchange resin is 1%-100%, such as 1%, 5%, 10%, 15%, 20%, 30%, 50%, 60%, 65%, 75%, 85%, 90%, 95%, 99%, 100%, or a range composed of any two of the above values. The quaternary ammonium type anion exchange resin under the foregoing embodiment has more excellent swelling resistance, and when it is used in the catalytic hydration reaction, it has excellent catalytic activity and target product selectivity.

[0042] According to a particularly preferred embodiment of the present invention, the hydrogenation degree of the anion exchange resin is 8%-90%, preferably 10%-60%, and more preferably 10%-50%. The quaternary ammonium type anion exchange resin under the foregoing embodiment has better swelling resistance, and when it is used in the catalytic hydration reaction, it has better catalytic activity and target product selectivity.

[0043] In the present invention, the hydrogenation degree is obtained by elemental analysis of a quaternary ammonium type anion exchange resin containing a styrene-diallylbenzene copolymer without hydrogenation (0%), a quaternary ammonium type anion exchange resin containing a fully hydrogenated (100%) styrene-diallylbenzene copolymer, and the quaternary ammonium type anion exchange resin after actual hydrogenation treatment.

[0044] The second aspect of the present invention provides a preparation method of the quaternary ammonium type anion exchange resin described in the present invention, and the preparation method includes:

[0045] S1 In the presence of a hydrogenation catalyst, a hydrogenation solvent and hydrogen, subject the halomethyl microspheres represented by formula (A) to a hydrogenation reaction to obtain hydrogenated halogen spheres;

[0046] S2 Quaternize and anion-exchange the hydrogenated halogen spheres;

[0047]

[0048] Wherein, It contains a styrene structural unit represented by formula (A1) and a diallylbenzene structural unit represented by formula (A2),

[0049]

[0050] 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.

[0051] In the present invention, the quaternary ammonium type anion exchange resin prepared by the preparation method of the present invention has good swelling resistance, has excellent catalyst activity when used as a catalyst in the catalytic hydration reaction containing an epoxide, and can maintain excellent catalytic activity even after long-term use.

[0052] According to a preferred embodiment of the present invention, 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, and preferably 100-140°C. The anion exchange resin prepared by the foregoing embodiment has better thermal stability and catalytic activity.

[0053] According to a preferred embodiment of the present invention, the conditions for 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 swelling resistance and catalytic activity.

[0054] According to a preferred embodiment of the present invention, the conditions for 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, and more preferably 5 - 10 hours. The anion exchange resin prepared by the foregoing embodiment has better swelling resistance and catalytic activity.

[0055] 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. Preferably, 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.

[0056] In the present invention, "optionally" means that the promoter may or may not be contained.

[0057] The catalyst described in the present invention can be a homogeneous hydrogenation catalyst or a heterogeneous hydrogenation catalyst.

[0058] According to the present invention, examples of the hydrogenation catalyst that can be listed 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).

[0059] According to a preferred embodiment of the present invention, 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 using the foregoing embodiment, the hydrogenation process can proceed more smoothly.

[0060] According to the present invention, the halomethyl microspheres can be obtained commercially or prepared by oneself. Preferably, the method for self-preparation includes: specifically, it can be understood that the structure of the styrene compound is shown in formula (A11), and the structure of the divinylbenzene is shown in formula (A21).

[0061]

[0062] 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).

[0063] 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, and suspension polymerization is preferred. Specifically, the method for preparing the haloalkyl microspheres includes: mixing a styrenic 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 carrying out a suspension polymerization reaction. Preferably, the conditions of the suspension polymerization reaction include: reacting at 65-75 °C with stirring 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, stopping stirring, aging the small balls at 90-98 °C for 1-4 h, and then carrying out post-treatment after suspension polymerization to obtain a styrenic ion exchange resin; preferably, the amount of the dispersant is 0.5-4 wt% of the mass of the styrenic compound; preferably, the amount of water is 150-300 wt% of the mass of the styrenic compound; preferably, the amount of the radical initiator is 1-5 wt% of the mass of the styrenic compound; examples of the radical initiator that can be cited 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 styrenic ion exchange resin is subjected to haloalkylation to obtain the haloalkyl microspheres.

[0064] According to the present invention, preferably, the method for haloalkylation includes: carrying out a haloalkylation reaction between the styrenic ion exchange resin and a haloalkylating agent in the presence of a Lewis acid catalyst, and then carrying out purification and separation; preferably, the Lewis acid catalyst is selected from at least one of ZnCl2, AlCl3, TiCl4, SbF5 and ZrCl4; preferably, the amount of the Lewis acid catalyst is 5-20 wt% of the mass of the styrenic ion exchange resin; preferably, the conditions of the haloalkylating agent 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 haloalkylation reaction, then washing with methanol, and finally drying.

[0065] According to the present invention, the crosslinking degree of the haloalkyl microspheres is 2%-20%, preferably 4%-10%.

[0066] According to the present invention, the amounts of the styrenic compound and the divinylbenzene can be selected according to the crosslinking degree required for the final quaternary ammonium type anion exchange resin, that is, the crosslinking degree referred to in the present invention = crosslinking agent mass / (monomer mass + crosslinking agent mass) * 100%; wherein the crosslinking agent is divinylbenzene and the monomer mass is the styrenic compound.

[0067] 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. Preferably, the particle size of the halomethyl microspheres is 0.4 - 1.2 mm.

[0068] According to a preferred embodiment of the present invention, the quaternization method includes: in the presence of an ammoniating solvent, a quaternizing reagent reacts with a hydrogen halide sphere for quaternization. By adopting the foregoing embodiment, the prepared anion exchange resin has better swelling resistance and catalytic activity.

[0069] According to a preferred embodiment of the present invention, the quaternizing reagent is a trialkylamine. Preferably, the alkyl groups in the trialkylamine are each independently a C1 - C 10 alkyl group, and each independently is an alkyl group of C1 - C4. By adopting the foregoing embodiment, the prepared anion exchange resin has better swelling resistance and catalytic activity.

[0070] According to a preferred embodiment of the present invention, the ammoniating solvent is at least one of acetonitrile, N,N - dimethylformamide, N,N - dimethylacetamide, and tetrahydrofuran.

[0071] According to a preferred embodiment of the present invention, the conditions of the quaternization reaction include: the reaction temperature is 40 - 90 °C; the reaction time is 10 - 48 hours.

[0072] According to the present invention, after the quaternization, the reaction system still contains the ammoniating solvent. The solid substance can be obtained as a hydrogen halide sphere by filtration, washing, and drying. Among them, when washing, in order to further remove the ammoniating solvent, a solvent can be used for washing, such as washing with deionized water and methanol in sequence.

[0073] According to the present invention, 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 an X - anion, the solid substance obtained by quaternization is subjected to an anion exchange reaction, and X - is selected from one or more of bicarbonate ion, hydroxide ion, bisulfite ion, formate ion, acetate ion, and citrate ion.

[0074] 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. Preferably, it is carried out with stirring at room temperature.

[0075] In the present invention, room temperature refers to 20 - 30 °C.

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

[0077] According to the present invention, as long as the anion exchange resin described in the present invention can be obtained through an anion exchange reaction, the amount of the salt solution containing X - anion and the solid substance (hydrogenated halogen sphere) obtained by quaternization is not particularly limited. Preferably, the solid substance obtained by quaternization: the salt solution containing X - anion salt solution = 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 water washing is preferably the washing liquid pH = 7, and the drying can be atmospheric drying or vacuum drying, preferably vacuum drying.

[0079] The third aspect of the present invention provides the application of the quaternary ammonium type anion exchange resin described in the present invention in the catalytic hydration reaction.

[0080] In the present invention, when the quaternary ammonium type anion exchange resin in the present invention is used for catalytic hydration, in the reaction, it has excellent catalytic activity and stability.

[0081] The fourth aspect of the present invention provides a method for catalytic hydration reaction of an epoxy compound-containing substance, the method comprising: using the quaternary ammonium type anion exchange resin described in the present invention as a catalyst, and in the presence of this catalyst, the epoxy compound-containing substance reacts with water in a catalytic hydration reaction.

[0082] In the present invention, when the quaternary ammonium type anion exchange resin in the present invention is used as a catalyst for the catalytic addition reaction of an epoxy compound-containing substance, the catalyst not only has good catalytic activity, but also can maintain excellent catalytic activity during long-term use.

[0083] According to a preferred embodiment of the present invention, the epoxy compound-containing substance 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, preferably each independently selected from hydrogen, methyl, ethyl, propyl, butyl, or phenyl.

[0086] According to a preferred embodiment of the present invention, the molar ratio of water to the epoxy compound is (1 - 50):1, preferably (6 - 20):1.

[0087] According to a preferred embodiment of the present invention, the conditions for the catalytic hydration reaction include: the reaction temperature is 40 - 180 °C, preferably 80 - 110 °C.

[0088] According to a preferred embodiment of the present invention, the conditions for the catalytic hydration reaction include: the reaction pressure is 0.1 - 10.0 MPa, preferably 1.0 - 2.5 MPa.

[0089] According to a preferred embodiment of the present invention, the conditions for the catalytic hydration reaction include: the liquid hourly space velocity is 0.1 - 6.0 h -1 , preferably 1.0 - 4.0 h -1 .

[0090] The present invention will be described in detail below through examples.

[0091] In the following examples and comparative examples: The prepared quaternary ammonium type anion exchange resin is used as a catalyst for the catalytic hydration reaction of an epoxy compound with water.

[0092] Calculation of reaction results:

[0093] The EO conversion rate and MEG selectivity are calculated by the following formulas:

[0094] C EO (%) = [n (MEG) + 2n (DEG) + 3n (TEG) / n 0(EO) ×100%

[0095] S EG (%) = n (MEG) / [n (MEG) + 2n (DEG) + 3n (TEG) ×100%

[0096] Where C EO is the EO conversion rate; S EG is the EG selectivity; n 0(EO) is the feed amount of EO, in mol; n (MEG) , n (DEG) and n (TEG) are the amounts of substance of ethylene glycol, diethylene glycol, and triethylene glycol in the product, in mol, respectively.

[0097] Example 1

[0098] 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, keep the temperature at 95 °C to age the microspheres for 2 h. After the product is washed with ethanol and then with water, and 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 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 A (particle size 0.4 - 1.2 mm);

[0099] 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; Subsequently, carry out a hydrogenation reaction at 100 °C and a pressure of 4.0 Mpa for 5 hours. After the reaction is completed, filter, wash with ethanol, and dry to obtain hydrogenated chlorinated microspheres A;

[0100] Quaternization reaction: In a 500 mL three-necked flask, add 30 g of hydrogenated chlorinated microspheres A, 50 ml of trimethylamine, and 200 mL of N,N-dimethylformamide, react at 60 °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 ammonium microspheres A; Ion exchange reaction: In a 1000 mL three-necked flask, add 30 g of hydrogenated ammonium microspheres A and 500 mL of deionized aqueous solution of NaHCO3 with a concentration of 0.8 mol / L, stir at room temperature for an ion exchange reaction for 24 hours; Subsequently, wash with deionized water until the pH of the washing liquid is 7, and after vacuum drying, obtain quaternary ammonium type anion exchange resin, denoted as Cat-A.

[0101] The TGA diagram of Cat-A is as Figure 1 shown; The FTIR diagram of Cat-A is as Figure 2 shown, and the elemental (C, H, N) analysis data of Cat-A is shown in Table 1.

[0102] The hydrogenation degree of Cat-A is 10%.

[0103] Table 1

[0104] C H N 64.90 8.08 5.56

[0105] Example 2

[0106] 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 and age the microspheres at 95 °C for 3 h. After the product is rinsed with ethanol and then with water, it is dried 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 ether, let it 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 it to room temperature, filter out the chlorination mother liquor, wash it with methanol, and dry it to obtain chloromethyl microspheres B (particle size 0.4 - 1.2 mm).

[0107] Hydrogenation reaction: In a 200-ml flask, add 40 g of chloromethyl microspheres B (resin matrix crosslinking degree 9%), 3.0 g of Ni-based catalyst (KMK - 2110), and 150 ml of acetone, stir evenly. Subsequently, carry out a hydrogenation reaction at 120 °C and 6.0 Mpa pressure for 8 h. After the reaction, filter, wash with ethanol, and dry to obtain hydrogenated chlorinated microspheres B.

[0108] Quaternization reaction: In a 500-mL three-necked flask, add 40 g of hydrogenated chlorinated microspheres B, 100 ml of tributylamine, and 200 mL of acetonitrile, react at 70 °C for 12 h, cool to room temperature, filter, wash successively with deionized water and methanol, and then dry at 60 °C under vacuum for 12 h to obtain hydrogenated ammonium microspheres B.

[0109] Ion exchange reaction: In a 1000-mL three-necked flask, add 30 g of hydrogenated ammonium microspheres B and 500 mL of deionized aqueous solution of NaOH with a concentration of 0.5 mol / L, stir at room temperature for an ion exchange reaction for 24 h. Subsequently, wash with deionized water until the washing solution pH = 7, and dry under vacuum to obtain quaternary ammonium type anion exchange resin, denoted as Cat-B.

[0110] The hydrogenation degree of Cat-B is 50%.

[0111] Example 3

[0112] Preparation of chloromethyl microsphere C: In a 500 ml three-necked flask, add 150 g of styrene, 3 g of divinylbenzene, 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 microspheres 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).

[0113] 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. Subsequently, carry out the hydrogenation reaction at 140 °C and 2.0 Mpa for 6 h. After the reaction, filter, wash with ethanol, and dry to obtain hydrogenated chlorosphere C.

[0114] Quaternization reaction: In a 500 mL three-necked flask, add 30 g of hydrogenated chlorosphere C, 80 ml of triethylamine, and 200 mL of N,N-dimethylformamide, react at 50 °C for 24 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 ammonium sphere C.

[0115] Ion exchange reaction: In a 1000 mL three-necked flask, add 30 g of hydrogenated ammonium sphere C and 500 mL of deionized aqueous solution of NaHCO3 with a concentration of 0.8 mol / L, stir at room temperature for the ion exchange reaction for 24 h. Subsequently, wash with deionized water until the washing solution pH = 7, and dry in vacuum to obtain quaternary ammonium type anion exchange resin, denoted as Cat-C.

[0116] The hydrogenation degree of Cat-C is 20%.

[0117] Example 4

[0118] Preparation of chloromethyl microspheres 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, react with stirring 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 and age the spheres at 95 °C for 2 h. The product is then washed 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 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 D (particle size 0.4 - 1.2 mm).

[0119] Hydrogenation reaction: In a 200 ml autoclave, add 50 g of chloromethyl microspheres D (resin matrix cross-linking degree is 14%), 2.5 g of Ni-based catalyst (KMK - 3110), and 100 ml of absolute ethanol, stir evenly; then carry out the hydrogenation reaction at 100 °C and 4.0 Mpa for 10 hours. After the reaction is completed, filter, wash with ethanol, and dry to obtain hydrogenated chlorinated spheres D.

[0120] Quaternization reaction: In a 500 mL three-necked flask, add 30 g of hydrogenated chlorinated spheres D, 60 ml of trimethylamine, and 200 mL of N,N-dimethylformamide, react at 60 °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 ammonium spheres D.

[0121] Ion exchange reaction: In a 1000 mL three-necked flask, add 30 g of hydrogenated ammonium spheres D and 500 mL of deionized aqueous solution of NaHCO3 with a concentration of 0.8 mol / L, stir at room temperature for the 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 quaternary ammonium type anion exchange resin, denoted as Cat-D.

[0122] The hydrogenation degree of Cat-D is 60%.

[0123] Example 5

[0124] Hydrogenation reaction: In a 200 ml autoclave, add 50 g of chloromethyl microspheres A in Example 1 (resin matrix cross-linking degree is 7%), 3.0 g of Ni-based catalyst (KMK - 5110), and 100 ml of absolute ethanol, stir evenly; then carry out the hydrogenation reaction at 100 °C and 4.0 Mpa for 15 hours. After the reaction is completed, filter, wash with ethanol, and dry to obtain hydrogenated chlorinated spheres E.

[0125] The quaternization reaction and ion exchange reaction of hydrogenated chlorine beads E were carried out according to the method of Example 1, and finally a quaternary ammonium type anion exchange resin was obtained, denoted as Cat-E.

[0126] The hydrogenation degree of Cat-E is 99%.

[0127] Example 6

[0128] Hydrogenation reaction: In a 200 ml autoclave, 50 g of the chloromethyl microspheres in Example 1 (the crosslinking degree of the resin matrix is 7%), 2.5 g of a Pd-based catalyst (GH555), and 100 ml of absolute ethanol were 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, it was filtered, washed with ethanol, and dried to obtain hydrogenated chlorine beads F;

[0129] The quaternization reaction and ion exchange reaction of hydrogenated chlorine beads E were carried out according to the method of Example 1, and finally a quaternary ammonium type anion exchange resin was obtained, denoted as Cat-F.

[0130] The hydrogenation degree of Cat-F is 5%.

[0131] Comparative Example 1

[0132] In a 500 mL three-necked flask, 50 g of the chloromethylated microspheres G in Example 1, 100 ml of trimethylamine, and 200 mL of N,N-dimethylformamide were added, and the reaction was carried out at 60 °C for 24 hours. After cooling to room temperature, it was filtered and washed successively with deionized water and methanol, and then dried in vacuo at 60 °C for 12 hours to obtain ammonium beads G;

[0133] In a 1000 mL three-necked flask, 50 g of ammonium beads G and 500 mL of a deionized aqueous solution of NaHCO3 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 it was washed with deionized water until the pH of the washing solution was 7, and after vacuum drying, a catalyst was obtained, denoted as Cat-G.

[0134] Example 7

[0135] The catalyst prepared in Example 1 was loaded into a fixed-bed reactor for the catalytic hydration reaction of alkylene oxide. The reaction conditions were as follows: The protective gas was inert gas high-purity nitrogen, the pressure was 1.2 MPa, the molar ratio of water to ethylene oxide was 5:1, and the liquid hourly space velocity was 1.0 h -1 , After stabilization, samples were taken for the determination of conversion and selectivity, and the results are shown in Table 2.

[0136] In Examples 8-17, the catalyst type, temperature, space velocity, and molar ratio were changed, and other reaction conditions were the same as those in Example 7, and the catalytic hydration reaction of ethylene oxide was carried out. The reaction results are shown in Table 2.

[0137] Table 2

[0138]

[0139]

[0140] Wherein:

[0141] When the catalyst Cat-A catalyzes the hydration reaction of ethylene oxide, after 240 hours, the conversion rate C of ethylene oxide EO is 95.7%, and the selectivity S of ethylene glycol EG is 98.1%.

[0142] When the catalyst Cat-B catalyzes the hydration reaction of ethylene oxide, after 240 hours, the conversion rate C of ethylene oxide EO is 95.0%, and the selectivity S of ethylene glycol EG is 98.3%.

[0143] When the catalyst Cat-C catalyzes the hydration reaction of ethylene oxide, after 360 hours, the conversion rate C of ethylene oxide EO is 94.7%, and the selectivity S of ethylene glycol EG is 98.4%.

[0144] When the catalyst Cat-D catalyzes the hydration reaction of ethylene oxide, after 240 hours, the conversion rate C of ethylene oxide EO is 87.9%, and the selectivity S of ethylene glycol EG is 95.9%.

[0145] When the catalyst Cat-E catalyzes the hydration reaction of ethylene oxide, after 288 hours, the conversion rate C of ethylene oxide EO is 86.3%, and the selectivity S of ethylene glycol EG is 95.1%.

[0146] When the catalyst Cat-F catalyzes the hydration reaction of ethylene oxide, after 240 hours, the conversion rate C of ethylene oxide EO is 90.9%, and the selectivity S of ethylene glycol EG is 97.6%.

[0147] When the catalyst Cat-G catalyzes the hydration reaction of ethylene oxide, after 200 hours, the conversion rate C of ethylene oxide EO decreases to 83.1%, and the selectivity S of ethylene glycol EG is 78.2%. At the same time, due to the swelling of the resin in the system, the system pressure gradually rises, the reactor is blocked, and the reaction stops.

[0148] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. 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. A quaternary ammonium type anion exchange resin, characterized in that, The anion exchange resin comprises: a resin matrix and a quaternary ammonium group connected to the resin matrix via 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 group or hydrogen, and R12 is an alkyl group or hydrogen; in formula (2), n is an integer between 0 and 2.

2. The anion exchange resin according to claim 1, wherein the anion exchange resin has the structure shown in formula (I), In formula (I), R1, R2, and R3 are each independently an alkyl group, and X - is an anion; Preferably, in formula (I), X - is selected from one or more of bicarbonate ion, hydroxide ion, bisulfite ion, formate ion, acetate ion and citrate ion; and / or In formula (I), R1, R2, and R3 are each independently a C1-C 10 alkyl group, preferably each independently a C1-C4 alkyl group.

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 group or hydrogen; and / or in formula (1), R12 is a C1-C4 alkyl group 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 degree of hydrogenation of the anion exchange resin is 1%-100%, preferably 8%-90%, and more preferably 10%-60%.

5. A method for preparing the quaternary ammonium type anion exchange resin according to any one of claims 1 to 4, characterized in that, The preparation method comprises: S1. In the presence of a hydrogenation catalyst, a hydrogenation solvent and hydrogen, subjecting the halo-methyl microspheres shown in formula (A) to a hydrogenation reaction to obtain hydrogenated halo-spheres; S2. Subjecting the hydrogenated halo-spheres to quaternization 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 in any one of claims 1-4; in formula (A2), the definition of n is the same as that of n 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 halo-methyl microspheres are obtained by polymerizing a styrene compound and divinylbenzene and then subjecting them to halo-methylation, and preferably the polymerization is suspension polymerization; and / or the crosslinking degree of the halo-methyl microspheres is 2%-20%, preferably 4%-10%; and / or the particle size of the halo-methyl microspheres is 0.4-1.2 mm.

8. The preparation method according to any one of claims 5-7, wherein the method of quaternization includes: in the presence of an ammoniating solvent, subjecting a quaternizing reagent and the hydrogenated halo-spheres to a quaternization reaction; Preferably, the quaternization reagent is a trialkylamine, preferably the alkyl groups in the trialkylamine are each independently a C1-C 10 alkyl group, each independently a C1-C4 alkyl group; and / or the ammoniating solvent is at least one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide and tetrahydrofuran; and / or the conditions of the quaternization reaction include: the reaction temperature is 40-90 °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 quaternization, where X - is selected from one or more of bicarbonate ions, hydroxide ions, bisulfite ions, formate ions, acetate ions, and citrate ions.

9. Use of the quaternary ammonium type anion exchange resin according to any one of claims 1-4 in a catalytic hydration reaction.

10. A method for the catalytic hydration reaction of an epoxy compound, characterized in that, The method comprises: using the quaternary ammonium type anion exchange resin according to any one of claims 1-4 as a catalyst, and in the presence of this catalyst, subjecting an epoxy compound-containing substance and water to a catalytic hydration reaction; Preferably, the epoxy compound-containing substance has the structure shown in 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 molar ratio of the water to the epoxy compound is (1 - 50):1, preferably (6 - 20):1; and / or the conditions for the catalytic hydration reaction include: The reaction temperature is 40 - 180 °C, preferably 80 - 110 °C; and / or The reaction pressure is 0.1 - 10.0 MPa, preferably 1.0 - 2.5 MPa; and / or The liquid hourly space velocity is 0.1 - 6.0 h -1 , preferably 1.0 - 4.0 h -1 .

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