Ion exchange resin catalysts, processes for their preparation and use

Abstract

This invention discloses an ion exchange resin catalyst, its preparation method, and its application. The chemical formula of the catalyst is: P1-PS-CH2N + R1R2R3M ‑ Wherein, P1 is styrene / divinylbenzene copolymer microspheres; PS is polystyrene segments; N + It is a quaternary ammonium cation; R1, R2, and R3 may be the same or different, and each is independently an alkyl group; M ‑ It is an anion. When the catalyst of this invention is used in the reaction of epoxides with deionized water to prepare diols, the catalyst has high catalytic efficiency, the products after the reaction are easy to separate, and the catalyst can be used continuously multiple times.

Description

Technical Field

[0001] This invention relates to an ion exchange resin catalyst, its preparation method, and its application. Background Technology

[0002] Ion exchange resins are a class of polymeric compounds with ion exchange groups. They utilize ion exchange to achieve separation and purification, thereby achieving purposes such as concentration, separation, purification, and refining. They are insoluble in common acid and alkali solutions and many organic solvents, exhibiting strong stability. Ion exchange resins are also commonly used as catalysts, widely applied in chemical reactions such as etherification, hydration, esterification, alkylation, condensation, decomposition, polymerization, and cyclization.

[0003] Typically, the functional groups of strongly basic anion exchange resins are quaternary ammonium groups, which can dissociate into OH groups in water. － It is strongly alkaline, and the positively charged groups on the resin matrix can adsorb and combine with anions in the solution, thereby producing anion exchange or alkaline catalysis. For example, Shell has developed a quaternary ammonium anion exchange resin and used it for the catalytic hydration of ethylene oxide, achieving an ethylene oxide conversion rate close to 100% and an ethylene glycol selectivity of up to 95%. Dow Chemical, using Dowex MSA-1 as a resin catalyst, achieved ethylene oxide conversion and ethylene glycol selectivity of over 95% and 96%, respectively, under conditions of a molar water ratio of 9:1, 99°C, and 1.2 MPa. Shvets et al. from Mendeleev University of Chemical Technology in Russia developed a bicarbonate-type anion exchange resin that, under conditions of a molar water ratio of 5:1–7:1, 80–130°C, and 0.8–1.6 MPa, catalyzed the hydration of ethylene oxide in a series-parallel plug flow reactor, achieving an ethylene oxide conversion rate >99% and an ethylene glycol selectivity between 93% and 96%.

[0004] Strongly basic ion exchange resins are typically obtained by chloromethylation and quaternization reactions of white spheres produced from styrene / divinylbenzene suspension polymerization. Currently, the exchange equivalent of commercially available strongly basic ion exchange resins is generally below 4.0 mmol / g, mainly because the quaternary ammonium group content is limited by the chlorine content in the resin matrix. Furthermore, the chlorine content of styrene / divinylbenzene suspension copolymers after chloromethylation is generally between 16% and 20%, making further increases difficult. This also affects the catalytic efficiency of strongly basic ion exchange resins as solid base catalysts, limiting their application in catalytic reactions.

[0005] CN104119466A discloses the synthesis of a bifunctional anion exchange resin with high exchange capacity. First, a chloromethylated resin is prepared by primary amination and quaternization reactions to obtain a bifunctional anion exchange resin with both weak and strong basic anion groups. However, the catalytic performance is not high.

[0006] As can be seen, the aforementioned strong base anion exchange resin catalyst materials have significant drawbacks. Therefore, how to appropriately increase the exchange equivalent of the resin, thereby improving the efficiency of the strong base anion exchange resin catalyst, has become a research direction for anion exchange resins. Summary of the Invention

[0007] To address the problem of poor catalytic performance of existing ion exchange resin catalysts, this invention provides a novel ion exchange resin catalyst and its preparation method. When the catalyst of this invention is used in the reaction of epoxides and deionized water to prepare diols, the catalyst exhibits high catalytic efficiency, easy separation of the reaction products, and the ability to be used repeatedly.

[0008] The inventors of this invention, through research, discovered the synthesis of a high-exchange-capacity bifunctional anion exchange resin disclosed in CN104119466A, with a total exchange equivalent of 6.3–7.9 mmol / g. While this resin catalyst exhibits a significantly higher exchange equivalent than commercially available anion exchange resins, it contains approximately 2.5–3.2 mmol / g of weakly basic functional groups. Due to the different catalytic activities of weak and strong basic groups, its high exchange equivalent advantage is not apparent in specific reactions such as the hydration of epoxides. Instead, the presence of weak and hydroxyl groups in the resin triggers ring-opening polymerization of epoxides, thus affecting the catalyst's catalytic performance. The inventors of this invention, through research, prepared and obtained an ion exchange resin catalyst with high catalytic efficiency, easily separable reaction products, and the ability to be reused multiple times.

[0009] The first aspect of this invention provides an ion exchange resin catalyst with the chemical formula: P1-PS-CH2N + R1R2R3M - ,

[0010] Wherein, P1 is styrene / divinylbenzene copolymer microspheres; PS is polystyrene segment; N + It is a quaternary ammonium cation; R1, R2, and R3 may be the same or different, and each is independently an alkyl group; M - It is an anion.

[0011] In this invention, the term "styrene / divinylbenzene copolymer microspheres" refers to copolymer microspheres of styrene and divinylbenzene.

[0012] In the above scheme, preferably, in formula I, R1, R2, and R3 are each independently an alkyl group. x H y x is any integer from 1 to 6, and y is any integer from 3 to 13; preferably, R1, R2, and R3 are n-butane (-C4H9).

[0013] In the above scheme, preferably, in formula I, M - It is selected from bicarbonate ions, hydroxide ions, bisulfite ions, formate ions, acetate ions, or citrate ions.

[0014] In the above scheme, preferably, the catalyst is obtained by polymerizing chloromethylated styrene / divinylbenzene copolymer microspheres as a resin matrix, and then sequentially performing chloromethylation, quaternization and ion exchange reactions.

[0015] A second aspect of the present invention provides a method for preparing an ion exchange resin catalyst, comprising:

[0016] S1: Chloromethylated styrene / divinylbenzene copolymer microspheres are mixed with a solvent, and the polymerization reaction of styrene is initiated in the presence of an initiator to obtain styrene-modified resin matrix P1;

[0017] S2: The styrene-modified resin matrix P1 obtained in step S1 is subjected to chloromethylation, quaternization and ion exchange reactions in sequence.

[0018] In the above scheme, preferably, the degree of crosslinking of the chloromethylated styrene / divinylbenzene copolymer microspheres is 1-15%, more preferably 2-8%.

[0019] In the above scheme, preferably, based on the total weight of the copolymer microspheres, the amount of the initiator is 0.1-5% by weight, and the amount of styrene is 5-20% by weight.

[0020] In the above scheme, preferably, the initiator includes cuprous chloride and 2,2'-bipyridine.

[0021] In the above scheme, preferably, the molar ratio of cuprous chloride to 2,2'-bipyridine is 1:2 to 1:5.

[0022] In the above scheme, preferably, the solvent is selected from at least one of 1,4-dioxane, toluene, tetrahydrofuran, and anisole.

[0023] In the above scheme, preferably, the conditions for the polymerization reaction include: a temperature of 80-110°C and a time of 1-3 hours.

[0024] In the above scheme, preferably, washing is performed after the polymerization reaction and before the chloromethylation reaction, for example, but not limited to washing with tetrahydrofuran.

[0025] In the above scheme, preferably, the chloromethylation reaction step includes: in the presence of zinc chloride, styrene-modified resin matrix P1 is subjected to chloromethylation reaction with a chloromethylation reaction reagent to obtain modified microspheres.

[0026] In the above scheme, preferably, the amount of zinc chloride used is 12-100% by weight, based on the weight of the styrene-modified resin matrix P1. In the chloromethylation reaction, zinc chloride can be a catalyst for the reaction.

[0027] In the above scheme, preferably, the chloromethylation reaction reagent is selected from chloromethyl ether, chloroethyl ether, chloromethyl ethyl ether or 1,4-dichloromethoxybutane.

[0028] In the above scheme, preferably, the weight ratio of styrene-modified resin matrix P1 to chloromethylation reagent is 1:2 to 6.

[0029] In the above scheme, preferably, the conditions for the chloromethylation reaction include: a temperature of 25-60°C and a time of 4-30 hours.

[0030] In the above scheme, preferably, after the chloromethylation reaction and before the quaternization reaction, the method further includes cooling to room temperature, filtering out the chlorination mother liquor, repeatedly washing with methanol, and drying. The drying process may include, for example but not limited to, drying at 100°C for 8 hours to obtain modified chlorine beads.

[0031] In the above scheme, preferably, the quaternization reaction step includes: quaternizing the modified microspheres, the quaternizing agent and N,N-dimethylformamide to obtain the modified ammonium spheres.

[0032] In the above scheme, preferably, the weight ratio of modified microspheres, quaternizing agent, and N,N-dimethylformamide is 1:0.3-2:5-15.

[0033] In the above scheme, preferably, the quaternizing agent is selected from at least one of trimethylamine, triethylamine, tripropylamine and tri-n-butylamine.

[0034] In the above scheme, preferably, the conditions for the quaternization reaction include: a temperature of 40–90°C and a time of 10–48 h.

[0035] In the above-described scheme, preferably, after the quaternization reaction and before the ion exchange reaction, the process further includes cooling to room temperature, filtering, washing successively with ethyl acetate, 0.1 mol / L HCl, deionized water, and methanol, and then drying. Vacuum drying conditions include, but are not limited to, drying at 60°C under vacuum for 12 hours.

[0036] In the above scheme, preferably, the steps of the ion exchange reaction include: washing the modified ammonium balls with a salt solution and washing them with water.

[0037] In the above scheme, preferably, the weight ratio of the modified ammonium spheres to the salt solution is 1:50 to 100; the concentration of the salt solution is 0.1 to 1 mol / L.

[0038] In the above scheme, preferably, the salt solution is selected from at least one of the following: a solution containing bicarbonate ions, a solution containing hydroxide ions, a solution containing bisulfite ions, and an organic acid metal salt solution.

[0039] In the above scheme, preferably, the organic acid is selected from at least one of formic acid, acetic acid and citric acid.

[0040] In the above scheme, preferably, the salt solution is selected from at least one of NaHCO3 aqueous solution, sodium citrate aqueous solution, sodium formate aqueous solution, sodium hydroxide aqueous solution, and potassium hydroxide aqueous solution.

[0041] In the above scheme, preferably, the water is washed until pH=7.

[0042] In some preferred embodiments of the present invention, the method for preparing the catalyst includes the following steps:

[0043] a) Polymerization: 200–600% by weight of solvent, 10–20% by weight of initiator system, and 5–20% by weight of styrene are added to chloromethylated styrene / divinylbenzene copolymer microspheres. The reaction flask is purged with high-purity nitrogen to replace the air and then sealed. The reaction is carried out at 80–110°C for 1–3 hours. After filtration and washing, the modified resin matrix is ​​obtained.

[0044] b) Chloromethylation reaction: Add 200-600% by weight of chloromethylation reagent and 12-100% by weight of zinc chloride catalyst to the modified resin matrix, react at 25-60°C for 4-30 hours, and obtain modified chlorospheres after filtration and washing.

[0045] c) Quaternization reaction: The mixture of the modified chlorine spheres, quaternization reagent, and N,N-dimethylformamide is reacted at 40-90°C for 10-48 hours. After the reaction is completed, the mixture is filtered and washed to obtain the modified ammonium spheres.

[0046] d) The modified ammonium spheres are washed with a salt solution, wherein the molar ratio of the modified ammonium spheres to the salt solution is 1:1 to 10; the concentration of the salt solution is 0.1 to 1 mol / L; after washing, the ion exchange resin catalyst is obtained by washing with deionized water until pH=7.

[0047] A third aspect of the present invention provides an ion exchange resin catalyst prepared by the above method, having the chemical formula: P1-PS-CH2N + R1R2R3M - ,

[0048] Wherein, P1 is styrene / divinylbenzene copolymer microspheres; PS is polystyrene segment; N +It is a quaternary ammonium cation; R1, R2, and R3 may be the same or different, and each is independently an alkyl group; M - It is an anion.

[0049] In the above scheme, preferably, in Formula I, R1, R2, and R3 are each independently an alkyl group CxHy, where x is any integer from 1 to 6 and y is any integer from 3 to 13; preferably, R1, R2, and R3 are n-butyl (-C4H9).

[0050] In the above scheme, preferably, in formula I, M - It is selected from bicarbonate ions, hydroxide ions, bisulfite ions, formate ions, acetate ions, or citrate ions.

[0051] A fourth aspect of the present invention provides a method for preparing a diol, wherein an epoxide alkane is reacted with water in the presence of an ion exchange resin catalyst, wherein the ion exchange resin catalyst is the catalyst described above or a catalyst prepared according to the preparation method described above.

[0052] In the above scheme, preferably, the water is deionized water.

[0053] In the above scheme, preferably, the epoxy alkane has the general structural formula shown in Formula I:

[0054]

[0055] R4-R7 may be the same or different, and each is independently selected from hydrogen, C1-C4 alkyl, and C6-C8 aryl; preferably selected from at least one of hydrogen, methyl, ethyl, propyl, and phenyl. More preferably, the alkyl oxide is selected from at least one of ethylene oxide, propylene oxide, and butane oxide.

[0056] In the above scheme, preferably, the reaction temperature is 40-150℃, and more preferably 80-110℃.

[0057] In the above scheme, preferably, the reaction pressure is 0.1 to 10 MPa, more preferably 1 to 2.5 MPa.

[0058] In the above scheme, preferably, the molar ratio of water to epoxide is 1 to 50:1, more preferably 6 to 20:1.

[0059] In the above scheme, preferably, the liquid space velocity of the reaction is 0.1 to 6 h⁻¹. -1 Preferably 2-6 hours -1 .

[0060] The beneficial effects of this invention are:

[0061] The catalyst of this invention is used in the reaction of epoxides and deionized water to prepare diols. The catalyst has high catalytic efficiency, the products after the reaction are easy to separate, and the catalyst can be used continuously multiple times, showing promise for industrial application. Detailed Implementation

[0062] To make the present invention easier to understand, the present invention will be described in detail below with reference to embodiments. These embodiments are for illustrative purposes only and are not limited to the scope of application of the present invention.

[0063] In the following examples and comparative examples, the chloromethylated styrene / divinylbenzene copolymer (chlorine content 10%) was purchased from Suqing Water Treatment Engineering Group Co., Ltd.

[0064]

Example 1

[0065] Preparation of ion exchange resin catalysts:

[0066] (1) Polymerization: 50.0 g of chloromethylated styrene / divinylbenzene copolymer (chlorine content 10%) with a crosslinking degree of 7% was added to a 500 mL flask, followed by 100 mL of toluene. The mixture was allowed to swell for 1 hour. Then, a mixture of 10 g styrene, 10 g cuprous chloride, and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine was 1:2) was added. The air in the flask was completely replaced with high-purity nitrogen, and the reaction was carried out at 110 °C for 1 hour. After the reaction was completed, the mixture was washed with tetrahydrofuran to obtain modified resin matrix 1.

[0067] (2) Chloromethylation: In a 500ml three-necked flask, add 40g of modified resin matrix 1 and 200ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 15g of zinc chloride, heat to 60℃ and react for 10 hours. After chloromethylation, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol, and dry at 100℃ for 8 hours to obtain modified chlorine ball 1.

[0068] (3) Quaternization reaction: 30 g of modified chlorine ball 1 (chlorine content 13%), tri-n-butylamine (100 mmol) and 200 ml of N,N-dimethylformamide were added to a 500 ml three-necked flask. The mixture was reacted at 60 °C for 24 hours, cooled to room temperature, filtered, and washed successively with ethyl acetate, 0.1 mol / L HCl, deionized water and methanol. Then it was dried under vacuum at 60 °C for 12 hours to obtain modified ammonium ball 1.

[0069] (4) Ion exchange reaction: 30 g of modified ammonium spheres 1 and 500 ml of 0.1 mol / L NaHCO3 deionized water solution were added to a 1000 ml three-necked flask and stirred at room temperature for 24 hours to carry out the ion exchange reaction. Then, the solution was washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the ion exchange resin catalyst Cat-1 was obtained.

[0070]

Example 2

[0071] Preparation of ion exchange resin catalysts:

[0072] (1) Polymerization: 60.0 g of chloromethylated styrene / divinylbenzene copolymer (chlorine content 10%) with a crosslinking degree of 2% was added to a 500 mL flask, followed by 150 mL of tetrahydrofuran. The mixture was allowed to swell for 1 hour. Then, 10 g of styrene, 9 g of a mixture of cuprous chloride and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine was 1:2) were added. The air in the flask was completely replaced with high-purity nitrogen, and the reaction was carried out at 100 °C for 2 hours. After the reaction was completed, the mixture was washed with tetrahydrofuran to obtain modified resin matrix 2.

[0073] (2) Chloromethylation: In a 500ml three-necked flask, add 50g of modified resin matrix 2 and 200ml of chloroethyl ether, let stand at room temperature for 3 hours, start stirring, add 20g of zinc chloride as a catalyst, heat to 40℃ and react for 12 hours. After chloromethylation, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol, and dry at 100℃ for 8 hours to obtain modified chlorinated spheres 2.

[0074] (3) Quaternization reaction: 30 g of modified chlorine ball 2 (chlorine content 12%), trimethylamine (110.0 mmol) and 200 ml of N,N-dimethylformamide were added to a 500 ml three-necked flask. The mixture was reacted at 40 °C for 15 hours, cooled to room temperature, filtered, and washed successively with ethyl acetate, 0.1 mol / L HCl, deionized water and methanol. Then it was dried under vacuum at 60 °C for 12 hours to obtain modified ammonium ball 2.

[0075] (4) Ion exchange reaction: 30 g of modified ammonium spheres 2 and 500 ml of 0.5 mol / L NaHCO3 deionized water solution were added to a 1000 ml three-necked flask and stirred at room temperature for 24 hours to carry out the ion exchange reaction. Then, the solution was washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the ion exchange resin catalyst Cat-2 was obtained.

[0076]

Example 3

[0077] Preparation of ion exchange resin catalysts:

[0078] (1) Polymerization: 50.0 g of chloromethylated styrene / divinylbenzene copolymer (chlorine content 10%) with a crosslinking degree of 7% was added to a 500 mL flask, followed by 200 mL of 1,4-dioxane, and the mixture was allowed to swell for 1 hour. Then, a mixture of 5 g styrene, 5 g cuprous chloride, and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine was 1:2) was added. The air in the flask was completely replaced with high-purity nitrogen, and the reaction was carried out at 80 °C for 3 hours. After the reaction was completed, the mixture was washed with tetrahydrofuran to obtain modified resin matrix 3.

[0079] (2) Chloromethylation: In a 500ml three-necked flask, add 40g of modified resin matrix 3 and 300ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 25g of zinc chloride as a catalyst, heat to 50℃ and react for 24 hours. After chloromethylation, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol, and dry at 100℃ for 8 hours to obtain modified chlorinated spheres 3.

[0080] (3) Quaternization reaction: 30 g of modified chlorine sphere 3 (chlorine content 15%), trimethylamine (130 mmol) and 200 ml of N,N-dimethylformamide were added to a 500 ml three-necked flask. The mixture was reacted at 50 °C for 36 hours, cooled to room temperature, filtered, and washed successively with ethyl acetate, 0.1 mol / L HCl, deionized water and methanol. Then it was dried under vacuum at 60 °C for 12 hours to obtain modified ammonium sphere 3.

[0081] (4) Ion exchange reaction: 30 g of modified ammonium spheres 3 and 500 ml of 0.2 mol / L NaHCO3 deionized water solution were added to a 1000 ml three-necked flask and stirred at room temperature for 24 hours to carry out the ion exchange reaction. Then, the solution was washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the ion exchange resin catalyst Cat-3 was obtained.

[0082]

Example 4

[0083] Preparation of ion exchange resin catalysts:

[0084] (1) Polymerization: 50.0 g of chloromethylated styrene / divinylbenzene copolymer (chlorine content 10%) with a crosslinking degree of 7% was added to a 500 mL flask, followed by 100 mL of toluene. The mixture was allowed to swell for 1 hour. Then, a mixture of 10 g styrene and 10 g cuprous chloride and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine was 1:2) was added. The air in the flask was completely replaced with high-purity nitrogen, and the reaction was carried out at 110 °C for 1 hour. After the reaction was completed, the mixture was washed with tetrahydrofuran to obtain modified resin matrix 4.

[0085] (2) Chloromethylation: In a 500ml three-necked flask, add 40g of modified resin matrix 4 and 200ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 15g of zinc chloride as a catalyst, heat to 60℃ and react for 10 hours. After chloromethylation, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol, and dry at 100℃ for 8 hours to obtain modified chlorinated spheres 4.

[0086] (3) Quaternization reaction: 30 g of modified chlorine spheres 4 (chlorine content 13%), tri-n-butylamine (100.0 mmol) and 200 ml of N,N-dimethylformamide were added to a 500 ml three-necked flask. The mixture was reacted at 60 °C for 24 hours, cooled to room temperature, filtered, and washed successively with ethyl acetate, 0.1 mol / L HCl, deionized water and methanol. Then it was dried under vacuum at 60 °C for 12 hours to obtain modified ammonium spheres 4.

[0087] (4) Ion exchange reaction: 30 g of modified ammonium balls and 500 ml of 0.1 mol / L sodium citrate deionized water were added to a 1000 ml three-necked flask and stirred at room temperature for 24 hours to carry out the ion exchange reaction. Then, the solution was washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the ion exchange resin catalyst Cat-4 was obtained.

[0088]

Example 5

[0089] Preparation of ion exchange resin catalysts:

[0090] (1) Polymerization: 60.0 g of chloromethylated styrene / divinylbenzene copolymer (chlorine content 10%) with a crosslinking degree of 2% was added to a 500 mL flask, followed by 150 mL of tetrahydrofuran. The mixture was allowed to swell for 1 hour. Then, 10 g of styrene and 9 g of a mixture of cuprous chloride / 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine was 1:2) were added. The air in the flask was completely replaced with high-purity nitrogen, and the reaction was carried out at 100 °C for 2 hours. After the reaction was completed, the mixture was washed with tetrahydrofuran to obtain modified resin matrix 5.

[0091] (2) Chloromethylation: In a 500ml three-necked flask, add 50g of modified resin matrix 5 and 200ml of chloroethyl ether, let stand at room temperature for 3 hours, start stirring, add 20g of zinc chloride as a catalyst, heat to 40℃ and react for 12 hours. After chloromethylation, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol, and dry at 100℃ for 8 hours to obtain modified chlorinated spheres 5.

[0092] (3) Quaternization reaction: 30 g of modified chlorine sphere 5 (chlorine content 12%), trimethylamine (110.0 mmol) and 200 ml of N,N-dimethylformamide were added to a 500 ml three-necked flask. The mixture was reacted at 40 °C for 15 hours, cooled to room temperature, filtered, and washed successively with ethyl acetate, 0.1 mol / L HCl, deionized water and methanol. Then it was dried under vacuum at 60 °C for 12 hours to obtain modified ammonium sphere 5.

[0093] (4) Ion exchange reaction: 30 g of modified ammonium spheres 5 and 500 ml of 0.5 mol / L sodium formate deionized water were added to a 1000 ml three-necked flask and stirred at room temperature for 24 hours to carry out the ion exchange reaction. Then, the solution was washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the ion exchange resin catalyst Cat-5 was obtained.

[0094]

Example 6

[0095] Preparation of ion exchange resin catalysts:

[0096] (1) Polymerization: 50.0 g of chloromethylated styrene / divinylbenzene copolymer (chlorine content 10%) with a crosslinking degree of 7% was added to a 500 mL flask, followed by 200 mL of 1,4-dioxane, and the mixture was allowed to swell for 1 hour. Then, a mixture of 5 g styrene, 5 g cuprous chloride, and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine was 1:2) was added, and the mixture was reacted at 80 °C for 3 hours. After the reaction was completed, the mixture was washed with tetrahydrofuran to obtain modified resin matrix 6.

[0097] (2) Chloromethylation: In a 500ml three-necked flask, add 40g of modified resin matrix 6 and 300ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 25g of zinc chloride as a catalyst, heat to 50℃ and react for 24 hours. After chloromethylation, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol, and dry at 100℃ for 8 hours to obtain modified chlorosphere 6.

[0098] (3) Quaternization reaction: 30 g of modified chlorine sphere 6 (chlorine content 15%), trimethylamine (130 mmol) and 200 ml of N,N-dimethylformamide were added to a 500 ml three-necked flask. The mixture was reacted at 50 °C for 36 hours, cooled to room temperature, filtered, and washed successively with ethyl acetate, 0.1 mol / L HCl, deionized water and methanol. Then it was dried under vacuum at 60 °C for 12 hours to obtain modified ammonium sphere 6.

[0099] (4) Ion exchange reaction: 30 g of modified ammonium spheres 6 were added to a 1000 ml three-necked flask, and 500 ml of 0.2 mol / L sodium hydroxide deionized water solution was added to carry out the ion exchange reaction at room temperature for 24 hours. Then, the solution was washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the ion exchange resin catalyst Cat-6 was obtained.

[0100]

Example 7

[0101] The ion exchange resin catalyst was prepared according to the method of Example 1, except that the chloromethylated styrene / divinylbenzene copolymer with a crosslinking degree of 7% in Example 1 was replaced with a chloromethylated styrene / divinylbenzene copolymer with a crosslinking degree of 1%. The resulting ion exchange resin catalyst was Cat-7.

[0102]

Example 8

[0103] The ion exchange resin catalyst was prepared according to the method of Example 1, except that the chloromethylated styrene / divinylbenzene copolymer with a crosslinking degree of 7% in Example 1 was replaced with a chloromethylated styrene / divinylbenzene copolymer with a crosslinking degree of 15%. The resulting ion exchange resin catalyst was Cat-8.

[0104]

Example 9

[0105] The ion exchange resin catalyst was prepared according to the method of Example 1, except that the chloromethylated styrene / divinylbenzene copolymer with a crosslinking degree of 7% in Example 1 was replaced with a chloromethylated styrene / divinylbenzene copolymer with a crosslinking degree of 20%. The resulting ion exchange resin catalyst was Cat-9.

[0106]

Example 10

[0107] The ion exchange resin catalyst was prepared according to the method of Example 1, except that the mixture of cuprous chloride and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine of 1:2) in Example 1 was replaced with a mixture of cuprous chloride and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine of 1:5). The ion exchange resin catalyst Cat-10 was obtained.

[0108]

Example 11

[0109] The ion exchange resin catalyst was prepared according to the method of Example 1, except that the mixture of cuprous chloride and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine of 1:2) in Example 1 was replaced with a mixture of cuprous chloride and 2,2'-bipyridine (molar ratio of cuprous chloride to 2,2'-bipyridine of 1:1). The ion exchange resin catalyst Cat-11 was obtained.

[0110]

Example 12

[0111] An ion exchange resin catalyst was prepared according to the method of Example 1, except that the 10 grams of styrene in Example 1 was replaced with 5 grams of styrene. The resulting ion exchange resin catalyst was Cat-12.

[0112] Comparative Example 1

[0113] Product D201 was purchased from Suqing Water Treatment Engineering Group Co., Ltd.

[0114] [Test Example]

[0115] The catalysts of Examples 1-12 and Comparative Example 1 were evaluated respectively.

[0116] 15g of catalyst was loaded into a fixed-bed reactor, and deionized water and ethylene oxide were subjected to a catalytic hydration reaction. The process conditions were as follows: reaction temperature 90℃, pressure 1.2MPa, water to ethylene oxide molar ratio 10:1, and reaction space velocity (FSV) as shown in Table 1. Samples were taken for conversion (C0). EO ,%) and selectivity (S EG The determination of ,% was performed using high-purity nitrogen as the protective gas, and the test results are shown in Table 1.

[0117] Table 1

[0118]

[0119]

[0120] The above description is merely a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, based on the technical teachings provided by the present invention and as common knowledge in the field, other equivalent modifications and improvements can be made, and these should also be considered within the scope of protection of the present invention.

Claims

1. A process for the preparation of a diol by reacting an alkylene oxide with water in the presence of an ion exchange resin catalyst, characterized in that, The ion exchange resin catalyst has the chemical formula: P1-PS-CH2N + R1R2R3M - , Wherein, P1 is styrene / divinylbenzene copolymer microspheres; PS is polystyrene segment; N + It is a quaternary ammonium cation; R1, R2, and R3 are each independently an alkyl C. x H y x is any integer from 1 to 6, and y is any integer from 3 to 13; M - Selected from bicarbonate ions, hydroxide ions, bisulfite ions, formate ions, acetate ions, or citrate ions; The catalyst is obtained by polymerizing styrene / divinylbenzene copolymer microspheres with chloromethylated resin matrix, followed by chloromethylation, quaternization and ion exchange reactions. Based on the total weight of the copolymer microspheres, the amount of styrene used is 5-20% by weight.

2. The production method according to claim 1, characterized by, R1, R2, and R3 are n-butane groups.

3. The production method according to claim 1 or 2, characterized by, The method for preparing the ion exchange resin catalyst includes: S1: Chloromethylated styrene / divinylbenzene copolymer microspheres are mixed with a solvent, and the polymerization reaction of styrene is initiated in the presence of an initiator to obtain styrene-modified resin matrix P1; S2: The styrene-modified resin matrix P1 obtained in step S1 is subjected to chloromethylation, quaternization and ion exchange reactions in sequence; Based on the total weight of the copolymer microspheres, the amount of styrene used is 5-20% by weight.

4. The production method according to claim 3, characterized by, The degree of crosslinking of the chloromethylated styrene / divinylbenzene copolymer microspheres is 2-8%; and / or, Based on the total weight of the copolymer microspheres, the amount of the initiator is 0.1~5% by weight; and / or, The initiator comprises cuprous chloride and 2,2'-bipyridine; and / or, The solvent is selected from at least one of 1,4-dioxane, toluene, tetrahydrofuran, and anisole; and / or, The conditions for the polymerization reaction include: a temperature of 80~110℃ and a time of 1~3h.

5. The preparation method according to claim 4, characterized in that, The molar ratio of cuprous chloride to 2,2'-bipyridine is 1:2 to 1:

5.

6. The preparation method according to claim 3, characterized in that, The steps of the chloromethylation reaction include: in the presence of zinc chloride, styrene-modified resin matrix P1 is subjected to a chloromethylation reaction with a chloromethylation reagent to obtain modified microspheres.

7. The production method according to claim 6, characterized by, Based on the weight of the styrene-modified resin matrix P1, the amount of zinc chloride used is 12~100% by weight; and / or, The chloromethylation reagent is selected from chloromethyl ether, chloroethyl ether, chloromethyl ethyl ether, or 1,4-dichloromethoxybutane; and / or, The weight ratio of styrene-modified resin matrix P1 to chloromethylation reagent is 1:2~6; and / or, The conditions for the chloromethylation reaction include: a temperature of 25~60℃ and a time of 4~30h.

8. The preparation method according to claim 3, characterized in that, The quaternization reaction includes: quaternizing modified microspheres, a quaternizing agent, and N,N-dimethylformamide to obtain modified ammonium spheres.

9. The production method according to claim 8, characterized by, The weight ratio of modified microspheres, quaternizing agent, and N,N-dimethylformamide is 1:0.3~2:5~15; and / or, The quaternizing agent is selected from at least one of trimethylamine, triethylamine, tripropylamine, and tri-n-butylamine; and / or, The conditions for the quaternization reaction include: a temperature of 40~90℃ and a time of 10~48h.

10. The preparation method according to claim 8, characterized in that, The steps of the ion exchange reaction include: washing the modified ammonium spheres with a salt solution and then washing them with water.

11. The method of claim 10, wherein, The weight ratio of the modified ammonium spheres to the salt solution is 1:50~100; the concentration of the salt solution is 0.1~1 mol / L; and / or, The salt solution is selected from at least one of the following: a solution containing bicarbonate ions, a solution containing hydroxide ions, a solution containing bisulfite ions, and an organic acid metal salt solution.

12. The method of claim 11, wherein, The organic acid is selected from at least one of formic acid, acetic acid, and citric acid; and / or, The salt solution is selected from at least one of NaHCO3 aqueous solution, sodium citrate aqueous solution, sodium formate aqueous solution, sodium hydroxide aqueous solution, and potassium hydroxide aqueous solution.

13. The production method according to claim 1 or 2, characterized by, The epoxide alkane has the general structural formula shown in Formula I: , formula I Wherein, R4-R7 may be the same or different, and each is independently selected from hydrogen, C1-C4 alkyl, and C6-C8 aryl; and / or, The reaction temperature between the epoxide and water is 40~150℃; and / or, The reaction pressure between the epoxide and water is 0.1~10 MPa; and / or, The molar ratio of water to epoxide is 1~50:1; and / or, The liquid hourly space velocity of the reaction of the alkylene oxide with water is from 0.1 to 6 h -1 .

14. The method of claim 13, wherein, R4-R7 may be the same or different, and each is independently selected from at least one of hydrogen, methyl, ethyl, propyl, and phenyl; and / or, The reaction temperature between the epoxide and water is 80~110℃; and / or, The reaction pressure between the epoxide and water is 1~2.5 MPa; and / or, The molar ratio of water to epoxide is 6~20:1; and / or, The liquid hourly space velocity of the reaction of the alkylene oxide with water is from 2 to 6 h -1 .

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