Method for contact reaction of epoxy compound and hydroxyl compound

Abstract

The invention relates to a contact reaction method of an epoxy compound and a hydroxyl compound. The method comprises the following steps: carrying out contact reaction on an epoxy compound and a hydroxyl compound in the presence of a catalyst; the catalyst comprises a resin matrix and a quaternary ammonium salt group grafted on the resin matrix, and alkyl grafted with the resin matrix on the quaternary ammonium salt group is an alkylene chain. According to the method disclosed by the invention, the epoxy compound and the hydroxyl compound are subjected to contact reaction, so that the conversion rate of the epoxy compound can reach more than 95% and the selectivity of the dialkyl glycol compound can reach more than 90% under relatively mild reaction conditions.

Description

Technical Field

[0001] This invention relates to a method for the contact reaction of an epoxy compound with a hydroxyl compound. Background Technology

[0002] Diethylene glycol (DEG) is a colorless, odorless, transparent, hygroscopic viscous liquid. It is readily soluble in polar solvents such as water, alcohols, acetone, diethyl ether, and ethylene glycol, and its chemical properties are similar to those of ethylene glycol (EG). Diethylene glycol can be used directly as a solvent for nitrocellulose, resins, oils, and printing inks; as a natural gas dehydrating agent; as an aromatic hydrocarbon separation and extraction agent; as a textile lubricant, softener, and finishing agent; and as an antifreeze component in brake fluids and compressor lubricating oils. It can also be used in the formulation of cleaning agents.

[0003] As a byproduct of the ethylene glycol production process via ethylene oxide hydration, the yield of diethylene glycol is constrained by the operating conditions of the ethylene glycol plant, typically accounting for 8-10% of the total ethylene glycol production. Currently, ethylene oxide / ethylene glycol production technology is mature, primarily supplied by large chemical companies such as Dow, SD, and Shell. The main process involves reacting ethylene oxide and excess water in a tubular reactor at 150-200°C and 1.5-2.5 MPa, directly hydrating them in the liquid phase to produce ethylene glycol, while simultaneously producing diethylene glycol, triethylene glycol, and polyethylene glycols as byproducts. In industrial production, the molar ratio of the main products is approximately EG:DEG:TEG = 100:10:1. The resulting dilute ethylene glycol solution is cooled via a heat exchanger and then pumped to an evaporator for concentration. After multi-effect evaporation, pure ethylene glycol, diethylene glycol, and triethylene glycol are obtained.

[0004] With the increase in downstream demand for diethylene glycol, the production capacity, output, and demand of diethylene glycol will all show an upward trend.

[0005] CN215538513U discloses a molecular distillation recovery device for polyethylene glycol, a byproduct of ethylene glycol processes. This device can achieve a high vacuum inside the molecular distillation unit, reduce the heating time of polyethylene glycol and heavy components in the material, shorten the distance between the heating surface and the condensation surface, prevent further polymerization or deterioration of heavy components in the material, and improve the recovery rate of polyethylene glycol.

[0006] CN112321397A discloses a new method for increasing triethylene glycol production in an EOEG unit. This method involves adding a diethylene glycol circulation pipeline or a crude diethylene glycol / triethylene glycol mixture circulation pipeline to the original process. The circulating diethylene glycol or the crude diethylene glycol / triethylene glycol mixture enters the hydration reactor, where it hydrates with ethylene oxide to produce triethylene glycol. This increases the concentration of diethylene glycol in the hydration reactor, thereby increasing triethylene glycol production.

[0007] The above methods for producing diethylene glycol are limited by the capacity of the EOEG unit, and can only adjust the output of diethylene glycol within a certain range, without fundamentally solving the production problem of diethylene glycol. Summary of the Invention

[0008] The purpose of this invention is to overcome the problems of low efficiency (few direct products and many by-products) and high temperature required in the direct reaction of epoxy compounds and hydroxyl compounds in the prior art, and to provide a method for the contact reaction of epoxy compounds and hydroxyl compounds. This method has the characteristics of high efficiency, mild reaction conditions and high raw material utilization.

[0009] To achieve the above objectives, the present invention provides a method for contact reaction of an epoxy compound and a hydroxyl compound, the method comprising: contact reaction of an epoxy compound and a hydroxyl compound under catalytic conditions; wherein the catalyst comprises a resin matrix and quaternary ammonium salt groups grafted onto the resin matrix, the quaternary ammonium salt groups being grafted onto the resin matrix via alkylene chains.

[0010] Through the above technical solution, the present invention has the following advantages:

[0011] By using the method of the present invention to react epoxy compounds with hydroxyl compounds, the conversion rate of epoxy compounds can reach more than 95% and the selectivity of direct reaction products can reach more than 90% under relatively mild reaction conditions. Attached Figure Description

[0012] Figure 1 This is the infrared spectrum of Cat-A2. Detailed Implementation

[0013] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] This invention provides a method for the contact reaction of an epoxy compound and a hydroxyl compound, the method comprising: contacting the epoxy compound and the hydroxyl compound under catalytic conditions; wherein the catalyst comprises a resin matrix and quaternary ammonium salt groups grafted onto the resin matrix, the quaternary ammonium salt groups being grafted onto the resin matrix via alkylene chains.

[0015] By using the method of the present invention to react epoxy compounds with hydroxyl compounds, the conversion rate of epoxy compounds can reach more than 95% and the selectivity of direct reaction products can reach more than 90% under relatively mild reaction conditions.

[0016] For example, when the alkylene chain is butylene, the catalyst has the structure shown in the following formula:

[0017]

[0018] In the formula, Resin matrix; *-N + R1R2R3X - It is a quaternary ammonium salt group; R1, R2, and R3 may be the same or different, and each is independently an alkyl group; X - It is an anion.

[0019] According to a preferred embodiment of the present invention, the resin matrix of the catalyst comprises at least two polystyrene segments connected by crosslinking agent structural units. These crosslinking agent structural units contain ester groups and / or phenylene groups. In this invention, the crosslinking agent structural units are provided by dialkenyl aromatics, polyalkenyl aromatics, and polyunsaturated acid alcohol ester compounds. By adopting the aforementioned preferred embodiment, the conversion rate of the raw material epoxy compound and the selectivity of the direct reaction product can be further improved.

[0020] In this invention, it should be noted that the polystyrene fragment may or may not contain substituents, the dialkenylbenzene is an aromatic compound containing two alkenyl groups, the polyalkenylbenzene is an aromatic compound containing two or more alkenyl groups, and the polyunsaturated acid alcohol ester is an ester compound containing two or more unsaturated hydrocarbon groups.

[0021] According to a preferred embodiment of the present invention, the total mass of polystyrene segments accounts for 20wt%-95wt% of the total mass of the resin matrix, for example, 20wt%, 30wt%, 40wt%, 50wt%, 55wt%, 60wt%, 70wt%, 80wt%, 95wt%, etc., preferably 70wt%-95wt%; the total mass of crosslinking agent structural units accounts for 5wt%-80wt% of the total mass of the resin matrix, for example, 5wt%, 10wt%, 20wt%, 25wt%, 30wt%, 40wt%, 50wt%, 55wt%, 60wt%, 70wt%, 80wt%, etc., preferably 5wt%-30wt%. By adopting the aforementioned preferred embodiment, the conversion rate of the raw material epoxy compound and the selectivity of the direct reaction product can be further improved.

[0022] According to a preferred embodiment of the present invention, the quaternary ammonium salt group in the catalyst is grafted onto the resin matrix via a C3-C5 alkylene chain. By adopting the aforementioned preferred embodiment, the conversion rate of the raw material epoxy compound and the selectivity of the direct reaction product can be further improved.

[0023] According to a preferred embodiment of the present invention, the hydrocarbon groups in the quaternary ammonium salt group are each independently selected from alkyl groups, preferably C1-C6 alkyl groups. By adopting the aforementioned preferred embodiment, the conversion rate of the raw material epoxide compound and the selectivity of the direct reaction product can be further improved.

[0024] In this invention, the types of anions in the catalyst can be conventionally selected in the art. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the anion of the quaternary ammonium salt group in the catalyst is at least one of bicarbonate ion, hydroxide ion, bisulfite ion, formate ion, acetate ion and citrate ion.

[0025] In this invention, there are no special requirements for the apparatus for the contact reaction. According to a preferred embodiment of the invention, the contact reaction is carried out in a fixed-bed reactor.

[0026] According to a preferred embodiment of the present invention, the catalyst is packed in at least three beds in the reactor, for example, four or five beds. By adopting the aforementioned preferred embodiment, the conversion rate of the feedstock epoxide and the selectivity of the direct reaction products can be further improved.

[0027] According to a preferred embodiment of the present invention, along the flow direction of the epoxide compound, the average particle size of the catalyst packed in each bed of the reactor increases layer by layer, with an increase of 0.1-0.5 mm / layer, for example, 0.2 mm / layer, 0.3 mm / layer, and 0.4 mm / layer. By adopting the aforementioned preferred embodiment, the conversion rate of the raw material epoxide compound and the selectivity of the direct reaction product can be further improved.

[0028] In this invention, the proportion of each component in the catalyst is not particularly limited, as long as the purpose of this invention can be achieved. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, based on the total mass of the catalyst, the content of the resin matrix in the catalyst is 30-80%, for example, it can be 40%, 50%, 60%, 70%, 80%, etc., preferably 40-70%; the content of quaternary ammonium salt groups is 15-65%, for example, it can be 20%, 30%, 40%, 50%, 60%, 65%, etc., preferably 30-50%; and the content of alkylene chains is 5-20%, for example, it can be 5%, 10%, 15%, etc., preferably 10-20%.

[0029] To further improve the conversion rate of the raw material epoxy compound and the selectivity of the direct reaction product, according to a preferred embodiment of the present invention, the mass ratio of the resin matrix to the quaternary ammonium salt group is controlled to be 0.8-4.5:1, for example, it can be 0.8:1, 1.5:1, 2:1, 3:1, etc., preferably 0.8-3:1. By adopting the aforementioned preferred scheme, the conversion rate of the raw material epoxy compound and the selectivity of the direct reaction product can be further improved.

[0030] The present invention does not have any special requirements for the preparation of the catalyst, and the conventional method in the art is usually used. The following is an illustrative description, but does not limit the scope of the present invention. The preparation method of the catalyst includes the following steps: (1) Preparation of resin matrix: In the presence of an initiator, styrene monomers and crosslinking monomers are mixed in a solvent to carry out a copolymerization reaction; (2) The resin groups are subjected to ammoniation reaction and ion exchange reaction in sequence.

[0031] In this invention, there are no special requirements for the choice of solvent. Generally, it is a deionized aqueous solution of the dispersant, such as a 2% deionized aqueous solution of gelatin.

[0032] In this invention, the type of styrene monomer can be a conventional choice in the art, wherein the styrene monomer is 1-(4-haloalkyl)-4-vinylbenzene, preferably in which the haloalkyl group is a bromoalkyl group. By adopting the aforementioned preferred embodiment, the prepared catalyst is more suitable for the method of this invention, further improving the conversion rate of the raw material epoxide and the selectivity of the diol compound.

[0033] According to a preferred embodiment of the present invention, the crosslinking monomer is selected from at least one of dialkenylbenzene, polyalkenylbenzene, and polyunsaturated acid alcohol esters, preferably dialkenylbenzene and / or polyalkenylbenzene. By adopting the aforementioned preferred embodiment, the prepared catalyst is more suitable for the method of the present invention, further improving the conversion rate of the raw material epoxy compound and the selectivity of the direct reaction product.

[0034] In this invention, the di-alkenylbenzene is an aromatic hydrocarbon compound containing two alkenyl groups, and the polyalkenylbenzene is an aromatic hydrocarbon compound containing more than two alkenyl groups. According to a preferred embodiment of this invention, the di-alkenylbenzene and / or polyalkenylbenzene are selected from one or more of divinylbenzene, diallylbenzene, 1,1-(4-vinylphenyl)methane, 1,2-bis(vinylphenyl)ethane, and tetra(4-vinylphenyl)methane.

[0035] In this invention, the polyunsaturated acid alcohol ester does not contain ester compounds with two or more unsaturated hydrocarbon groups. According to a preferred embodiment of this invention, the polyunsaturated acid alcohol ester is selected from one or more of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate.

[0036] In this invention, no special requirements are made for the selection of the initiator. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptanenitrile, lauroyl peroxide, and cumene hydroperoxide.

[0037] In this invention, the conditions for the copolymerization reaction are generally within the conventional range in the art. According to a preferred embodiment of the invention, the conditions for the copolymerization reaction include: a polymerization temperature of 60-100°C. The copolymerization reaction time can be adjusted depending on the temperature and other conditions, for example, it can be 8-24 hours.

[0038] To further improve the performance of the catalyst, making it more suitable for the present invention, and to increase the conversion rate of the raw material epoxy compound and the selectivity of the diol compound, according to a preferred embodiment of the present invention, the copolymerization reaction is first carried out at 65-75°C for 1-3 hours, then heated to 80-85°C for 2-6 hours, and finally heated to 90-98°C for 3-6 hours.

[0039] In this invention, the conditions for the ammoniation reaction are not particularly required and are generally conventional conditions in the art. According to a preferred embodiment of the invention, the ammoniation reaction conditions include: a weight ratio of polymer, ammoniation reagent, and solvent of 1:0.3-3:3.5-15 based on the weight of the polymer. According to a preferred embodiment of the invention, the ammoniation reaction conditions further include: a temperature of 40-90°C, preferably 50-80°C. According to a preferred embodiment of the invention, the ammoniation reaction conditions further include: a time of 10-48 hours, preferably 15-30 hours.

[0040] According to a preferred embodiment of the present invention, the ammoniation reaction conditions further include: the ammoniation reagent is a C1-C6 organic amine, preferably selected from one or more of trimethylamine, triethylamine, tripropylamine, tri-n-butylamine, N,N-dimethylethylamine and / or diethylpropylamine.

[0041] In this invention, the solvent used for ammoniation is not particularly limited. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the solvent used for ammoniation is selected from one or more of N,N-dimethylformamide, acetonitrile, N,N-dimethylacetamide and tetrahydrofuran.

[0042] In this invention, the ammoniation product is filtered, washed and dried to obtain ammoniation microspheres. The methods and conditions for filtration, washing and drying are usually conventional choices in the art and are not limited in this invention.

[0043] In this invention, the conditions for the ion exchange reaction are not particularly required and are generally conventional conditions in the art. According to a preferred embodiment of the invention, the conditions for the ion exchange reaction include: the weight ratio of the ammonified microspheres to the X--containing solution is 1:10-100, preferably 1:10-40; the concentration of the X--containing solution is 0.1-1 mol / L; and / or the temperature is 25-40℃; and / or the time is 5-12 h.

[0044] In this invention, the product after ion exchange is washed and dried to obtain ion exchange resin. The washing and drying methods and conditions are usually conventional choices in the art and are not limited in this invention.

[0045] In this invention, generally speaking, any epoxide compound can be reacted using the method of this invention. Studies have found that epoxide compounds with 0-4 alkyl and / or aryl substituted alkylene oxides are more suitable for the method of this invention, especially when the epoxide compound is ethylene oxide.

[0046] The alkyl and / or aryl groups can be conventional choices in the art; in this invention, the alkyl group is selected as C1-C6 alkyl, and the aryl group is selected as C6-C6 alkyl. 10 Aryl groups can react more effectively, thus achieving the purpose of this invention.

[0047] In this invention, there are no particular requirements for the type of hydroxyl compound. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the hydroxyl compound is selected from at least one of ethylene glycol, diethylene glycol and triethylene glycol, preferably ethylene glycol.

[0048] According to a preferred embodiment of the present invention, the conditions for the contact reaction include a temperature of 40-180°C, preferably 70-110°C.

[0049] According to a preferred embodiment of the present invention, the conditions for the contact reaction include: a pressure of 0.1-10.0 MPa, preferably 0.8-2.5 MPa.

[0050] According to a preferred embodiment of the present invention, the conditions for the contact reaction include: the molar ratio of the hydroxyl compound to the epoxide is (1-50):1, preferably (10-15):1.

[0051] According to a preferred embodiment of the present invention, the conditions for the contact reaction include a liquid hourly space velocity (LHSV) of 0.1-6.0 h⁻¹. -1 Preferably, it is 0.5-4.0h. -1 .

[0052] Conducting the reaction under the aforementioned preferred contact conditions ensures that the reaction achieves high conversion rates and target product selectivity under mild conditions.

[0053] The present invention will be described in detail below through examples. In the following examples, the EO conversion rate and DEG and TriEG selectivity are calculated by the following formula:

[0054] C EO (%) = [n (DEG) +2n (TriEG) +3n (TetraEG) ] / n 0(EO) ×100%

[0055] S DEG (%) = n (DEG) / [n (DEG) +2n (TriEG) +3n (TetraEG) ]×100%

[0056] S TriEG (%) = n (TriEG) / [n (DEG) +2n (TriEG) +3n (TetraEG) ]×100%

[0057] Where C EO For EO conversion rate; S DEG For DEG selectivity; S TriEG For TriEG selectivity; n 0(EO) n represents the amount of EO fed, in mol. (DEG) n (TriEG) and n (TetraEG) These represent the amounts of diethylene glycol, triethylene glycol, and tetraethylene glycol in the product, in moles.

[0058] The raw materials were purchased from Sinopharm Chemical Reagent Co., Ltd., and all reagents used were commercially available products. Divinylbenzene was a mixture of isomers with a content of 80%.

[0059] Example 1

[0060] Resin preparation: 70.0 g of 1-(4-bromobutyl)-4-vinylbenzene, 5.0 g of divinylbenzene, and 2.0 g of benzoyl peroxide were added to a three-necked flask and mixed thoroughly. Then, 300 ml of a 2% deionized gelatin aqueous solution was added, and the mixture was stirred for 1 hour. The temperature was then gradually increased to 65°C for 2 hours, then to 85°C for 5 hours, and finally to 97°C for 4 hours. After the reaction was completed, the supernatant was poured off, and the remaining polymer solid was washed with 85°C deionized water, then with room temperature deionized water, filtered, and dried in a vacuum oven at 50°C to obtain polymer A1.

[0061] Ammoniation reaction: 40 g of the prepared polymer A1 was added to a three-necked flask, followed by 30 g of trimethylamine and 250 ml of N,N-dimethylformamide. The mixture was reacted at 60 °C for 24 hours. After cooling to room temperature, the mixture was filtered, washed with ethyl acetate, deionized water, and methanol, and then dried under vacuum at 50 °C to obtain ammoniation microspheres A1.

[0062] Ion exchange: In a three-necked flask, for every 40 g of the prepared ammonium-modified microspheres A1, 500 ml of a 1.0 mol / L deionized water solution of NaHCO3 was added, and the mixture was stirred at room temperature for 12 hours. Then, the mixture was washed with deionized water until the pH of the washing solution was 7, and after vacuum drying, the ion exchange resin Cat-A1 was obtained.

[0063] Example 2

[0064] Resin preparation: 50 g of 1-(4-bromobutyl)-4-vinylbenzene, 10 g of 1,2-bis(4-vinylphenyl)ethane, and 1.5 g of benzoyl peroxide were added to a three-necked flask and mixed thoroughly. Then, 250 ml of a 2% deionized gelatin aqueous solution was added, and the mixture was stirred for 1 hour. The temperature was then gradually increased to 70°C for 1 hour, then to 85°C for 4 hours, and finally to 98°C for 5 hours. After the reaction was complete, the supernatant was poured off, and the remaining polymer solid was washed with 85°C deionized water, then with room temperature deionized water, filtered, and dried in a vacuum oven at 50°C to obtain polymer A2.

[0065] Ammoniation reaction: 50 g of the prepared polymer A2 was added to a three-necked flask, followed by 25 g of trimethylamine and 250 ml of N,N-dimethylformamide. The mixture was reacted at 50 °C for 20 hours. After cooling to room temperature, the mixture was filtered, washed with ethyl acetate, deionized water, and methanol, and then dried under vacuum at 50 °C to obtain ammoniation microspheres A2.

[0066] Ion exchange: In a three-necked flask, for every 40 g of the prepared ammonium-modified microspheres A2, 500 ml of a 0.8 mol / L deionized NaOH solution was added, and the mixture was stirred at room temperature for 12 hours. Subsequently, the solution was washed with deionized water until the pH of the washings reached 7, and then vacuum dried to obtain the ion exchange resin Cat-A2. The infrared spectrum was measured as follows. Figure 1 As shown.

[0067] Example 3

[0068] Resin preparation: 50 g of 1-(4-bromobutyl)-4-vinylbenzene, 20 g of 1,2-bis(vinylphenyl)ethane, and 3.0 g of benzoyl peroxide were added to a three-necked flask and mixed thoroughly. Then, 300 ml of a 2% deionized gelatin aqueous solution was added, and the mixture was stirred for 1 hour. The temperature was then gradually increased to 65°C for 1.5 hours, then to 80°C for 6 hours, and finally to 95°C for 6 hours. After the reaction was complete, the supernatant was poured off, and the remaining polymer solid was washed with 85°C deionized water, then with room temperature deionized water, filtered, and dried in a vacuum oven at 50°C to obtain polymer A3.

[0069] Ammoniation reaction: 50 g of the prepared polymer A3 was added to a three-necked flask, followed by 20 g of trimethylamine and 250 ml of N,N-dimethylformamide. The mixture was reacted at 45 °C for 2 hours, cooled to room temperature, filtered, washed with ethyl acetate, deionized water, and methanol, and then dried under vacuum at 50 °C to obtain ammoniation microspheres A3.

[0070] Ion exchange: In a three-necked flask, for every 40 g of the prepared ammonium-modified microspheres A3, 500 ml of a 1.0 mol / L deionized water solution of NaHCO3 was added, and the mixture was stirred at room temperature for 12 hours. Then, it was washed with deionized water until the pH of the washing solution was 7, and after vacuum drying, the ion exchange resin Cat-A3 was obtained.

[0071] Example 4

[0072] Same as Example 1, except that:

[0073] In the resin preparation process, divinylbenzene is replaced with 1,2-bis(4-vinylphenyl)ethane to obtain the ion exchange resin Cat-A4.

[0074] Example 5

[0075] Same as Example 1, except that:

[0076] During the resin preparation process, the amount of divinylbenzene added was changed to 0.5 grams to obtain the ion exchange resin Cat-A5.

[0077] Example 6

[0078] Same as Example 1, except that:

[0079] During the resin preparation process, 1-(4-bromobutyl)-4-vinylbenzene was replaced with 1-(4-bromomethyl)-4-vinylbenzene to obtain the ion exchange resin Cat-A6.

[0080] Example 7

[0081] Same as Example 1, except that:

[0082] During the resin preparation process, 30.0 g of 1-(4-bromobutyl)-4-vinylbenzene and 50 g of divinylbenzene were used to obtain the ion exchange resin Cat-A7.

[0083] Comparative Example 1

[0084] Resin preparation: 35.0 g of 1-(4-bromobutyl)-4-vinylbenzene, 5.0 g of divinylbenzene, and 2.0 g of benzoyl peroxide were added to a 500 mL three-necked flask and mixed thoroughly. Then, 300 mL of a 2% deionized gelatin aqueous solution was added, and the mixture was stirred for 1 hour. The temperature was then gradually increased to 65 °C for 2 hours, then to 85 °C for 5 hours, and finally to 97 °C for 4 hours. After the reaction was completed, the supernatant was poured off, and the remaining polymer solid was washed with 85 °C deionized water, then with room temperature deionized water, filtered, and dried in a vacuum oven at 50 °C to obtain polymer D1.

[0085] Polymer D1 prepared in Comparative Example 1 was placed in toluene and swollen for 1 hour. Then, a mixture of 35 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 the modified resin matrix.

[0086] Chloromethylation of the modified resin matrix: In a 500ml three-necked flask, add 40g of the prepared modified resin matrix 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 chlorinated spheres.

[0087] Modified chloride spheres were subjected to ammoniation and ion exchange under the same conditions as in Example 1 to obtain ion exchange resin Cat-A8.

[0088] Example 8

[0089] In a fixed-bed reactor, catalysts Cat-A1 to Cat-A8 were sieved into microspheres with an average particle size of 0.6 mm and packed in three layers for the contact reaction of ethylene oxide and ethylene glycol. The reaction conditions and results are listed in Table 1.

[0090] Example 9

[0091] The catalyst Cat-A1 was sieved into three types of microspheres with average particle sizes of 0.4 mm, 0.6 mm and 0.8 mm, respectively, and applied to the contact reaction of ethylene oxide and ethylene glycol. The reaction was carried out in a fixed-bed reactor with the feed material fed from the top. The reactor was set with three catalyst beds from top to bottom, which were sequentially filled with the three types of microspheres of 0.4 mm, 0.6 mm and 0.8 mm obtained by sieving.

[0092] The reaction conditions were: temperature 80℃, pressure 1.2MPa, and space velocity 0.6h. -1 The molar ratio of alcohol to alkane is 12.

[0093] The reaction results were: EO conversion rate 99.0%, DEG selectivity 97.2%, and TriEG selectivity 2.8%.

[0094] Table 1

[0095]

[0096] 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 inventive concept, 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 considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for reacting an epoxy compound with a hydroxyl compound, characterized in that, The method includes: reacting an epoxide compound with a hydroxyl compound under catalytic conditions; The catalyst comprises a resin matrix and quaternary ammonium salt groups grafted onto the resin matrix, the quaternary ammonium salt groups being grafted onto the resin matrix via alkylene chains.

2. The method according to claim 1, wherein, The resin matrix of the catalyst comprises at least two polystyrene segments connected by crosslinking agent structural units, wherein the crosslinking agent structural units contain ester groups and / or phenylene groups; and / or The total mass of polystyrene segments accounts for 20wt%-95wt% of the total mass of the resin matrix, preferably 70wt%-95wt%; the total mass of crosslinking agent structural units accounts for 5wt%-80wt% of the total mass of the resin matrix, preferably 5wt%-30wt%.

3. The method according to claim 1 or 2, wherein, In the catalyst, the quaternary ammonium salt group is grafted onto the resin matrix via a C3-C5 alkylene chain; and / or In the quaternary ammonium salt group, each hydrocarbon group is independently selected from alkyl groups, preferably C1-C6 alkyl groups; and / or The anion of the quaternary ammonium salt group in the catalyst is at least one of bicarbonate ion, hydroxide ion, bisulfite ion, formate ion, acetate ion and citrate ion.

4. The method according to any one of claims 1-3, wherein, The contact reaction is carried out in a fixed-bed reactor; and / or The catalyst is packed in at least three beds in the reactor; and / or Along the flow direction of the epoxy compound, the average particle size of the catalyst packed in each bed of the reactor increases layer by layer, with an increase of 0.1-0.5 mm / layer.

5. The method according to any one of claims 1-4, wherein, Based on the total mass of the catalyst, the catalyst, The resin matrix content is 30-80%, preferably 40-70%, the quaternary ammonium salt group content is 15-65%, preferably 30-50%, and the alkylene chain content is 5-20%, preferably 10-20%. Preferably, the mass ratio of resin matrix to quaternary ammonium salt groups is 0.8-4.5:1, and more preferably 0.8-3:

1.

6. The method according to any one of claims 1-5, wherein, The method for preparing the catalyst includes the following steps: (1) Preparation of resin matrix: Styrene monomers and crosslinking monomers are mixed in a solvent in the presence of an initiator to carry out copolymerization reaction; (2) The resin groups undergo ammoniation and ion exchange reactions in sequence.

7. The method according to claim 6, wherein, The styrene monomer is 1-(4-haloalkyl)-4-vinylbenzene, preferably in which the haloalkyl group in 1-(4-haloalkyl)-4-vinylbenzene is a bromalkyl group; and / or The crosslinking monomer is selected from at least one of dialkenylbenzene, polyalkenylbenzene, and polyunsaturated acid alcohol esters, preferably dialkenylbenzene and / or polyalkenylbenzene; and / or The initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptanenitrile, lauroyl peroxide, and cumene hydroperoxide; and / or The conditions for the copolymerization reaction include: a polymerization temperature of 60-100℃; and / or a time of 8-24h; preferably, the copolymerization reaction is first carried out at 65-75℃ for 1-3 hours, then heated to 80-85℃ for 2-6 hours, and finally heated to 90-98℃ for 3-6 hours.

8. The method according to any one of claims 1-7, wherein, The epoxy compound is an alkylene oxide with 0-4 alkyl and / or aryl substituted groups, preferably ethylene oxide. Preferably, the alkyl group is a C1-C6 alkyl group, and the aryl group is a C6-C6 alkyl group. 10 Aryl.

9. The method according to any one of claims 1-8, wherein, The hydroxyl compound is selected from at least one of ethylene glycol, diethylene glycol, and triethylene glycol, preferably ethylene glycol.

10. The method according to any one of claims 1-9, wherein, The conditions for the contact reaction include: The temperature is 40-180℃, preferably 70-110℃; and / or The pressure is 0.1-10.0 MPa, preferably 0.8-2.5 MPa; and / or The molar ratio of the hydroxyl compound to the epoxide is (1-50):1, preferably (10-15):1; and / or Liquid space velocity is 0.1-6.0 h⁻¹ -1 Preferably, it is 0.5-4.0h. -1 .

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