Method for co-producing diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof

Abstract

The invention relates to a method for co-producing diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof. The method comprises the following steps: carrying out contact reaction on ethylene oxide and a derivative thereof and ethylene glycol in the presence of a styrene copolymer; the styrene copolymer is modified by cyclic quaternary ammonium salt and has a structure as shown in the following formula (1): the styrene copolymer is a styrene copolymer matrix, R is an alkylene chain, R1 is an alkylene chain, R2 is an alkyl group, X <-> is an anion, and R and N together form a 5-10-membered aliphatic heterocyclic ring. According to the method disclosed by the invention, ethylene oxide and derivatives thereof have excellent conversion rate, the selectivity of polyethylene glycol is high, and co-production of diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof can be realized.

Description

Technical Field

[0001] This invention relates to a method for the co-production of diethylene glycol and its derivatives, and triethylene glycol and its derivatives. Background Technology

[0002] Polyethylene glycols, including diethylene glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol (TTEG), have a wide range of applications. For example, diethylene glycol is a colorless, odorless, transparent, hygroscopic viscous liquid with chemical properties similar to ethylene glycol (EG). Directly, diethylene glycol can be used as a solvent for nitrocellulose, resins, oils, and printing inks; a natural gas dehydrating agent; an aromatic hydrocarbon separation and extraction agent; a textile lubricant, softener, and finishing agent; and also as an antifreeze component in brake fluids and compressor lubricating oils. It can also be used to formulate cleaning agents. Triethylene glycol has wide applications in the pharmaceutical, coating, textile, printing and dyeing, food, papermaking, cosmetics, leather, photography, printing, and metal processing industries. It can be used as a solvent for aromatic hydrocarbon extraction, a solvent for rubber and nitrocellulose, and as an additive for diesel fuel and rocket fuel.

[0003] Diethylene glycol and triethylene glycol are both byproducts of the ethylene glycol production process via ethylene oxide hydration. Their yield is constrained by the operating conditions of the ethylene glycol plant. In general industrial production, the molar ratio of the main products is approximately EG:DEG:TEG = 100:10:1. Currently, ethylene oxide / ethylene glycol production technology is mature, primarily provided 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℃ 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. 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] CN115991634A discloses a method for producing triethylene glycol, in which ethylene oxide and diethylene glycol are mixed in a static mixer and then reacted at elevated temperatures to produce triethylene glycol. This method can be used to retrofit existing EO / EG plants, significantly increasing the yield of the byproduct triethylene glycol. The preparation process is simple, has a high yield, and allows for flexible production based on market changes.

[0005] It is evident that the current production of polyethylene glycols (such as diethylene glycol and triethylene glycol) is limited by the capacity of EOEG units. Summary of the Invention

[0006] The purpose of this invention is to overcome the problem of low production efficiency of polyethylene glycol in the prior art, and to provide a method for co-producing diethylene glycol and its derivatives and triethylene glycol and its derivatives, which has the characteristics of high polyethylene glycol preparation efficiency.

[0007] To achieve the above objectives, the present invention provides a method for co-producing diethylene glycol and its derivatives and triethylene glycol and its derivatives, the method comprising: contacting ethylene oxide and its derivatives with ethylene glycol in the presence of a styrene copolymer;

[0008] The styrene copolymer is modified with a cyclic quaternary ammonium salt and has the structure shown in formula (1):

[0009]

[0010] It is a styrene copolymer matrix, where R is an alkylene chain, R1 is an alkylene chain, R2 is an alkyl group, and X is an alkyl group. - It is an anion, and R together with N forms a 5-10 membered aliphatic heterocycle.

[0011] Through the above technical solution, the present invention has the following advantages:

[0012] The method of the present invention exhibits excellent conversion rates of ethylene oxide and its derivatives, and high selectivity for polyethylene glycols, enabling the co-production of diethylene glycol and its derivatives and triethylene glycol and its derivatives. The selectivity of triethylene glycol and its derivatives reaches more than 15%, and in preferred embodiments, it can reach more than 20%. Attached Figure Description

[0013] Figure 1 This is the infrared spectrum of the ion exchange resin Cat-A1. Detailed Implementation

[0014] 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.

[0015] In this invention, "derivative" refers to a substance derived from which hydrogen atoms in the matrix are replaced by hydrocarbon groups.

[0016] This invention provides a method for co-producing diethylene glycol and its derivatives and triethylene glycol and its derivatives, the method comprising: contacting ethylene oxide and its derivatives with ethylene glycol in the presence of a styrene copolymer;

[0017] The styrene copolymer is modified with a cyclic quaternary ammonium salt and has the structure shown in formula (1):

[0018]

[0019] In equation (1), It is a styrene copolymer matrix, where R is an alkylene chain, R1 is an alkylene chain, R2 is an alkyl group, and X is an alkyl group. - It is an anion, and R together with N forms a 5-10 membered aliphatic heterocycle.

[0020] The method of the present invention exhibits excellent conversion rates of ethylene oxide and its derivatives, and high selectivity for polyethylene glycols, enabling the co-production of diethylene glycol and its derivatives, as well as triethylene glycol and its derivatives.

[0021] In this invention, there are no special requirements for the selection of ethylene oxide and its derivatives. This invention uses ethylene oxide as an example to illustrate the solution of this invention.

[0022] According to a preferred embodiment of the present invention, R and N in formula (1) together form a 6-8 membered aliphatic heterocycle. By adopting the aforementioned preferred embodiment, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycols can be further improved.

[0023] According to a preferred embodiment of the present invention, the styrene copolymer matrix is ​​a gel-type styrene-crosslinker copolymer matrix. By adopting the aforementioned preferred embodiment, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycols can be further improved.

[0024] According to a preferred embodiment of the present invention, the degree of crosslinking of the gel-type styrene-crosslinker copolymer matrix is ​​1-15%. For example, it can be 2%, 5%, 8%, 10%, 15%, etc. By adopting the aforementioned preferred embodiment, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycol can be further improved.

[0025] According to a preferred embodiment of the present invention, the styrene-crosslinker copolymer matrix comprises 30-60 wt% by mass, for example, 40 wt%, 50 wt%, 60 wt%, etc., preferably 30-50 wt%. By adopting the aforementioned preferred embodiment, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycol can be further improved.

[0026] According to a preferred embodiment of the present invention, the crosslinking agent in the styrene copolymer matrix is ​​a di-alkenylbenzene and / or a poly-alkenylbenzene and / or a polyunsaturated acid alcohol ester, preferably a di-alkenylbenzene and / or a poly-alkenylbenzene. By adopting the aforementioned preferred embodiment, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycol can be further improved.

[0027] 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, and the polyalkenylbenzene is an aromatic compound containing two or more alkenyl groups. The polyunsaturated acid alcohol ester is an ester compound that does not contain two or more unsaturated hydrocarbon groups. According to a preferred embodiment of the present invention, the dialkenylbenzene 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. According to a preferred embodiment of the present 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.

[0028] According to a preferred embodiment of the present invention, in formula (1), R is a straight-chain or branched alkylene chain of C1-C10, preferably a straight-chain or branched alkylene chain of C2-C5. By adopting the aforementioned preferred embodiment, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycols can be further improved.

[0029] According to a preferred embodiment of the present invention, in formula (1), R1 is a straight-chain or branched alkylene chain of C2-C10, preferably a straight-chain or branched alkylene chain of C3-C6. By adopting the aforementioned preferred embodiment, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycols can be further improved.

[0030] According to a preferred embodiment of the present invention, in formula (1), R2 is a C1-C6 straight-chain or branched alkyl group. By adopting the aforementioned preferred embodiment, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycols can be further improved.

[0031] In this invention, there is no particular limitation on the type of X- in formula (1), and it is usually a conventional choice 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, X- is selected from at least one of bicarbonate ions, hydroxide ions, bisulfite ions, and organic acid ions, preferably bicarbonate ions. By adopting the aforementioned preferred scheme, the conversion rate of ethylene oxide and its derivatives and the selectivity of polyethylene glycol can be further improved.

[0032] 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.

[0033] 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.

[0034] According to a preferred embodiment of the present invention, along the ethylene oxide flow direction, 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 feedstock epoxide and the selectivity of the direct reaction products can be further improved.

[0035] In this invention, there are no special requirements for the preparation method of styrene copolymers, and conventional choices in the art can be made. According to a preferred embodiment of the present invention, the preparation method of the styrene copolymer includes the following steps: (a) preparing a saturated aliphatic nitrogen heterocyclic functionalized styrene copolymer matrix; (b) subjecting the saturated aliphatic nitrogen heterocyclic functionalized styrene copolymer matrix prepared in step (a) to ammoniation and ion exchange reactions in sequence.

[0036] According to a preferred embodiment of the present invention, step (a) involves copolymerization of 4-vinylphenylalkylazacycloalkanes and a crosslinking agent as comonomers in the presence of an initiator. For example, the 4-vinylphenylalkylazacycloalkanes may be: (1-[2-(4-vinylphenyl)ethyl]pyrrolidine) or 4-vinylbenzylpyrrolidine. By employing the aforementioned preferred embodiments, the styrene copolymer catalyst of the present invention can be prepared more simply and efficiently.

[0037] In this invention, the copolymerization reaction is carried out in a solvent, which is generally water containing a dispersant. No particular limitation is made here. This invention uses a 2% deionized gelatin aqueous solution to illustrate the advantages of this scheme.

[0038] In this invention, in order to prepare a catalyst more suitable for this method and further improve the catalytic effect, according to a preferred embodiment of the invention, the mass ratio of the 4-vinylphenylalkylazacycloalkanes to the crosslinking agent is controlled to be 85-99:1-15.

[0039] In this invention, there is no particular limitation on the amount of crosslinking agent and initiator fed. According to a preferred embodiment of this invention, the mass ratio of crosslinking agent to initiator is 1-15:0.1-5.

[0040] In this invention, the type of initiator can be a conventional choice in the art. The following is an illustrative example, but does not limit the scope of the invention. The initiator is selected from one or more of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptanenitrile, lauroyl peroxide, and cumene hydroperoxide.

[0041] In this invention, there are no special requirements for the conditions of the ammoniation reaction, 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, the conditions of the ammoniation reaction include: a temperature of 40-90°C, preferably 50-80°C. The ammoniation time can usually be adjusted according to the ammoniation temperature, for example, a time of 10-48 hours, preferably 15-30 hours.

[0042] According to a preferred embodiment of the present invention, the ammonizing agent for ammoniation is a halogenated C1-C6 alkane, preferably selected from one or more of bromoethane, chloropropane, bromobutane, bromopentane, bromohexane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, iodoethane, iodopropane, iodobutane, iodopentane, and iodohexane.

[0043] In this invention, there are no particular restrictions on the amount of material added during ammoniation. 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 weight ratio of styrene copolymer, ammoniation reagent and solvent is 1:0.3-3:3.5-15. At this time, the molar ratio of nitrogen element to halogen in the ammoniation reagent in the reaction system is ≤1, as long as sufficient ammoniation is ensured.

[0044] According to a preferred embodiment of the present invention, the solvent used during ammoniation is selected from one or more of N,N-dimethylformamide, acetonitrile, N,N-dimethylacetamide and tetrahydrofuran.

[0045] In this invention, there are no special requirements for the conditions of the ion exchange reaction, 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, the conditions of the ion exchange reaction include: a temperature of 25-40°C and a time of 5-12 hours.

[0046] In this invention, there is no particular limitation on the amount of raw materials fed in the ion exchange reaction. 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 weight ratio of ammonium-modified microspheres to the X--containing solution is 1:10-100, preferably 1:10-40.

[0047] In this invention, the concentration of the solution containing X- is not particularly limited, for example, it is 0.1-1 mol / L.

[0048] According to a preferred embodiment of the present invention, the conditions for the contact reaction include: a reaction temperature of 40-180°C, preferably 90-120°C.

[0049] According to a preferred embodiment of the present invention, the conditions for the contact reaction include: a reaction 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 ethylene glycol to ethylene oxide and its derivatives is (1-50):1, preferably (3-8):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 0.5-2.0h -1 .

[0052] In this invention, by optimizing the contact reaction conditions as described above, the catalytic effect can be further improved, and the conversion rate of raw materials and the yield of the target product can be increased.

[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: 60.0 g of 1-[2-(4-vinylphenyl)ethyl]pyrrolidine, 7.0 g of divinylbenzene, and 1.5 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 hour, then to 85°C for 5 hours, and finally to 98°C for 6 hours. After the reaction was complete, the supernatant was poured off, and the remaining polymer solid was washed with 85°C hot 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: For every 30 g of the prepared polymer A1 added to a three-necked flask, 30 g of bromoethane was added, followed by 250 ml of N,N-dimethylformamide. The mixture was reacted at 40 °C for 30 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 30 g of the prepared ammonium-modified microspheres A1, 500 ml of a 1.0 mol / L deionized NaHCO3 aqueous solution was added and stirred at room temperature for 12 hours. The solution was then washed with deionized water until the pH of the washing solution reached 7, and vacuum dried to obtain the ion exchange resin Cat-A1. The infrared spectrum was measured as follows. Figure 1 As shown.

[0063] Example 2

[0064] Resin preparation: 60.0 g of 1-[2-(4-vinylphenyl)ethyl]pyrrolidine, 10.0 g of divinylbenzene, and 2 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 70°C for 1 hour, then to 85°C for 6 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 hot 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: For every 40 g of the prepared polymer A2 added to a three-necked flask, 30 g of bromopropane and 300 ml of N,N-dimethylformamide were added. 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 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 stirred at room temperature for 10 hours; then the solution was washed with deionized water until the pH of the washing solution was 7, and then dried under vacuum to obtain the ion exchange resin Cat-A2.

[0067] Example 3

[0068] Resin preparation: 60.0 g of 1-[2-(4-vinylphenyl)ethyl]pyrrolidine, 3.0 g of divinylbenzene, and 0.5 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 70°C for 1.5 hours, 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 hot 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: For every 50 g of the prepared polymer A3 added to a three-necked flask, 40 g of chloropropane and 300 ml of tetrahydrofuran were added. The reaction was carried out at 45 °C for 30 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 A3.

[0070] Ion exchange: In a three-necked flask, for every 50 g of the prepared ammonium-modified microspheres A3, 800 ml of a 0.8 mol / L deionized water solution of NaHCO3 was added and stirred at room temperature for 10 hours; then the solution was washed with deionized water until the pH of the washing solution was 7, and then dried under vacuum to obtain the ion exchange resin Cat-A3.

[0071] Example 4

[0072] Same as Example 1, except that the comonomer 1-[2-(4-vinylphenyl)ethyl]pyrrolidine was replaced with 1-[2-(4-vinylphenyl)ethyl]piperidine to prepare the ion exchange resin Cat-A4.

[0073] Example 5

[0074] Same as Example 1, except that the amount of divinylbenzene used was 35 grams to prepare the ion exchange resin Cat-A5.

[0075] Example 6

[0076] Same as Example 1, except that the comonomer 1-[2-(4-vinylphenyl)ethyl]pyrrolidine was replaced with 4-vinylbenzylpyrrolidine to prepare the ion exchange resin Cat-A6.

[0077] Example 7

[0078] In a fixed-bed reactor, ethylene oxide and ethylene glycol were reacted in the presence of the ion exchange resins of Examples 1-6. The ion exchange resins of Examples 1-6 were all sieved into microspheres with an average particle size of 0.6 mm and packed in three layers. The reaction conditions and results are shown in Table 1.

[0079] Example 8

[0080] 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.

[0081] The reaction conditions were: temperature 90℃, pressure 1.2MPa, and space velocity 0.6h. -1 The molar ratio of alcohols to alkane is 5.

[0082] The reaction results were: EO conversion rate 97.1%, DEG selectivity 76.5%, and TriEG selectivity 23.5%.

[0083] Table 1

[0084]

[0085] 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 co-producing diethylene glycol and its derivatives and triethylene glycol and its derivatives, characterized in that, The method includes: reacting ethylene oxide and its derivatives with ethylene glycol in the presence of a styrene copolymer; The styrene copolymer is modified with a cyclic quaternary ammonium salt and has the structure shown in formula (1): In equation (1), It is a styrene copolymer matrix, where R is an alkylene chain, R1 is an alkylene chain, R2 is an alkyl group, and X is an alkyl group. - It is an anion, and R together with N forms a 5-10 membered aliphatic heterocycle.

2. The method according to claim 1, wherein, In the formula (1), R and N together form a 6-8 member aliphatic heterocycle.

3. The method according to claim 1 or 2, wherein, The styrene copolymer matrix is ​​preferably a gel-type styrene-crosslinking agent copolymer matrix. The degree of crosslinking of the gel-type styrene-crosslinker copolymer matrix is ​​1-15%; and / or In the styrene copolymer, the styrene copolymer matrix accounts for 30-60 wt% by mass, preferably 30-50 wt%.

4. The method according to any one of claims 1-3, wherein, The crosslinking agent in the styrene copolymer matrix is ​​a di-alkenylbenzene and / or a poly-alkenylbenzene and / or a poly-unsaturated acid alcohol ester, preferably a di-alkenylbenzene and / or a poly-alkenylbenzene.

5. The method according to any one of claims 1-4, wherein, In the above formula (1), R is a C1-C10 straight-chain or branched alkylene chain, preferably a C2-C5 straight-chain or branched alkylene chain; and / or R1 is a C2-C10 straight-chain or branched alkylene chain, preferably a C3-C6 straight-chain or branched alkylene chain; and / or R2 is a C1-C6 straight-chain or branched alkyl group; and / or X- is selected from at least one of bicarbonate ion, hydroxide ion, bisulfite ion, and organic acid ion.

6. The method according to any one of claims 1-5, 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 ethylene oxide, 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.

7. The method according to any one of claims 1-6, wherein, The preparation method of the styrene copolymer includes the following steps: (a) Preparation of saturated aliphatic nitrogen heterocyclic functionalized styrene copolymer matrix; (b) The saturated aliphatic nitrogen heterocyclic functionalized styrene copolymer matrix prepared in step (a) is subjected to ammoniation and ion exchange reactions in sequence.

8. The method according to claim 7, wherein, Step (a) involves copolymerization using 4-vinylphenylalkylazacycloalkanes and a crosslinking agent as comonomers in the presence of an initiator. Preferably, in the copolymerization reaction, The mass ratio of 4-vinylphenylalkylazacycloalkanes to crosslinking agents is 85-99:1-15; and / or The mass ratio of crosslinking agent to initiator is 1-15:0.1-5.

9. The method according to claim 7, wherein, The conditions for the ammoniation reaction include: a temperature of 40-90℃, preferably 50-80℃; and / or a time of 10-48h, preferably 15-30h; and / or The ammonifying reagent used for ammonification is a halogenated C1-C6 alkane, preferably selected from one or more of bromoethane, chloropropane, bromobutane, bromopentane, bromohexane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, iodoethane, iodopropane, iodobutane, iodopentane, and iodohexane. and / or The conditions for the ion exchange reaction include: a temperature of 25-40°C; and / or a time of 5-12 hours.

10. The method according to any one of claims 1-9, wherein, The conditions for the contact reaction include: The reaction temperature is 40-180℃, preferably 90-120℃; and / or The reaction pressure is 0.1-10.0 MPa, preferably 0.8-2.5 MPa; and / or, The molar ratio of ethylene glycol to ethylene oxide and its derivatives is (1-50):1, preferably (3-8):1; and / or Liquid space velocity is 0.1-6.0 h⁻¹ -1 Preferably, it is 0.5-2.0h. -1 .

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