Preparation method of anion exchange resin

Abstract

The invention discloses a preparation method of anion exchange resin, and relates to the field of materials. Comprising the following steps: reacting a styrene-divinylbenzene polymer with a chlorine-containing compound in a solvent in the presence of a catalyst to obtain a first compound; reacting the first compound with a Grignard reagent to obtain a second compound; reacting the second compound with alkyl halide to obtain a third compound; and reacting the third compound with an amination reagent to obtain the anion exchange resin. The preparation method comprises the following steps: reacting a chlorine-containing compound with polystyrene-divinylbenzene spherical particles to obtain chlorine balls; reacting the chloromethylated beads with a Grignard reagent, and finally aminating through an aminating agent to obtain the thermal-stability strong-base anion exchange resin. The strong-base anion exchange resin overcomes the defect of poor thermal stability of the existing strong-base anion exchange resin, and has better heat resistance and longer service life than the traditional strong-base anion exchange resin.

Description

Technical Field

[0001] The present application relates to the field of material technology, and in particular to a method for preparing an anion exchange resin. Background Art

[0002] Strong alkaline anion exchange resin is an important type of adsorption material and is currently widely used in sewage treatment, electronics, petrochemicals and other fields.

[0003] Among the many strong alkaline anion exchange products currently on the market, the most widely used products are prepared by styrene-divinylbenzene polymerization (white ball preparation), chloromethylation of chloromethyl ether (chlorine ball preparation), and amination of reagents such as trimethylamine and triethylamine.

[0004] However, the anion exchange resins prepared by the existing preparation methods have poor heat resistance and thermal stability, which limits their application. Summary of the invention

[0005] The present application provides a method for preparing an anion exchange resin to solve the problem of poor thermal stability of existing resins.

[0006] In a first aspect, the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0007] reacting a styrene-divinylbenzene polymer with a chlorine-containing compound in a solvent under a catalyst environment to obtain a first compound;

[0008] reacting the first compound with a Grignard reagent to obtain a second compound;

[0009] reacting the second compound with an alkyl halide to obtain a third compound;

[0010] The third compound is reacted with an amination agent to obtain an anion exchange resin.

[0011] The present invention obtains chlorine balls by reacting chlorine-containing compounds with polystyrene-divinylbenzene spherical particles; reacts the chlorine balls with a Grignard reagent, and finally aminates with an aminating agent to obtain a heat-stable strong base anion exchange resin. The defect of the current strong base anion exchange resin having poor heat stability is solved. The strong base anion exchange resin of the present invention has better heat resistance and longer service life than the traditional strong base anion exchange resin.

[0012] In some embodiments, the chlorine-containing compound includes at least one of chloromethyl ether and chloroacetyl chloride. Using at least one of chloromethyl ether and chloroacetyl chloride can provide raw materials for chloromethylation, ensuring that the chloromethylation reaction proceeds smoothly; and / or,

[0013] The catalyst comprises at least one of ferric chloride, antimony chloride, aluminum chloride and zinc chloride. Using at least one of the above catalysts can increase the reaction rate of chloromethylation and shorten the time used for chloromethylation; and / or,

[0014] The solvent includes at least one of methylal, benzene, toluene, ethylene dichloride and chloroform. Using at least one of the above solvents can expand the volume of the polystyrene-divinylbenzene spherical particles, increase the contact area between the polystyrene-divinylbenzene spherical particles and the chlorination reagent, and improve the efficiency of the chloromethylation reaction.

[0015] In some embodiments, the crosslinking degree of the styrene-divinylbenzene polymer is 2 to 10. Within this range, the crosslinking degree of the styrene-divinylbenzene polymer can ensure that the chlorine content in the chlorine balls produced by the reaction is appropriate. If the chlorine content of the chlorine balls is too low, the number of groups available for reaction in subsequent reactions will be reduced, resulting in a low exchange capacity of the final product. If the chlorine content of the chlorine balls is too high, the mechanical strength of the final product will be too low; and / or,

[0016] The particle size of the styrene-divinylbenzene polymer is 0.2-0.6 mm. Within this range, the styrene-divinylbenzene polymer can be ensured to expand evenly and the chloromethylation in the reaction system can be fully carried out; and / or,

[0017] The water content of the styrene-divinylbenzene polymer is 0.1-3.8%. When the water content of the styrene-divinylbenzene polymer is within this range, it is possible to avoid excessive water in the styrene-divinylbenzene polymer reacting with the chlorinating agent to release heat, thereby destroying the polymer structure and reducing the mechanical strength of the final product.

[0018] In some embodiments, the styrene-divinylbenzene polymer is reacted with a chlorine-containing compound in a solvent under a catalyst environment to obtain the first compound:

[0019] The mass ratio of styrene-divinylbenzene polymer, catalyst and chlorine-containing compound is 1:(0.2-0.6):(3-4). Within this range, the mass ratio of styrene-divinylbenzene polymer, catalyst and chlorine-containing compound can ensure that the chlorine content of chlorine ball is appropriate. Too low chlorine content of chlorine ball will lead to a reduction in the number of groups available for reaction in subsequent reactions, resulting in a low exchange capacity of the final product. Too high chlorine content of chlorine ball will lead to too low mechanical strength of the final product; and / or,

[0020] The reaction time is 3 to 16 hours. Within this range, the chlorine content of the chlorine ball can be ensured to be appropriate. Too low a chlorine content of the chlorine ball will lead to a reduction in the number of groups available for reaction in subsequent reactions, resulting in a low exchange capacity of the final product. Too high a chlorine content of the chlorine ball will lead to too low mechanical strength of the final product; and / or,

[0021] The reaction temperature is 5-60°C. When the reaction temperature is within this range, the appropriate chlorine content in the chlorine ball can be ensured. Too low a chlorine content in the chlorine ball will lead to a reduction in the number of groups available for reaction in subsequent reactions, resulting in a low exchange capacity of the final product. Too high a chlorine content in the chlorine ball will lead to too low mechanical strength of the final product.

[0022] In some embodiments, the grignard reagent includes at least one of methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, tert-butyl bromide, isopropylmagnesium bromide, n-butylmagnesium chloride, isopropylmagnesium chloride, n-butyllithium, tri-n-butylmagnesium lithium, isopropylmagnesium chloride-lithium chloride and benzylmagnesium chloride. By using at least one of the above grignard reagents, the chlorine ball structure can have groups that can react with alkyl halides.

[0023] In some embodiments, the first compound is reacted with a Grignard reagent to obtain a second compound:

[0024] The mass ratio of the first compound to the Grignard reagent is 1:(4-10). Within this range, the Grignard reagent can react with sufficient reaction sites on the chlorine ball structure; and / or,

[0025] The reaction time is 2 to 30 hours. Within this range, the Grignard reagent can react with sufficient reaction sites on the chlorine ball structure and ensure that the reaction reaches equilibrium; and / or,

[0026] The reaction temperature is 20-90°C. When the reaction temperature is within this range, the Grignard reagent can react with sufficient reaction sites on the chlorine ball structure. If the reaction temperature is too low, it will fail to react with the reaction sites. If the temperature is too high, the morphology of some Grignard reagents will change.

[0027] In some embodiments, the alkyl halide includes at least one of 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,6-dibromohexane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane and 1,6-diiodohexane. Using at least one of the above alkyl halide can ensure reaction with the group on the second compound so that the product has a long-chain structure, avoids direct connection between the benzyl carbon atom and the quaternary nitrogen atom, and makes the final product heat-resistant.

[0028] In some embodiments, the second compound is reacted with an alkyl halide to obtain a third compound:

[0029] The mass ratio of the second compound to the alkyl halide is 1:(3-10). Within this range, the reaction can be fully carried out. If the mass ratio is too low, the second compound cannot fully react; and / or,

[0030] The reaction time is 1 to 30 hours. Within this range, the reaction can be ensured to proceed fully. If the reaction time is too short, the reaction cannot reach full equilibrium; and / or,

[0031] The reaction temperature is 80-130° C. Within this range, the reaction can be ensured to proceed fully. If the reaction temperature is too low, the number of groups in the third compound that can react with the subsequent amination reagent will be too small, thereby reducing the exchange capacity of the final product. If the reaction temperature is too high, the pore structure will be destroyed, thereby reducing the mechanical strength of the final product.

[0032] In some embodiments, the aminating agent includes at least one of trimethylamine, trimethylamine hydrochloride aqueous solution, triethylamine, tripropylamine, tributylamine, triethylamine hydrochloride aqueous solution, dimethylethanolamine, dimethylpropanolamine, dioctylethanolamine, pyridine, picoline, lutidine, ethylpyridine, diethylpyridine and methyldiethanolamine. Using at least one of the above aminating agents can ensure that the aminating agent and the long-chain group of the third compound undergo group exchange, so that the final product has exchange capacity.

[0033] In some embodiments, the third compound is reacted with an aminating agent to obtain an anion exchange resin:

[0034] The mass ratio of the third compound to the aminating agent is such that the amination can be fully carried out. If the amount of the aminating agent is too low, some groups on the final third compound cannot react with the aminating agent, resulting in too low exchange capacity of the final product; and / or,

[0035] The reaction temperature is 10-80° C. Within this range, the reaction can be ensured to proceed fully. If the reaction temperature is too low, the amination reaction cannot proceed. If the reaction temperature is too high, part of the amination reagent will boil and evaporate and the pore structure of the final product will be destroyed, thereby reducing the mechanical strength. And / or,

[0036] The reaction time is 2 to 24 hours. Within this range, the reaction can be ensured to proceed fully. If the reaction time is too short, some groups on the final third compound cannot react with the amination reagent, resulting in too low exchange capacity of the final product. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solution and advantages of the present application clearer, the technical solution of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present application.

[0038] Strong alkaline anion exchange resin is an important type of adsorption material and is currently widely used in sewage treatment, electronics, petrochemicals and other fields.

[0039] Among the many strong alkaline anion exchange products currently on the market, the most widely used products are prepared by styrene-divinylbenzene polymerization (white ball preparation), chloromethylation of chloromethyl ether (chlorine ball preparation), and amination of reagents such as trimethylamine and triethylamine.

[0040] However, the anion exchange resin prepared by the existing preparation method has poor heat resistance. At high temperatures, the quaternary ammonium salt functional group decomposes, resulting in the attenuation of its exchange capacity. The poor heat resistance and thermal stability limit its application.

[0041] For example, the preparation of long-chain haloalkyl styrene polymers can be achieved by suspension polymerization of long-chain bromoalkyl styrene monomers and then copolymerization with divinylbenzene. However, the preparation of this monomer requires the use of magnesium chips for the Grignard reaction. The overall reaction process needs to be controlled at about minus 170°C, and the reaction is strong. The control conditions are relatively harsh, the production cost is extremely high, and it is not conducive to large-scale production. By mixing a 1-12 carbon long-chain halogenated alcohol and a solvent, adding a trimethylamine aqueous solution to react, adding a chlorine ball, and adding sodium methoxide to react, a heat-stable strong base anion exchange resin is obtained. The white ball is acylated with sulfuryl chloride, and then aminated with N, N-dialkyl long-chain diamine to extend the length of the intermediate arm chain to prepare a heat-stable strong base anion exchange resin. These technologies use chlorine balls for reaction, and extend the intermediate arm chain between the chloromethyl group and the benzene ring in the chlorine ball to meet the thermal stability of the resin after amination. Although the heat resistance of the resin has been improved, the inter-arm chains of similar structures contain oxygen and nitrogen. The presence of these elements is not conducive to the improvement of heat resistance, and the improvement of its thermal stability is limited.

[0042] In view of this, the present application provides a method for preparing an anion exchange resin to solve the problem of poor thermal stability of existing resins.

[0043] In a first aspect, the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0044] reacting a styrene-divinylbenzene polymer with a chlorine-containing compound in a solvent under a catalyst environment to obtain a first compound;

[0045] reacting the first compound with a Grignard reagent to obtain a second compound;

[0046] reacting the second compound with an alkyl halide to obtain a third compound;

[0047] The third compound is reacted with an amination agent to obtain an anion exchange resin.

[0048] The present invention obtains chlorine balls by reacting chlorine-containing compounds with polystyrene-divinylbenzene spherical particles; reacts the chlorine balls with a Grignard reagent, and finally aminates with an aminating agent to obtain a heat-stable strong base anion exchange resin. The defect of the current strong base anion exchange resin having poor heat stability is solved. The strong base anion exchange resin of the present invention has better heat resistance and longer service life than the traditional strong base anion exchange resin.

[0049] The first compound is washed with a solvent, and the solvent used is at least one of methanol, ethanol, acetone, methylal, benzene, toluene, dichloroethane, chloroform and water.

[0050] The third compound is washed with a solvent, and the solvent used is at least one of dimethylformamide, dimethyl sulfoxide, methylal, benzene, toluene, dichloroethane, chloroform, methanol, ethanol and acetone.

[0051] The fourth compound is washed with a solvent, and the solvent used is at least one of dimethylformamide, dimethyl sulfoxide, methylal, benzene, toluene, dichloroethane, chloroform, methanol, ethanol, acetone, water, sodium chloride aqueous solution, sodium sulfate aqueous solution, sodium hydroxide aqueous solution and hydrochloric acid aqueous solution.

[0052] In combination with the first aspect, in some embodiments provided in the present application, the chlorine-containing compound includes at least one of chloromethyl ether and chloroacetyl chloride. Using at least one of chloromethyl ether and chloroacetyl chloride can provide raw materials for chloromethylation and ensure that the chloromethylation reaction proceeds smoothly.

[0053] In combination with the first aspect, in some embodiments provided in the present application, the catalyst includes at least one of ferric chloride, antimony chloride, aluminum chloride and zinc chloride. Using at least one of the above catalysts can increase the reaction rate of chloromethylation and shorten the time used for chloromethylation.

[0054] In combination with the first aspect, in some embodiments provided in the present application, the solvent includes at least one of methylal, benzene, toluene, dichloroethane and chloroform. Using at least one of the above solvents can expand the volume of the polystyrene-divinylbenzene spherical particles, increase the contact area between the polystyrene-divinylbenzene spherical particles and the chlorination reagent, and improve the efficiency of the chloromethylation reaction.

[0055] In combination with the first aspect, in some embodiments provided in the present application, the crosslinking degree of the styrene-divinylbenzene polymer is 2 to 10. The crosslinking degree of a polymer refers to the number and degree of stable connections formed between polymer molecular chains through chemical bonds or physical effects. The crosslinking degree of the styrene-divinylbenzene polymer is within this range, which can ensure that the chlorine content in the chlorine balls produced by the reaction is appropriate. Too low a chlorine content in the chlorine balls will lead to a reduction in the number of groups available for reaction in subsequent reactions, resulting in a low exchange capacity of the final product. Too high a chlorine content in the chlorine balls will lead to too low a mechanical strength of the final product.

[0056] In combination with the first aspect, in some embodiments provided in the present application, the particle size of the styrene-divinylbenzene polymer is 0.2 to 0.6 mm. The particle size of the styrene-divinylbenzene polymer within this range can ensure uniform expansion of the styrene-divinylbenzene polymer and ensure that the chloromethylation performed in the reaction system is fully carried out.

[0057] In combination with the first aspect, in some embodiments provided in the present application, the water content of the styrene-divinylbenzene polymer is 0.1 to 3.8%. Within this range of the water content of the styrene-divinylbenzene polymer, it is possible to avoid excessive water in the styrene-divinylbenzene polymer from reacting with the chlorinating agent to release heat, thereby destroying the polymer structure and causing a reduction in the mechanical strength of the final product.

[0058] In combination with the first aspect, in some embodiments provided in the present application, the styrene-divinylbenzene polymer is reacted with a chlorine-containing compound in a solvent under a catalyst environment to obtain a first compound in which the mass ratio of the styrene-divinylbenzene polymer, the catalyst and the chlorine-containing compound is 1:(0.2~0.6):(3~4). The mass ratio of the styrene-divinylbenzene polymer, the catalyst and the chlorine-containing compound is within this range, and the Grignard reagent can react with sufficient reaction sites on the chlorine ball structure.

[0059] In combination with the first aspect, in some embodiments provided in the present application, the styrene-divinylbenzene polymer is reacted with a chlorine-containing compound in a solvent under a catalyst environment to obtain a first compound: the reaction time is 3 to 16 hours. The reaction time is within this range to ensure that the chlorine content of the chlorine ball is appropriate. Too low a chlorine content of the chlorine ball will lead to a reduction in the number of groups available for reaction in subsequent reactions, resulting in a low exchange capacity of the final product. Too high a chlorine content of the chlorine ball will lead to too low mechanical strength of the final product.

[0060] In combination with the first aspect, in some embodiments provided in the present application, the styrene-divinylbenzene polymer is reacted with a chlorine-containing compound in a solvent under a catalyst environment to obtain a first compound: the reaction temperature is 5 to 60°C. The reaction temperature is within this range to ensure that the chlorine content is appropriate. Too low a chlorine content will lead to a reduction in the number of groups available for reaction in subsequent reactions, resulting in a low exchange capacity of the final product. Too high a chlorine content will lead to too low mechanical strength of the final product.

[0061] In combination with the first aspect, in some embodiments provided in the present application, the grignard reagent includes at least one of methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, tert-butyl bromide, isopropylmagnesium bromide, n-butylmagnesium chloride, isopropylmagnesium chloride, n-butyllithium, tri-n-butylmagnesium lithium, isopropylmagnesium chloride-lithium chloride and benzylmagnesium chloride. By using at least one of the above grignard reagents, the chlorine ball structure can have groups that meet the requirements for reacting with alkyl halides.

[0062] In combination with the first aspect, in some embodiments provided in the present application, the first compound is reacted with a Grignard reagent to obtain a second compound: the mass ratio of the first compound to the Grignard reagent is 1:(3~10). When the mass ratio of the first compound to the Grignard reagent is within this range, the Grignard reagent can react with sufficient reaction sites on the chlorine ball structure.

[0063] In combination with the first aspect, in some embodiments provided in the present application, the first compound is reacted with a Grignard reagent to obtain a second compound: the reaction time is 2 to 30 hours. The reaction time within this range can allow the reagent to react with sufficient reaction sites on the chlorine ball structure and ensure that the reaction reaches equilibrium.

[0064] In combination with the first aspect, in some embodiments provided in the present application, the first compound is reacted with a Grignard reagent to obtain a second compound: the reaction temperature is 20 to 90°C. Within this reaction temperature range, the Grignard reagent can react with sufficient reaction sites on the chlorine ball structure. If the reaction temperature is too low, it will lead to the inability to react with the reaction sites. If the temperature is too high, the morphology of some Grignard reagents may change.

[0065] In combination with the first aspect, in some embodiments provided in the present application, the alkyl halide includes at least one of 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,6-dibromohexane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane and 1,6-diiodohexane. Using at least one of the above alkyl halide can ensure reaction with the group on the second compound so that the product has a long-chain structure, avoiding direct connection between the benzyl carbon atom and the quaternary nitrogen atom, so that the final product has heat resistance.

[0066] In combination with the first aspect, in some embodiments provided in the present application, the second compound is reacted with an alkyl halide to obtain a third compound: In combination with the first aspect, in some embodiments provided in the present application, the second compound is reacted with an alkyl halide to obtain a third compound: The mass ratio of the second compound to the alkyl halide is 1:(3~10). The mass ratio of the second compound to the alkyl halide is within this range, which can ensure that the reaction is fully carried out. If the mass is too low, the second compound will not be able to complete the reaction completely.

[0067] In combination with the first aspect, in some embodiments provided in the present application, the second compound is reacted with a halogenated alkane to obtain a third compound: the reaction time is 1 to 30 hours. The reaction time within this range can ensure that the reaction proceeds fully. If the reaction time is too short, the reaction may not reach full equilibrium.

[0068] In combination with the first aspect, in some embodiments provided in the present application, the second compound is reacted with a halogenated alkane to obtain a third compound: the reaction temperature is 80 to 130°C. The reaction temperature within this range can ensure that the reaction proceeds fully. If the reaction time is too short, the reaction may not reach full equilibrium.

[0069] In combination with the first aspect, in some embodiments provided in the present application, the aminating agent includes at least one of trimethylamine, trimethylamine hydrochloride aqueous solution, triethylamine, tripropylamine, tributylamine, triethylamine hydrochloride aqueous solution, dimethylethanolamine, dimethylpropanolamine, dioctylethanolamine, pyridine, picoline, lutidine, ethylpyridine, diethylpyridine and methyldiethanolamine. Using at least one of the above aminating agents can ensure that the aminating agent and the long-chain group of the third compound undergo group exchange, so that the final product has exchange capacity.

[0070] In combination with the first aspect, in some embodiments provided in the present application, the third compound is reacted with an aminating agent to obtain an anion exchange resin: the mass ratio of the third compound to the aminating agent is 1:(2-10). The mass ratio of the third compound to the aminating agent is within this range to ensure that the amination is fully carried out. If the amount of the aminating agent is low, some groups on the final third compound will not be able to react with the aminating agent, resulting in too low an exchange capacity of the final product.

[0071] In combination with the first aspect, in some embodiments provided in the present application, the third compound is reacted with an aminating agent to obtain an anion exchange resin: the reaction temperature is 10 to 80° C. The reaction temperature within this range can ensure that the reaction is fully carried out. If the reaction temperature is too low, the amination reaction cannot proceed. If the reaction temperature is too high, part of the aminating agent will boil and evaporate and the pore structure of the final product will be destroyed, thereby reducing the mechanical strength.

[0072] In combination with the first aspect, in some embodiments provided in the present application, the third compound is reacted with an amination reagent to obtain an anion exchange resin: the reaction time is 2 to 24 hours. The reaction time within this range can ensure that the reaction is fully carried out. If the reaction time is too short, some groups on the final third compound will not be able to react with the amination reagent, resulting in too low an exchange capacity of the final product.

[0073] The technical solution provided in this application is described in detail below in conjunction with embodiments.

[0074] Example 1

[0075] Example 1 of the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0076] Use polystyrene-divinylbenzene polymer spherical particles with a crosslinking degree of 7, a particle size of 0.20 mm, and a moisture content of 0.2%, add 3 times the mass of polystyrene-divinylbenzene polymer spherical particles of chloromethyl ether and stir for 5 hours, add 0.2 times the mass of polystyrene-divinylbenzene polymer spherical particles of zinc chloride as a catalyst, and react for 12 hours at 45°C. After the reaction is completed, use methylal to wash and dry at 25°C to obtain the first compound chloroalkylated polystyrene-divinylbenzene resin, i.e., chlorospheres.

[0077] The first compound, chlorine ball, is swelled in 2 times the mass of methylal, and then 5 times the mass of Grignard reagent is added and mixed, and then reacted at 60° C. for 16 hours under anhydrous and oxygen-free conditions to obtain a second compound, wherein the Grignard reagent is isopropyl magnesium chloride dissolved in tetrahydrofuran.

[0078] The second compound is added with 1,3-dibromopropane in an amount 10 times the mass of the chlorine ball, and reacted at 100° C. for 16 hours under anhydrous and oxygen-free conditions. After filtering, the mixture is washed with ethanol and dried to obtain a third compound.

[0079] The third compound is swelled in 2 times the mass of methylal, and 4 times the mass of trimethylamine aqueous solution (mass concentration is 30%) is added, and the mixture is reacted at 35° C. for 8 hours. After the reaction is completed, the mixture is washed with pure water and dried to obtain a strongly basic anion exchange resin.

[0080] Example 2

[0081] Example 2 of the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0082] Use polystyrene-divinylbenzene polymer spherical particles with a crosslinking degree of 2, a particle size of 0.25 mm, and a moisture content of 3.8%, add chloromethyl ether 4 times the mass of the polystyrene-divinylbenzene polymer spherical particles, stir for 5 hours, add antimony chloride 0.6 times the mass of the polystyrene-divinylbenzene polymer spherical particles as a catalyst, and react for 16 hours at 5°C. After the reaction is completed, wash with benzene at 25°C and dry to obtain the first compound chloroalkylated polystyrene-divinylbenzene resin, i.e., chlorine balls.

[0083] The first compound, chlorine ball, is swelled in 2 times the mass of methylal, and then 4 times the mass of Grignard reagent is added and mixed, and then reacted at 20° C. for 30 hours under anhydrous and oxygen-free conditions to obtain a second compound, wherein the Grignard reagent is tri-n-butyl magnesium lithium dissolved in tetrahydrofuran.

[0084] The second compound is added with 1,4-dibromobutane in an amount three times the mass of the chlorine ball, and reacted at 130° C. for 1 hour under anhydrous and oxygen-free conditions. After filtering, the mixture is washed with ethanol and dried to obtain a third compound.

[0085] The third compound is swelled in 2 times the mass of methylal, and 10 times the mass of dimethylpropanolamine aqueous solution (mass concentration is 30%) is added, and the mixture is reacted at 80° C. for 2 hours. After the reaction is completed, the mixture is washed with pure water and dried to obtain a strongly basic anion exchange resin.

[0086] Example 3

[0087] Example 3 of the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0088] Use polystyrene-divinylbenzene polymer spherical particles with a crosslinking degree of 10, a particle size of 0.6 mm, and a moisture content of 2.0%, add 3.5 times the mass of polystyrene-divinylbenzene polymer spherical particles of chloromethyl ether and stir for 5 hours, add 0.4 times the mass of polystyrene-divinylbenzene polymer spherical particles of aluminum chloride as a catalyst, and react at 60°C for 2 hours. After the reaction is completed, use toluene to wash and dry at 25°C to obtain the first compound chloroalkylated polystyrene-divinylbenzene resin, i.e., chlorospheres.

[0089] After the first compound, chlorine ball, is swollen in 2 times the mass of methylal, 10 times the mass of Grignard reagent is added and mixed, and then reacted at 90° C. for 2 hours under anhydrous and oxygen-free conditions to obtain a second compound, wherein the Grignard reagent is propylmagnesium bromide dissolved in tetrahydrofuran.

[0090] The second compound is added with 1,6-dibromohexane in an amount of 5 times the mass of the chlorine ball, and reacted at 80° C. for 30 hours under anhydrous and oxygen-free conditions. After filtering, the mixture is washed with ethanol and dried to obtain a third compound.

[0091] The third compound is swelled in 2 times the mass of methylal, and 2 times the mass of diethylpyridine (mass concentration is 30%) is added, and the mixture is reacted at 10° C. for 24 hours. After the reaction is completed, the mixture is washed with pure water and dried to obtain a strongly basic anion exchange resin.

[0092] Example 4

[0093] Example 4 of the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0094] Use polystyrene-divinylbenzene polymer spherical particles with a crosslinking degree of 5, a particle size of 0.35 mm, and a moisture content of 1.5%, add 2 times the mass of polystyrene-divinylbenzene polymer spherical particles of chloromethyl ether and stir for 5 hours, add 0.1 times the mass of polystyrene-divinylbenzene polymer spherical particles of zinc chloride as a catalyst, and react for 10 hours at 35°C. After the reaction is completed, use toluene to wash and dry at 25°C to obtain the first compound chloroalkylated polystyrene-divinylbenzene resin, i.e., chlorospheres.

[0095] After the first compound chlorine ball is swelled in 2 times the mass of methylal, 3 times the mass of Grignard reagent is added and mixed, and then reacted at 50°C for 20 hours under anhydrous and oxygen-free conditions to obtain a second compound, wherein the Grignard reagent is n-butylmagnesium chloride dissolved in tetrahydrofuran.

[0096] The second compound was added with 1,5-diiodopentane in an amount twice the mass of the chlorine ball, and reacted at 110° C. for 20 hours under anhydrous and oxygen-free conditions. After filtering, the mixture was washed with ethanol and dried to obtain a third compound.

[0097] The third compound is swelled in 2 times the mass of methylal, and 1 times the mass of dioctylethanolamine aqueous solution (mass concentration is 30%) is added, and the mixture is reacted at 45° C. for 6 hours. After the reaction is completed, the mixture is washed with pure water and dried to obtain a strongly basic anion exchange resin.

[0098] Example 5

[0099] Example 5 of the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0100] Use polystyrene-divinylbenzene polymer spherical particles with a crosslinking degree of 15, a particle size of 0.80 mm, and a moisture content of 0.05%, add chloroacetyl chloride 5 times the mass of the polystyrene-divinylbenzene polymer spherical particles, stir for 5 hours, add ferric chloride 0.7 times the mass of the polystyrene-divinylbenzene polymer spherical particles as a catalyst, and react for 20 hours at 4°C. After the reaction is completed, use chloroform to wash and dry at 25°C to obtain the first compound chloroalkylated polystyrene-divinylbenzene resin, i.e., chlorine balls.

[0101] After the first compound chlorine ball is swollen in 2 times the mass of methylal, 12 times the mass of Grignard reagent is added and mixed, and then reacted at 10°C for 40 hours under anhydrous and oxygen-free conditions to obtain a second compound, wherein the Grignard reagent is isopropyl magnesium chloride dissolved in tetrahydrofuran.

[0102] The second compound is added with 1,2-diiodoethane in an amount of 12 times the mass of the chlorine ball, and reacted at 70° C. for 48 hours under anhydrous and oxygen-free conditions. After filtering, the mixture is washed with ethanol and dried to obtain a third compound.

[0103] The third compound is swelled in 2 times the mass of methylal, and 12 times the mass of triethylamine (mass concentration is 30%) is added, and the mixture is reacted at 5° C. for 48 hours. After the reaction is completed, the mixture is washed with pure water and dried to obtain a strongly basic anion exchange resin.

[0104] Example 6

[0105] Example 6 of the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0106] Use polystyrene-divinylbenzene polymer spherical particles with a crosslinking degree of 2, a particle size of 0.15 mm, and a moisture content of 4.2%, add 3.8 times the mass of polystyrene-divinylbenzene polymer spherical particles of chloromethyl ether and stir for 5 hours, add 0.4 times the mass of polystyrene-divinylbenzene polymer spherical particles of zinc chloride as a catalyst, and react at 70°C for 2 hours. After the reaction is completed, use methylal to wash and dry at 25°C to obtain the first compound chloroalkylated polystyrene-divinylbenzene resin, i.e., chlorospheres.

[0107] After the first compound, chlorine ball, is swollen in 2 times the mass of methylal, 6 times the mass of Grignard reagent is added and mixed, and then reacted at 100° C. for 1 hour under anhydrous and oxygen-free conditions to obtain a second compound, wherein the Grignard reagent is tri-n-butyl magnesium lithium dissolved in tetrahydrofuran.

[0108] The second compound was added with 1,5-diiodopentane in an amount of 8 times the mass of the chlorine ball, and reacted at 150° C. for 0.5 hour under anhydrous and oxygen-free conditions. After filtering, the mixture was washed with ethanol and dried to obtain a third compound.

[0109] The third compound is swelled in 2 times the mass of methylal, 6 times the mass of methyldiethanolamine (mass concentration is 30%) is added, and the mixture is reacted at 90° C. for 1 hour. After the reaction is completed, the mixture is washed with pure water and dried to obtain a strongly basic anion exchange resin.

[0110] Comparative Example 1

[0111] Comparative Example 1 of the present application provides a method for preparing an anion exchange resin, comprising the following steps:

[0112] Preparation of polystyrene-divinylbenzene polymer: 40g of styrene, 6g of divinylbenzene, 0.5g of initiator benzoyl peroxide and 20g of porogen polyethylene glycol are stirred and mixed to obtain a first mixed material; 100mL of 1mol / L sodium chloride solution and 1g of carboxymethyl cellulose are added to a three-necked flask, and the mixture is stirred and heated until all dissolved to obtain a second mixed material; the first mixed material is added to the three-necked flask by a tubular injection method, and the mixture is stirred and heated to 80°C for reaction for 12h; after the reaction is completed, the mixture is filtered, and the obtained solid material is washed with water and air-dried, and then sieved to obtain a polystyrene-divinylbenzene polymer with a particle size of 0.3-0.5mm;

[0113] Preparation of chloromethylated polystyrene-divinylbenzene polymer: 5 g of polystyrene-divinylbenzene polymer and 25 g of chloromethyl ether are placed in a three-necked flask and swelled for 1 hour at room temperature; then 10 g of catalyst zinc chloride is added to the three-necked flask and reacted at 45° C. for 24 hours; after the reaction is completed, the solid material is filtered and washed with anhydrous ethanol and deionized water in turn and then air-dried to obtain chloromethylated polystyrene-divinylbenzene polymer;

[0114] Preparation of anion exchange resin: In a three-necked flask equipped with a thermometer, a reflux condenser and an electric stirrer, 5 g of chloromethylated polystyrene-divinylbenzene polymer and 100 mL of n-butanol were added, and the mixture was swollen at room temperature for 1 h; then 2 g of sodium hydroxide was added to the three-necked flask, the system temperature was controlled to be 60° C., and 10 g of triethylamine was added dropwise at a rate of 2.5 g / min to the three-necked flask; after the addition was completed, the mixture was reacted at 60° C. for 12 h; after the reaction was completed, the mixture was filtered, and the obtained solid material was washed with deionized water and toluene in turn and filtered to obtain anion exchange resin.

[0115] Performance Testing

[0116] The anion exchange resins prepared by the preparation methods of Examples 1 to 6 and Comparative Example 1 were subjected to thermal stability tests and high temperature resistance tests. The specific test methods are as follows:

[0117] Thermal degradation reduction rate of strong groups: thermal stability test according to DL / T953-2018;

[0118] Functional group shedding time: Under the condition of 100°C, record the time required for the sample exchange capacity to drop to 30% of the original exchange capacity. The test method for the sample exchange capacity can be measured using GB / T 5760-2000.

[0119] The test results are shown in Table 1.

[0120] Table 1 Anion exchange resin performance test results of Examples 1 to 6 and Comparative Example 1

[0121]

[0122]

[0123] As can be seen from Table 1, since Comparative Example 1 does not use alkyl halide to react with the second compound, its thermal degradation reduction rate of the strong group is lower than that of Examples 1-6.

[0124] The key to improving the high temperature resistance of anion exchange resin in the present application is to use alkyl halides to react with the second compound to avoid direct connection between the benzyl carbon atom and the quaternary nitrogen atom. If the benzyl carbon atom is directly connected to the quaternary nitrogen atom, the quaternary amine base will be unstable when heated, and some groups will fall off under high temperature conditions, and some strong bases will become weak bases, which will reduce the exchange capacity of the resin. The resin prepared by this patent can avoid this defect due to its long chain structure.

[0125] In summary, a chlorine ball is obtained by reacting a chlorine-containing compound with polystyrene-divinylbenzene spherical particles; the chlorine ball is reacted with a Grignard reagent, and finally aminated with an aminating agent to obtain a heat-stable strong base anion exchange resin. The defect of the current strong base anion exchange resin having poor heat stability is solved, and the strong base anion exchange resin of the present application has better heat resistance and longer service life than the traditional strong base anion exchange resin.

[0126] In the description of this specification, the description with reference to the terms "one embodiment / method", "some embodiments / methods", "example", "specific example" or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment / method or example are included in at least one embodiment / method or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment / method or example. Moreover, the specific features, structures, materials or characteristics described may be combined in a suitable manner in any one or more embodiments / methods or examples. In addition, those skilled in the art may combine and combine the different embodiments / methods or examples described in this specification and the features of the different embodiments / methods or examples, unless they are contradictory.

[0127] It should be noted that, in the present application, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment. In the absence of more restrictions, the elements defined by the sentence "comprise one..." do not exclude the existence of other identical elements in the process, method, article or equipment including the elements. In the present application, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically stipulated.

[0128] The above description is only a specific implementation of the present application, so that those skilled in the art can understand or implement the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest range consistent with the principles and novel features applied for herein.

Claims

1. A method for preparing an anion exchange resin, characterized in that: The following steps are involved: reacting a styrene-divinylbenzene polymer with a chlorine-containing compound in a solvent under a catalyst environment to obtain a first compound; reacting the first compound with a Grignard reagent to obtain a second compound; reacting the second compound with an alkyl halide to obtain a third compound; The third compound is reacted with an amination agent to obtain an anion exchange resin.

2. The method for preparing an anion exchange resin according to claim 1, wherein: The chlorine-containing compound comprises at least one of chloromethyl ether and chloroacetyl chloride; and / or, The catalyst comprises at least one of ferric chloride, antimony chloride, aluminum chloride and zinc chloride; and / or, The solvent includes at least one of methylal, benzene, toluene, toluene and chloroform.

3. The method for preparing an anion exchange resin according to claim 1, wherein: The crosslinking degree of the styrene-divinylbenzene polymer is 2 to 10; and / or, The particle size of the styrene-divinylbenzene polymer is 0.2 to 0.6 mm; and / or, The water content of the styrene-divinylbenzene polymer is 0.1-3.8%.

4. The method for preparing an anion exchange resin according to claim 1, wherein: The styrene-divinylbenzene polymer is reacted with a chlorine-containing compound in a solvent under a catalyst environment to obtain a first compound: The mass ratio of styrene-divinylbenzene polymer, catalyst and chlorine-containing compound is 1:(0.2-0.6):(3-4); and / or, The reaction time is 3 to 16 hours; and / or, The reaction temperature is 5-60°C.

5. The method for preparing an anion exchange resin according to claim 1, characterized in that: The Grignard reagent includes at least one of methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, tert-butyl bromide, isopropylmagnesium bromide, n-butylmagnesium chloride, isopropylmagnesium chloride, n-butyllithium, tri-n-butylmagnesium lithium, isopropylmagnesium chloride-lithium chloride and benzylmagnesium chloride.

6. The method for preparing an anion exchange resin according to claim 1, characterized in that: The first compound is reacted with a Grignard reagent to obtain a second compound: The mass ratio of the first compound to the Grignard reagent is 1:(4-10); and / or, The reaction time is 2 to 30 hours; and / or, The reaction temperature is 20-90°C.

7. The method for preparing an anion exchange resin according to claim 1, characterized in that: The alkyl halide includes at least one of 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,6-dibromohexane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane and 1,6-diiodohexane.

8. The method for preparing an anion exchange resin according to claim 1, characterized in that: The second compound is reacted with an alkyl halide to obtain a third compound: The mass ratio of the second compound to the alkyl halide is 1:(3-10); and / or, The reaction time is 1 to 30 hours; and / or, The reaction temperature is 80-130°C.

9. The method for preparing an anion exchange resin according to claim 1, characterized in that: The amination reagent includes at least one of trimethylamine, trimethylamine hydrochloride aqueous solution, triethylamine, tripropylamine, tributylamine, triethylamine hydrochloride aqueous solution, dimethylethanolamine, dimethylpropanolamine, dioctylethanolamine, pyridine, picoline, lutidine, ethylpyridine, diethylpyridine and methyldiethanolamine.

10. The method for preparing an anion exchange resin according to claim 1, characterized in that: The third compound is reacted with an aminating agent to obtain an anion exchange resin: The mass ratio of the third compound to the amination reagent is 1:(2-10); and / or, The reaction temperature is 10 to 80°C; and / or, The reaction time is 2 to 24 hours.

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