A monomer containing both a triquaternary ammonium salt ion and a trivinylbenzene structure, its preparation method and application, an anion exchange resin, its preparation method and application

Abstract

The present invention provides a monomer containing both triquaternary ammonium ions and trivinylbenzene structure, and its preparation method and application, an anion exchange resin and its preparation method and application, relating to the technical field of ion exchange resins. The monomer provided by the present invention contains both triquaternary ammonium ions and trivinylbenzene structure, and has high reactivity. The monomer can undergo free radical polymerization under the initiation of an initiator to prepare an anion exchange resin. The three active styrenes in the monomer structure endow the anion exchange membrane resin with a high crosslinking density, and the three quaternary ammonium ion structures ensure that the prepared anion exchange resin has a high ion exchange capacity. The prepared anion exchange resin has important potential application values in the fields of environmental protection, new energy, etc.

Description

Technical Field

[0001] The present invention relates to the technical field of ion exchange resins, and particularly relates to a monomer containing both triquaternary ammonium ions and trivinylbenzene structures, its preparation method and application, an anion exchange resin, its preparation method and application. Background Art

[0002] Anion exchange resins are an important class of functional polymer materials and have important application values in fields such as environmental protection water treatment, new energy battery electrolytes, natural medicine purification, and oil extraction. Ionized vinylbenzene monomers are key monomers for preparing anion exchange resins, and such monomers can be prepared into corresponding anion exchange resins through free radical polymerization under the action of initiators.

[0003] Quaternary ammonium salt type vinylbenzene monomers are an important part of ionized vinylbenzene monomers. Currently reported quaternary ammonium salt type vinylbenzene monomers usually contain only one quaternary ammonium ion and one active vinylbenzene structure, such as (4-vinylbenzyl) trimethylammonium chloride, 1-(p-vinylbenzyl)-1-methylpiperidinium chloride, etc. Due to the difficulty in synthesis process, there are few reports on monomers containing two or more quaternary ammonium ions and vinylbenzene structures. The synergistic introduction of multiple vinylbenzenes and quaternary ammonium ions can further improve the ion exchange capacity of the corresponding anion exchange resin while increasing the crosslinking density of the resin. Therefore, the design and preparation of ionized monomers containing multiple quaternary ammonium ions and multiple vinylbenzene structures have important academic research and practical application values. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a monomer containing both triquaternary ammonium ions and trivinylbenzene structures, its preparation method and application, an anion exchange resin, its preparation method and application. The synthesis process of the monomer containing both triquaternary ammonium ions and trivinylbenzene structures provided by the present invention is convenient and has a high yield. This monomer can be used to prepare an anion exchange resin with a high crosslinking density and a high ion exchange capacity through initiation by an initiator and free radical polymerization.

[0005] To achieve the above-mentioned invention purposes, the present invention provides the following technical solutions:

[0006] The present invention provides a monomer containing both triquaternary ammonium ions and trivinylbenzene structures, having the structure shown in Formula I:

[0007]

[0008] The present invention provides a preparation method for the monomer containing both triquaternary ammonium ions and trivinylbenzene structures as described in the above technical solution, including the following steps:

[0009] Mix tris(N,N-dimethylaminopropyl)amine, p-chloromethylstyrene and a polar organic solvent, and carry out a quaternization reaction to obtain the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure.

[0010] Preferably, the molar ratio of tris(N,N-dimethylaminopropyl)amine to p-chloromethylstyrene is 1:3 - 4;

[0011] The polar organic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide.

[0012] Preferably, the temperature of the quaternization reaction is 40 - 60 °C and the time is 1 - 3 h.

[0013] The present invention provides the application of the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure described in the above technical solution or the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure prepared by the preparation method described in the above technical solution in the preparation of anion exchange resins.

[0014] The present invention provides an anion exchange resin, and the raw materials for preparation include vinyl monomers, initiators and solvents; the vinyl monomers include the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure described in the above technical solution or the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure prepared by the preparation method described in the above technical solution.

[0015] Preferably, the vinyl monomers further include other water-soluble vinyl monomers;

[0016] The other water-soluble vinyl monomers include at least one of N-hydroxyacrylamide, acrylamide, acrylic acid and N-vinyl-2-pyrrolidone; the mass ratio of the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure to the other water-soluble vinyl monomers is 1.1 - 9:1;

[0017] The mass of the initiator is 1 - 2% of the mass of the vinyl monomers;

[0018] The solvent includes water.

[0019] The present invention provides the preparation method of the anion exchange resin described in the above technical solution, including the following steps: mix the vinyl monomers, initiators and solvents, and carry out a free radical polymerization reaction to obtain the anion exchange resin.

[0020] Preferably, the temperature of the free radical polymerization reaction is 80 - 90 °C and the time is 0.5 - 1.5 h.

[0021] The present invention provides the use of the anion exchange resin described in the above technical solution or the anion exchange resin prepared by the preparation method described in the above technical solution in water treatment, electrolytes, substance purification or oil extraction.

[0022] The structure monomer containing both triquaternary ammonium ions and trivinylbenzene provided by the present invention has both triquaternary ammonium ions and a trivinylbenzene structure in the structure shown in Formula I, and has a very high reactivity. This ionized vinylbenzene monomer can undergo free radical polymerization under the initiation of an initiator to prepare an anion exchange resin. The three active styrenes in the monomer structure endow the anion exchange membrane resin with a high crosslinking density, and the three quaternary ammonium ion structures ensure that the prepared anion exchange resin has a high ion exchange capacity. The anion exchange resin has important potential application values in fields such as environmental protection and new energy.

[0023] The preparation method of the structure monomer containing both triquaternary ammonium ions and trivinylbenzene provided by the present invention has a simple synthesis process, is easy to operate, has a high product yield, is easy to separate, has a low production cost, is green and environmentally friendly, and is suitable for industrial production.

[0024] The anion exchange resin provided by the present invention has a high crosslinking density and a high ion exchange capacity, and has important potential application values in environmental protection and new energy fields such as water treatment, electrolytes, substance purification, and oil extraction.

[0025] The preparation method of the anion exchange resin provided by the present invention has a simple process, is easy to operate, has a high product yield, is easy to separate, has a low production cost, is green and environmentally friendly, and is suitable for industrial production.

[0026] Furthermore, the present invention prepares a high crosslinking density anion exchange resin with a controllable ion exchange capacity by introducing other water-soluble vinyl monomers into the anion exchange resin through free radical polymerization. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 1H NMR spectrum of tris(4-vinylbenzyl-N,N-dimethylammonium chloride-tripropyl)amine prepared in Example 1 1 HNMR spectrum.

[0028] Figure 2 Infrared spectrum of tris(4-vinylbenzyl-N,N-dimethylammonium chloride-tripropyl)amine prepared in Example 1 DETAILED DESCRIPTION OF THE EMBODIMENTS

[0029] The present invention provides a structure monomer containing both triquaternary ammonium ions and trivinylbenzene, with the chemical name of tris(4-vinylbenzyl-N,N-dimethylammonium chloride-tripropyl)amine, having the structure shown in Formula I:

[0030]

[0031] In the present invention, the melting point of the monomer containing both triquaternary ammonium ions and trivinylbenzene structure is preferably 220 - 221 °C.

[0032] The present invention provides a preparation method of the monomer containing both triquaternary ammonium ions and trivinylbenzene structure as described in the above technical solution, comprising the following steps: mixing tris(N,N-dimethylaminopropyl)amine, p-chloromethylstyrene and a polar organic solvent, and carrying out a quaternization reaction to obtain the monomer containing both triquaternary ammonium ions and trivinylbenzene structure.

[0033] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0034] In the present invention, the preparation route of the monomer containing both triquaternary ammonium ions and trivinylbenzene structure is as follows:

[0035]

[0036] In the present invention, the molar ratio of tris(N,N-dimethylaminopropyl)amine to p-chloromethylstyrene is preferably 1:3 - 4, more preferably 1:3.2 - 3.8, and further preferably 1:3.4 - 3.5.

[0037] In the present invention, the polar organic solvent preferably includes at least one of N-methylpyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide. In the present invention, the mass of the polar organic solvent is preferably 2 - 4 times the total mass of tris(N,N-dimethylaminopropyl)amine and p-chloromethylstyrene, more preferably 2.5 - 3.5 times, and further preferably 3 - 3.5 times.

[0038] The present invention has no special limitation on the mixing, and it is only necessary to mix the raw materials evenly, such as stirring and mixing.

[0039] In the present invention, the temperature of the quaternization reaction is preferably 40 - 60 °C, more preferably 45 - 55 °C, and further preferably 50 °C; the time of the quaternization reaction is preferably 1 - 3 h, more preferably 1.5 - 2.5 h, and further preferably 2 h.

[0040] After completing the quaternization reaction, the present invention preferably further includes: cooling the reaction system obtained from the quaternization reaction to room temperature and then performing solid-liquid separation, washing the obtained solid product and then drying it to obtain the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure. In the present invention, the solid-liquid separation preferably includes filtration, suction filtration or centrifugal separation. In the present invention, the washing solvent preferably includes tetrahydrofuran and / or ethyl acetate. In the present invention, the drying temperature is preferably 80-120 °C, more preferably 100-110 °C; the drying time is preferably 4-10 h, more preferably 5-8 h; the drying preferably includes vacuum drying.

[0041] The present invention provides the use of the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure described in the above technical solution or the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure prepared by the preparation method described in the above technical solution in the preparation of anion exchange resins.

[0042] The present invention provides an anion exchange resin, and the preparation raw materials include vinyl monomers, initiators and solvents; the vinyl monomers include the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure described in the above technical solution or the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure prepared by the preparation method described in the above technical solution.

[0043] In the present invention, the water-soluble vinyl monomer preferably further includes other water-soluble vinyl monomers; the other water-soluble vinyl monomers preferably include at least one of N-hydroxyacrylamide, acrylamide, acrylic acid and N-vinyl-2-pyrrolidone. In the present invention, when the water-soluble vinyl monomer is the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure and other water-soluble vinyl monomers, the mass ratio of the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure and other water-soluble vinyl monomers is preferably 1.1-9:1, more preferably 1:2-5.

[0044] In the present invention, when the vinyl monomer is the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure, the structural unit of the anion exchange resin has the structural formula shown in Formula II:

[0045]

[0046] Among them, when the vinyl monomer is the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure, represents the repetition of the structural unit in the polymer structure. When the vinyl monomer is the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure and other water-soluble vinyl monomers, represents the repetition of the structural unit and other water-soluble vinyl monomers in the polymer structure; n is the repetition of the structural unit.

[0047] The present invention uses a monomer containing both a triquaternary ammonium ion and a trivinylbenzene structure as a raw material for preparation. The synergistic introduction of multiple vinylbenzenes and multiple quaternary ammonium ions can further improve the ion exchange capacity of the resin while increasing the crosslinking density of the anion exchange resin. After introducing other water-soluble vinyl monomers, the capacity of the anion exchange resin can be regulated, thereby obtaining an anion exchange resin with the required ion exchange capacity.

[0048] In the present invention, the initiator is preferably a water-soluble initiator, more preferably including persulfate, and further preferably ammonium persulfate and / or potassium persulfate. In the present invention, the mass of the initiator is preferably 1-2% of the mass of the water-soluble vinyl monomer, more preferably 1.2-1.8%, and further preferably 1.4-1.5%.

[0049] In the present invention, the solvent preferably includes water. In the present invention, the mass of the solvent is preferably 3-5 times the mass of the water-soluble vinyl monomer, more preferably 3.5-4.5 times, and further preferably 4 times.

[0050] The present invention provides a method for preparing the anion exchange resin described in the above technical solution, including the following steps: mixing a water-soluble vinyl monomer, an initiator, and a solvent, and performing a free radical polymerization reaction to obtain an anion exchange resin.

[0051] The present invention has no special limitation on the mixing, as long as the raw materials can be mixed evenly, specifically such as stirring and mixing.

[0052] In the present invention, the temperature of the free radical polymerization reaction is preferably 80-90 °C, more preferably 82-88 °C, and further preferably 84-85 °C; the time of the free radical polymerization reaction is preferably 0.5-1.5 h, more preferably 1 h; the free radical polymerization reaction is preferably carried out under stirring conditions.

[0053] In the present invention, the preparation route of the anion exchange resin is as follows:

[0054]

[0055] The present invention provides the application of the anion exchange resin described in the above technical solution or the anion exchange resin prepared by the preparation method described in the above technical solution in water treatment, electrolytes, substance purification, or oil extraction.

[0056] In the present invention, the electrolyte preferably includes the electrolyte of a new energy battery.

[0057] In the present invention, the substance purification preferably includes the purification of natural extracts or the purification of chemically synthesized substances, and the natural extracts preferably include natural drugs.

[0058] The anion exchange resin provided by the present invention has a high crosslinking density and a high ion exchange capacity, and the ion exchange capacity of the anion exchange resin can be regulated by introducing other water-soluble vinyl monomers. The anion exchange resin provided by the present invention has important potential application values in the fields of water treatment, electrolytes, substance purification, oil exploitation, etc., and has important academic research and practical application values.

[0059] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. The described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Any modifications, equivalent replacements, improvements, etc. made to the embodiments of the present invention under the premise of not making creative efforts shall fall within the protection scope of the present invention according to the technical essence and general principles of the present invention.

[0060] The following are the raw materials and drugs used in the examples:

[0061] p-Chloromethylstyrene (purity 99%), Shandong Xingshun New Materials Co., Ltd.;

[0062] Tris(N,N-dimethylaminopropyl)amine (purity 98%), N-hydroxyacrylamide (purity 99%), acrylamide (purity 99%), acrylic acid (purity 99%) and N-vinyl-2-pyrrolidone (purity 99%): Shanghai Macklin Biochemical Co., Ltd.;

[0063] Ammonium persulfate, potassium persulfate, N-methylpyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide: Shanghai Sinopharm Chemical Reagent Co., Ltd., chemically pure.

[0064] The test method for the chloride ion exchange capacity is the amount of substance of chloride ions (unit mmol) divided by the mass of the resin (unit g).

[0065] Example 1

[0066] 27.247 g (0.1 mol) of tris(N,N-dimethylaminopropyl)amine and 61.04 g (0.4 mol) of p-chloromethylstyrene were respectively added to a 500 mL dry three-necked flask equipped with mechanical stirring and a condenser. 200 mL of N-methylpyrrolidone was added, and the temperature was raised to 60 °C and stirred for 1 h to obtain a solid-liquid mixture. The reaction was terminated, the reaction solution was filtered, and the product was washed with tetrahydrofuran. Further dried in a vacuum oven at 80 °C for 10 h to obtain tris(4-vinylbenzyl-N,N-dimethylammonium chloride-tripropyl)amine containing both triquaternary ammonium ions and trivinylbenzene structural monomers, with a yield of 93%. 1HNMR(CDCl3, 400 MHz): 7.64 (d, 6H), 7.57 (d, 6H), 6.74 - 6.81 (m, 3H), 5.93 (d, 3H), 5.37 (d, 3H), 4.83 (s, 6H), 3.67 (m, 6H), 3.07 (s, 18H), 2.46 (m, 6H), 1.96 (m, 6H); The proton absorption peaks in the NMR spectrum are shown in the attachment Figure 1 for the attribution. FT-IR (KBr) / cm -1 : 3023, 2964, 2827, 1641, 1473; The absorption peaks at 2827 - 3023 cm -1 in the IR spectrum are characteristic absorption peaks of alkyl groups, and the absorption peak at 1641 cm -1 is the characteristic absorption peak of the C=C double bond, and the absorption peak at 1473 cm -1 is the characteristic absorption peak of C-N.

[0067] Example 2

[0068] 27.247 g (0.1 mol) of tris(N,N-dimethylaminopropyl)amine and 45.78 g (0.3 mol) of p-chloromethylstyrene were respectively added to a 500 mL dry three-necked flask equipped with a mechanical stirrer and a condenser. 260 mL of N,N-dimethylacetamide was added, and the temperature was raised to 40 °C and stirred for 3 h to obtain a solid-liquid mixture. The reaction was terminated, the reaction solution was filtered, and the product was washed with ethyl acetate. It was further dried in a vacuum oven at 120 °C for 4 h to obtain tris(4-vinylbenzyl-N,N-dimethylammonium chloride-tripropyl)amine containing both triquaternary ammonium ions and trivinylbenzene structural monomers, with a yield of 91%.

[0069] Example 3

[0070] 27.247 g (0.1 mol) of tris(N,N-dimethylaminopropyl)amine and 53.41 g (0.35 mol) of p-chloromethylstyrene were respectively added to a 500 mL dry three-necked flask equipped with a mechanical stirrer and a condenser. 240 of N,N-dimethylformamide was added, and the temperature was raised to 50 °C and stirred for 2 h to obtain a solid-liquid mixture. The reaction was terminated, the reaction solution was filtered, and the product was washed with tetrahydrofuran. It was further dried in a vacuum oven at 100 °C for 6 h to obtain tris(4-vinylbenzyl-N,N-dimethylammonium chloride-tripropyl)amine containing both triquaternary ammonium ions and trivinylbenzene structural monomers, with a yield of 92%.

[0071] The polymerization of the monomer containing both triquaternary ammonium ions and trivinylbenzene structure and the preparation of its anion exchange resin are as follows.

[0072] Application Example 1

[0073] 7.3034 g (0.01 mol) of N - hydroxyacrylamide and tris(4 - vinylbenzyl - N,N - dimethylammonium chloride - tripropyl)amine containing both tri - quaternary ammonium ions were added to a 250 mL three - necked flask equipped with a mechanical stirrer and a condenser. Water with a mass 3 - 5 times that of the monomers was added as a solvent. After stirring until the system became clear, potassium persulfate at 1 - 2% of the monomer mass was added as an initiator. The temperature was raised to 90 °C and stirred for 0.5 h. The product was filtered and washed with water, and after drying, an anion - exchange resin with a high cross - link density and ion - exchange capacity (chloride ion - exchange capacity of 4.107 mmol / g) was obtained, with a yield of 95%.

[0074] Application Example 2

[0075] 0.8115 g (0.008 mol) of N - hydroxyacrylamide and 7.3034 g (0.01 mol) of tris(4 - vinylbenzyl - N,N - dimethylammonium chloride - tripropyl)amine were added to a 250 mL three - necked flask equipped with a mechanical stirrer and a condenser. Water with a mass 3 - 5 times that of the monomers was added as a solvent. After stirring until the system became clear, ammonium persulfate at 1 - 2% of the monomer mass was added as an initiator. The temperature was raised to 85 °C and stirred for 1 h. The product was filtered and washed with water, and after drying, an anion - exchange resin with a high cross - link density and ion - exchange capacity (chloride ion - exchange capacity of 3.697 mmol / g) was obtained, with a yield of 96%.

[0076] Application Example 3

[0077] 1.466 g (0.0145 mol) of N - hydroxyacrylamide and 7.3034 g (0.01 mol) of tris(4 - vinylbenzyl - N,N - dimethylammonium chloride - tripropyl)amine were added to a 250 mL three - necked flask equipped with a mechanical stirrer and a condenser. Water with a mass 3 - 5 times that of the monomers was added as a solvent. After stirring until the system became clear, ammonium persulfate at 1 - 2% of the monomer mass was added as an initiator. The temperature was raised to 80 °C and stirred for 1.5 h. The product was filtered and washed with water, and after drying, an anion - exchange resin with a high cross - link density and ion - exchange capacity (chloride ion - exchange capacity of 3.421 mmol / g) was obtained, with a yield of 96%.

[0078] Application Example 4

[0079] 6.5718 g (0.065 mol) of N - hydroxyacrylamide and 7.3034 g (0.01 mol) of tris(4 - vinylbenzyl - N,N - dimethylammonium chloride - tripropyl)amine were added to a 250 mL three - necked flask equipped with a mechanical stirrer and a condenser. Water with a mass 3 - 5 times that of the monomer was added as a solvent. After stirring until the system became clear, ammonium persulfate with a mass of 1 - 2% of the monomer was added as an initiator. The temperature was raised to 80 °C and the reaction was stirred for 1 h. The product was filtered and washed with water. After drying, an anion - exchange resin with a high cross - link density and ion - exchange capacity (chloride ion - exchange capacity of 2.162 mmol / g) could be obtained, and the yield was 96%.

[0080] The above - mentioned is only the preferred embodiment of the present invention. It should be pointed out that for those of ordinary skill in the art of this technology, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A monomer containing triquaternary ammonium salt ions and trivinylbenzene structure, having a structure shown in Formula I:

2. The method for preparing a monomer containing triquaternary ammonium salt ions and trivinylbenzene structure according to claim 1, comprising the following steps: The tri(N,N-dimethylaminopropyl)amine, p-chloromethylstyrene and a polar organic solvent are mixed and subjected to a quaternization reaction to obtain the monomer containing both triquaternary ammonium salt ions and trivinylbenzene structures.

3. The preparation method according to claim 2, characterized in that: The molar ratio of tris(N,N-dimethylaminopropyl)amine to p-chloromethylstyrene is 1:3-4; The polar organic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide.

4. The preparation method according to claim 2 or 3, characterized in that: The temperature of the quaternization reaction is 40-60° C. and the time is 1-3 hours.

5. Use of the monomer containing triquaternary ammonium salt ions and trivinylbenzene structures as claimed in claim 1 or the monomer containing triquaternary ammonium salt ions and trivinylbenzene structures obtained by the preparation method according to any one of claims 2 to 4 in the preparation of anion exchange resin.

6. An anion exchange resin, the preparation raw materials of which include vinyl monomer, initiator and solvent; the vinyl monomer is a monomer containing triquaternary ammonium salt ions and trivinyl benzene structures at the same time, or a mixture of a monomer containing triquaternary ammonium salt ions and trivinyl benzene structures at the same time and other water-soluble vinyl monomers; the monomer containing triquaternary ammonium salt ions and trivinyl benzene structures at the same time is the monomer containing triquaternary ammonium salt ions and trivinyl benzene structures at the same time as claimed in claim 1 or the monomer containing triquaternary ammonium salt ions and trivinyl benzene structures at the same time obtained by the preparation method described in any one of claims 2 to 4; the other water-soluble vinyl monomer is N-hydroxyacrylamide.

7. The anion exchange resin according to claim 6, characterized in that The mass ratio of the triquaternary ammonium salt ion and trivinylbenzene structure monomer to other water-soluble vinyl monomers is 1.1 to 9:1; The mass of the initiator is 1-2% of the mass of the ethylene monomer; The solvent includes water.

8. The method for preparing the anion exchange resin according to claim 6 or 7, comprising the following steps: The vinyl monomer, the initiator and the solvent are mixed and subjected to free radical polymerization reaction to obtain an anion exchange resin.

9. The preparation method according to claim 8, characterized in that: The temperature of the free radical polymerization reaction is 80-90° C. and the time is 0.5-1.5 h.

10. Use of the anion exchange resin according to any one of claims 6 to 7 or the anion exchange resin prepared by the preparation method according to any one of claims 8 to 9 in water treatment, electrolytes, material purification or oil extraction.

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