Acrylonitrile-based polymers containing quaternary ammonium salt groups, and methods of making and using the same

Abstract

This invention relates to an acrylonitrile polymer containing quaternary ammonium salt groups, its preparation method, and its applications. The acrylonitrile polymer is prepared by reacting an acrylonitrile polymer, a polyamine, an aldehyde compound, and a quaternary ammonium salt containing epoxy groups. The polyacrylonitrile resin containing quaternary ammonium salt groups prepared in this invention exhibits a strong adsorption capacity for fluoride ions in wastewater and can be regenerated using NaCl aqueous solution. Furthermore, the preparation method of the fluoride ion adsorption resin in this invention is simple, the raw materials are inexpensive and readily available, and it has broad prospects for industrialization.

Description

Technical Field

[0001] This invention relates to the field of ion exchange resins, and more specifically, to an acrylonitrile polymer containing quaternary ammonium salt groups, its preparation method, and its applications. Background Technology

[0002] While fluoride is an essential trace element for the human body, excessive intake can lead to diseases such as osteoporosis. With industrial development, fluoride pollution in environmental water bodies has become increasingly severe. In recent years, standards for healthy drinking water have become increasingly stringent. According to the World Health Organization (WHO), the fluoride content in drinking water should not exceed 1.5 mg / L. Therefore, the treatment of fluoride-containing drinking water and industrial fluoride-containing wastewater has always been a key focus of research in the field of water treatment.

[0003] Currently, there are many methods for treating fluoride-containing wastewater both domestically and internationally, including adsorption, precipitation, electrodialysis, and co-distillation. Among these, adsorption is widely used due to its low secondary pollution, high adsorption efficiency, low energy consumption, and regenerability. Adsorption primarily utilizes the interaction between specific functional groups or elements in the adsorbent material and fluoride ions to remove fluoride ions from the water. Developing materials with high adsorption efficiency, regeneration capabilities, and mild regeneration conditions without secondary pollution is the current development direction for fluoride ion adsorption materials. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing fluoride ion adsorption resins, such as poor adsorption effect and easy secondary pollution caused by regeneration. The invention provides an acrylonitrile polymer containing quaternary ammonium salt groups, an acrylonitrile polymer resin with fluoride ion adsorption function, a method for preparing the same, and the application of the fluoride ion adsorption resin in the field of water treatment.

[0005] One objective of this invention is to provide an acrylonitrile polymer containing quaternary ammonium salt groups, which is prepared by reacting an acrylonitrile polymer, a polyamine, an aldehyde compound, and a quaternary ammonium salt containing epoxy groups.

[0006] A second objective of this invention is to provide a method for preparing the acrylonitrile polymer, comprising reacting the acrylonitrile polymer with a polyamine and an aldehyde compound to obtain an amino-modified acrylonitrile polymer, and then reacting the amino-modified acrylonitrile polymer with a quaternary ammonium salt containing an epoxy group.

[0007] The acrylonitrile polymer is polyacrylonitrile and its derivatives, preferably at least one of polyacrylonitrile, acrylonitrile-acrylic acid copolymer, acrylonitrile-methyl acrylate copolymer, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-itaconic acid copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-methylacrylonitrile copolymer, acrylonitrile-acrylate copolymer, and ethylene-propylene-styrene-acrylonitrile copolymer, more preferably at least one of polyacrylonitrile, acrylonitrile-methyl acrylate copolymer, and acrylonitrile-itaconic acid copolymer.

[0008] The aldehyde compound is preferably at least one of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, n-pentanaldehyde, n-heptanaldehyde, benzaldehyde, and paraformaldehyde, and more preferably at least one of formaldehyde, acetaldehyde, propionaldehyde, and paraformaldehyde.

[0009] The polyamine is preferably at least one of 1,3,5-triaminobenzene, melamine, diethylenetriamine, tetraethylenepentamine, polyethyleneimine, polyethylene polyamine, and polyetheramine, and more preferably at least one of polyethyleneimine and polyethylene polyamine.

[0010] The quaternary ammonium salt containing epoxy groups is a halide quaternary ammonium salt, preferably at least one selected from 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltriethylammonium chloride, 1,2-epoxypropyldimethyldodecylammonium chloride, diethyl-2,3-epoxypropyl-[3-(methyldimethoxy)]silylpropylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltriethylammonium bromide, 1,2-epoxypropyldimethyldodecylammonium bromide, and diethyl-2,3-epoxypropyl-[3-(methyldimethoxy)]silylpropylammonium bromide.

[0011] Preferably, the preparation method of the acrylonitrile polymer containing quaternary ammonium salt groups of the present invention may include the following steps:

[0012] (1) Disperse acrylonitrile polymers in a solution containing polyamines and aldehydes, and heat to react to obtain amino-modified acrylonitrile polymers.

[0013] (2) The amino-modified acrylonitrile polymer obtained in step (1) is added to a solution of quaternary ammonium salt containing epoxy groups, and the reaction is heated to obtain acrylonitrile polymer containing quaternary ammonium salt groups.

[0014] In step (1):

[0015] Based on 100 parts of solution, the content of acrylonitrile polymer is 0.5 to 20 parts, preferably 1 to 10 parts.

[0016] Based on 100 parts of solution, the content of polyamine is 0.1 to 10 parts, preferably 0.1 to 5 parts.

[0017] Based on 100 parts of solution, the content of aldehyde compounds is 0.1 to 5 parts, preferably 0.1 to 3 parts.

[0018] The reaction time is 1 to 24 hours, preferably 3 to 12 hours; the reaction temperature is 25 to 100°C, preferably 50 to 80°C.

[0019] In step (2):

[0020] Based on 100 parts of solution, the content of quaternary ammonium salt containing epoxy groups is 1 to 20 parts, preferably 2 to 10 parts;

[0021] The mass ratio of amino-modified acrylonitrile polymer to quaternary ammonium salt containing epoxy groups is (0.01-20):1, preferably (0.1-10):1.

[0022] The reaction temperature is 20–80℃, preferably 25–40℃; the reaction time is 1–12 h, preferably 2–6 h.

[0023] The third objective of this invention is to provide an acrylonitrile polymer resin obtained by the aforementioned preparation method.

[0024] The resin molecule contains quaternary ammonium salt groups and is prepared by reacting acrylonitrile polymer micron powder with polyamines, aldehyde compounds and quaternary ammonium salts containing epoxy groups.

[0025] The preparation of the resin preferably includes two processes: first, polyacrylonitrile and its derivatives react with aldehyde compounds and polyamines through the Mannich reaction to generate amino-modified polyacrylonitrile polymer powder; then, quaternary ammonium salt groups are modified onto the powder surface through the ring-opening reaction of amino and epoxy groups.

[0026] The polyacrylonitrile resin containing quaternary ammonium salt groups prepared in this invention has a strong adsorption capacity for fluoride ions in wastewater and can be regenerated by using NaCl aqueous solution.

[0027] The fourth objective of this invention is to provide the application of the acrylonitrile polymer containing quaternary ammonium salt groups or the acrylonitrile polymer resin in the field of water treatment.

[0028] The acrylonitrile polymers or acrylonitrile polymer resins described above can be applied in the field of water treatment, for example, for fluoride ion adsorption.

[0029] Through in-depth research, the inventors of this invention discovered that the quaternary ammonium salt groups on the modified polyacrylonitrile polymer molecular chain can undergo ion exchange with fluoride ions, thereby removing fluoride ions from water. At the same time, the resin after removing fluoride ions can be regenerated by soaking in sodium chloride aqueous solution. The regeneration method is simple, green and environmentally friendly, and has great potential for industrial application.

[0030] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0031] Figure 1 The infrared spectrum of polyacrylonitrile (PAN) powder modified with 2,3-epoxypropyltrimethylammonium chloride (PAN-NH4Cl) is shown. Detailed Implementation

[0032] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0033] This invention provides a polyacrylonitrile-based fluoride ion adsorption resin, the molecular structure of which contains quaternary ammonium salt groups. It is prepared by reacting acrylonitrile polymer micron powder with polyamines, aldehyde compounds and quaternary ammonium salts containing epoxy groups.

[0034] According to a preferred embodiment of the present invention, the acrylonitrile polymer is polyacrylonitrile and its derivatives, more preferably one of acrylonitrile-acrylic acid copolymer, acrylonitrile-methyl acrylate copolymer, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-itaconic acid copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-methyl acrylonitrile copolymer, acrylonitrile-acrylate copolymer, and ethylene-propylene-styrene-acrylonitrile copolymer, and even more preferably at least one of polyacrylonitrile, acrylonitrile-methyl acrylate copolymer, and acrylonitrile-itaconic acid copolymer.

[0035] According to a preferred embodiment of the present invention, the aldehyde compound is at least one of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, n-pentanaldehyde, n-heptanaldehyde, benzaldehyde, and paraformaldehyde, more preferably at least one of formaldehyde, acetaldehyde, propionaldehyde, and paraformaldehyde.

[0036] According to a preferred embodiment of the present invention, the polyamine is at least one selected from 1,3,5-triaminobenzene, melamine, diethylenetriamine, tetraethylenepentamine, polyethylene polyamine, polyethyleneimine, and polyetheramine, more preferably at least one selected from polyethyleneimine and polyethylene polyamine.

[0037] According to a preferred embodiment of the present invention, the quaternary ammonium salt containing epoxy groups is selected from one or more of 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltriethylammonium chloride, 1,2-epoxypropyldimethyldodecylammonium chloride, diethyl-2,3-epoxypropyl-[3-(methyldimethoxy)]silylpropylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltriethylammonium bromide, 1,2-epoxypropyldimethyldodecylammonium bromide, and diethyl-2,3-epoxypropyl-[3-(methyldimethoxy)]silylpropylammonium bromide.

[0038] The following describes the reaction mechanism of one embodiment of the preparation method of acrylonitrile polymers: taking polyacrylonitrile, formaldehyde, and polyethyleneimine as examples, firstly, polyacrylonitrile reacts with formaldehyde and polyethyleneimine in a Mannich reaction to generate amino-modified polyacrylonitrile; then, the amino group reacts with the epoxy group in a ring-opening reaction to complete the modification of the quaternary ammonium salt group onto the surface of the polyacrylonitrile particles.

[0039]

[0040] According to a preferred embodiment of the present invention, the method for preparing acrylonitrile polymer resin may include the following steps:

[0041] (1) Disperse acrylonitrile polymer powder in deionized water, add polyamine and aldehyde compounds, disperse evenly by ultrasonication, and then heat and react under stirring; after filtration and rinsing with deionized water, amino-modified acrylonitrile polymer powder is obtained.

[0042] (2) The polymer powder obtained in step (1) is added to an aqueous solution of a quaternary ammonium salt containing epoxy groups. After heating and reacting, the mixture is filtered and washed with deionized water to obtain acrylonitrile polymer powder modified with quaternary ammonium salt.

[0043] According to the method for preparing acrylonitrile polymer resin of the present invention, in step 1, the mass concentration of the acrylonitrile polymer is based on 100 parts of solution, and the content of the acrylonitrile polymer is 0.5 to 20 parts, preferably 1 to 10 parts, and more preferably 1 to 5 parts.

[0044] The mass concentration of the polyamine, based on 100 parts of solution, is 0.1 to 10 parts, preferably 0.1 to 5 parts, and more preferably 0.1 to 3 parts.

[0045] The mass concentration of the aldehyde compound, based on 100 parts of solution, is 0.1 to 5 parts, preferably 0.1 to 3 parts, and more preferably 0.1 to 2.5 parts.

[0046] According to the method for preparing acrylonitrile polymer resin of the present invention, in step 1, the reaction time is 1h to 24h, preferably 3h to 12h; the reaction temperature is 25℃ to 100℃, preferably 50℃ to 80℃.

[0047] According to the method for preparing acrylonitrile polymer resin of the present invention, in step 2, the mass concentration of the quaternary ammonium salt containing epoxy groups is based on 100 parts of solution, and the content of the quaternary ammonium salt containing epoxy groups is 1 to 20 parts, preferably 2 to 10 parts, and more preferably 2 to 5 parts.

[0048] The mass ratio of the amino-modified acrylonitrile polymer to the quaternary ammonium salt containing epoxy groups is (0.01-20):1, preferably (0.1-10):1, and more preferably (0.1-5):1.

[0049] According to the method for preparing acrylonitrile polymer resin of the present invention, in step 2, the reaction temperature is 20℃~80℃, preferably 25℃~40℃; the reaction time is 1h~12h, preferably 2h~6h.

[0050] The present invention will be described in detail below through embodiments.

[0051] In the following embodiments and comparative examples:

[0052] (1) The infrared absorption spectrum of the resin was measured by a Nicolet 6700 infrared spectrometer in single reflectance mode.

[0053] (2) Adsorption capacity test for fluoride ions: 0.1 g of adsorption resin was dispersed in 100 mL of sodium fluoride solution, the concentration of fluoride ions in the solution was 20 mg / L, and the solution was shaken at room temperature for 24 h; the supernatant was taken and the mercury ion concentration was determined by ICP method, and then the fluoride ion removal rate was calculated:

[0054] R = (C p -C f ) / C p ×100%,

[0055] Where R is the fluoride ion removal rate, and C p C represents the concentration of fluoride ions in the original solution. f This represents the concentration of fluoride ions in the solution after adsorption.

[0056] (3) Resin regeneration experiment: 0.1 g of resin that had adsorbed fluoride ions was dispersed in 100 mL of 1 mol / L NaCl aqueous solution and shaken at room temperature for 24 h; after filtration, the resin was rinsed with deionized water. The resulting resin was then dispersed again in sodium fluoride solution of the above concentration under the same experimental conditions, and the fluoride ion removal rate of the regenerated resin was calculated.

[0057] Additionally, in the following embodiments and comparative examples:

[0058] Polyacrylonitrile (number average molecular weight 70,000), acrylonitrile-methyl acrylate copolymer (number average molecular weight 100,000), and acrylonitrile-itaconic acid copolymer (number average molecular weight 120,000) were purchased from Maclean Biochemical Technology Co., Ltd.; polyethyleneimine (number average molecular weight 10,000), polyethylene polyamine, diethylenetriamine, tetraethylenepentamine, 1,3,5-triaminobenzene, 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltriethylammonium chloride, 1,2-epoxypropyldimethyldodecylammonium chloride, and 2,3-epoxypropyltrimethylammonium bromide were all purchased from Bailingwei Technology Co., Ltd.; formaldehyde, acetaldehyde, and propionaldehyde were purchased from Sinopharm Chemical Reagent Co., Ltd.

[0059] Comparative Example 1

[0060] 5g of polyacrylonitrile powder was dispersed in 100g of an aqueous solution containing 1% polyethyleneimine and 0.5% formaldehyde. After reacting at 60°C for 3 hours, the mixture was filtered and repeatedly washed with deionized water to obtain amino-modified polyacrylonitrile powder D1.

[0061] 0.1 g of resin D1 was dispersed in 100 mL of 20 mg / L sodium fluoride aqueous solution and shaken at room temperature for 24 h. The supernatant and the original solution were used to determine the fluoride ion concentration by ICP method, and then the fluoride ion removal rate was calculated. The above resin adsorbing fluoride ions was dispersed in 100 mL of 1 mol / L NaCl aqueous solution, shaken for 24 h, and then filtered to obtain regenerated resin. The removal rate of fluoride ions by the regenerated resin was then tested using the same method.

[0062] Example 1

[0063] 1 g of polyacrylonitrile powder was dispersed in 100 g of an aqueous solution containing 1 wt% polyethyleneimine and 0.5 wt% formaldehyde. After reacting at 60 °C for 3 h, the mixture was filtered and repeatedly washed with deionized water to obtain amino-modified polyacrylonitrile powder. Then, 10 g of the powder was dispersed in 100 g of an aqueous solution containing 5 wt% 2,3-epoxypropyltrimethylammonium chloride. After reacting at 40 °C for 6 h, the mixture was filtered, repeatedly washed with deionized water, and dried to obtain quaternary ammonium salt-modified polyacrylonitrile powder N1.

[0064] Figure 1This is the infrared spectrum of polyacrylonitrile (PAN) powder modified with 2,3-epoxypropyltrimethylammonium chloride (PAN-NH4Cl) in Example 1. Figure 1 It can be seen that after modification of PAN powder, at 964 cm⁻¹ -1 and 3389cm -1 New absorption peaks appeared at the locations, corresponding to the ammonium chloride group and the hydroxyl group generated after the ring-opening of the epoxy, respectively. This proves that the ammonium chloride group was successfully modified into PAN powder through a two-step modification method.

[0065] 0.1 g of resin N1 was dispersed in 100 mL of a 20 mg / L sodium fluoride aqueous solution and shaken at room temperature for 24 h. The supernatant and the original solution were used to determine the fluoride ion concentration by ICP method, and then the fluoride ion removal rate was calculated. The above resin adsorbing fluoride ions was dispersed in 100 mL of a 1 mol / L NaCl aqueous solution and shaken for 24 h. After filtration, the regenerated resin was obtained. The removal rate of fluoride ions by the regenerated resin was then tested using the same method.

[0066] Example 2

[0067] 10g of acrylonitrile-methyl acrylate copolymer powder was dispersed in 100g of an aqueous solution containing 2.5 wt% polyethylene polyamine and 2.5 wt% formaldehyde. After reacting at 60℃ for 3h, the mixture was filtered and repeatedly washed with deionized water to obtain amino-modified polyacrylonitrile powder. Then, 1g of this powder was dispersed in 100g of an aqueous solution containing 3 wt% 2,3-epoxypropyltriethylammonium chloride. After reacting at 40℃ for 6h, the mixture was filtered, repeatedly washed with deionized water, and dried to obtain quaternary ammonium salt modified polyacrylonitrile powder N2.

[0068] 0.1 g of resin N2 was dispersed in 100 mL of 20 mg / L sodium fluoride aqueous solution and shaken at room temperature for 24 h. The supernatant and the original solution were taken and the fluoride ion concentration was determined by ICP method, and then the fluoride ion removal rate was calculated. The above resin adsorbing fluoride ions was dispersed in 100 mL of 1 mol / L NaCl aqueous solution and shaken for 24 h. After filtration, the regenerated resin was obtained. The removal rate of fluoride ions by the regenerated resin was then tested using the same method.

[0069] Example 3

[0070] 1 g of acrylonitrile-itaconic acid copolymer powder was dispersed in 100 g of an aqueous solution containing 0.1 wt% diethylenetriamine and 0.1 wt% formaldehyde. After reacting at 60 °C for 3 h, the mixture was filtered and repeatedly washed with deionized water to obtain amino-modified polyacrylonitrile powder. Then, 10 g of this powder was dispersed in 100 g of an aqueous solution containing 3 wt% 1,2-epoxypropyldimethyldodecylammonium chloride. After reacting at 40 °C for 6 h, the mixture was filtered, repeatedly washed with deionized water, and dried to obtain quaternary ammonium salt modified polyacrylonitrile powder N3.

[0071] 0.1 g of resin N3 was dispersed in 100 mL of 20 mg / L sodium fluoride aqueous solution and shaken at room temperature for 24 h. The supernatant and the original solution were used to determine the fluoride ion concentration by ICP method, and then the fluoride ion removal rate was calculated. The above resin adsorbing fluoride ions was dispersed in 100 mL of 1 mol / L NaCl aqueous solution and shaken for 24 h. After filtration, the regenerated resin was obtained. The removal rate of fluoride ions by the regenerated resin was then tested using the same method.

[0072] Example 4

[0073] The preparation method of Example 1 was followed, except that tetraethylenepentamine was used instead of polyethyleneimine to prepare quaternary ammonium salt modified polyacrylonitrile powder N4.

[0074] 0.1 g of resin N4 was dispersed in 100 mL of a 20 mg / L sodium fluoride aqueous solution and shaken at room temperature for 24 h. The supernatant and the original solution were used to determine the fluoride ion concentration by ICP method, and then the fluoride ion removal rate was calculated. The above resin adsorbing fluoride ions was dispersed in 100 mL of a 1 mol / L NaCl aqueous solution and shaken for 24 h. After filtration, the regenerated resin was obtained. The removal rate of fluoride ions by the regenerated resin was then tested using the same method.

[0075] Example 5

[0076] The preparation method of Example 1 was followed, except that 1,3,5-triaminobenzene was used instead of polyethyleneimine to prepare quaternary ammonium salt modified polyacrylonitrile powder N5.

[0077] 0.1 g of resin N5 was dispersed in 100 mL of a 20 mg / L sodium fluoride aqueous solution and shaken at room temperature for 24 h. The supernatant and the original solution were used to determine the fluoride ion concentration by ICP method, and then the fluoride ion removal rate was calculated. The above resin that adsorbed fluoride ions was dispersed in 100 mL of a 1 mol / L NaCl aqueous solution and shaken for 24 h. After filtration, the regenerated resin was obtained. The removal rate of fluoride ions by the regenerated resin was then tested using the same method.

[0078] Example 6

[0079] The preparation method of Example 1 was followed, except that 2,3-epoxypropyltrimethylammonium bromide was used instead of 2,3-epoxypropyltrimethylammonium chloride to prepare quaternary ammonium salt modified polyacrylonitrile powder N6.

[0080] 0.1 g of resin N6 was dispersed in 100 mL of a 20 mg / L sodium fluoride aqueous solution and shaken at room temperature for 24 h. The supernatant and the original solution were used to determine the fluoride ion concentration by ICP method, and then the fluoride ion removal rate was calculated. The above resin adsorbing fluoride ions was dispersed in 100 mL of a 1 mol / L NaCl aqueous solution and shaken for 24 h. After filtration, the regenerated resin was obtained. The removal rate of fluoride ions by the regenerated resin was then tested using the same method.

[0081] Table 1

[0082]

[0083] As can be seen from Table 1, the polyacrylonitrile adsorption resin containing quaternary ammonium groups prepared in this invention has excellent adsorption performance for fluoride ions, and the removal rate of fluoride ions in water with a fluoride ion concentration of 20 mg / L can reach more than 84%; after regeneration with NaCl aqueous solution, the removal rate of fluoride ions by the resin still reaches more than 80%.

Claims

1. An acrylonitrile polymer containing a quaternary ammonium salt group, which is prepared by reacting an acrylonitrile polymer with a polyamine and an aldehyde compound to obtain an amino-modified acrylonitrile polymer, and then reacting the amino-modified acrylonitrile polymer with a quaternary ammonium salt containing an epoxy group. The acrylonitrile polymer is at least one selected from polyacrylonitrile, acrylonitrile-acrylic acid copolymer, acrylonitrile-methyl acrylate copolymer, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-itaconic acid copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-methylacrylonitrile copolymer, acrylonitrile-acrylate copolymer, and ethylene-propylene-styrene-acrylonitrile copolymer; the polyamine is at least one selected from 1,3,5-triaminobenzene, melamine, diethylenetriamine, tetraethylenepentamine, polyethyleneimine, polyethylenepolyamine, and polyetheramine; the aldehyde compound is methyl... At least one of aldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, n-pentanaldehyde, n-heptanaldehyde, benzaldehyde, and paraformaldehyde; wherein the quaternary ammonium salt containing an epoxy group is at least one of 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltriethylammonium chloride, 1,2-epoxypropyldimethyldodecylammonium chloride, diethyl-2,3-epoxypropyl-[3-(methyldimethoxy)]silylpropylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltriethylammonium bromide, 1,2-epoxypropyldimethyldodecylammonium bromide, and diethyl-2,3-epoxypropyl-[3-(methyldimethoxy)]silylpropylammonium bromide.

2. A method for preparing an acrylonitrile polymer according to claim 1, comprising reacting the acrylonitrile polymer with a polyamine and an aldehyde compound to obtain an amino-modified acrylonitrile polymer, and then reacting the amino-modified acrylonitrile polymer with a quaternary ammonium salt containing an epoxy group.

3. The method of claim 2, wherein Includes the following steps: (1) Disperse the acrylonitrile polymer in a solution containing polyamines and aldehydes, and heat to react to obtain an amino-modified acrylonitrile polymer; (2) Add the amino-modified acrylonitrile polymer obtained in step (1) to a solution containing an epoxy group of quaternary ammonium salt, and heat to react to obtain an acrylonitrile polymer containing quaternary ammonium salt groups.

4. The preparation method according to claim 3, characterized in that... In step (1): Based on 100 parts of solution, the content of acrylonitrile polymer is 0.5-20 parts; the content of polyamine is 0.1-10 parts; and the content of aldehyde compound is 0.1-5 parts.

5. The preparation method according to claim 4, characterized in that: Based on 100 parts of solution, the content of acrylonitrile polymer is 1 to 10 parts; the content of polyamine is 0.1 to 5 parts; and the content of aldehyde compound is 0.1 to 3 parts.

6. The preparation method according to claim 3, characterized in that... In step (1): The reaction time is 1~24h; the reaction temperature is 25~100℃.

7. The preparation method according to claim 6, characterized in that: The reaction time is 3~12h; the reaction temperature is 50~80℃.

8. The preparation method according to claim 3, characterized in that... In step (2): Based on 100 parts of solution, the content of quaternary ammonium salt containing epoxy groups is 1 to 20 parts; The mass ratio of amino-modified acrylonitrile polymers to quaternary ammonium salts containing epoxy groups is (0.01~20):

1.

9. The preparation method according to claim 8, characterized in that: Based on 100 parts of solution, the content of quaternary ammonium salt containing epoxy groups is 2 to 10 parts; The mass ratio of amino-modified acrylonitrile polymers to quaternary ammonium salts containing epoxy groups is (0.1~10):

1.

10. The preparation method according to claim 3, characterized in that... In step (2): The reaction temperature is 20~80℃; the reaction time is 1~12h.

11. The preparation method according to claim 10, characterized in that: The reaction temperature is 25~40℃; the reaction time is 2~6h.

12. The application of the acrylonitrile polymer containing quaternary ammonium salt groups as described in claim 1 in the field of water treatment.

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