A polycyano-containing bis(diallylammonium)betaine and its preparation method

Abstract

The present invention uses organic polyamines, N-glycidyl-N,N-diallyl-N-alkylammonium chloride, acrylonitrile, propane sultone, or γ-butyrolactone as primary raw materials. Through classic ring-opening, addition, and quaternization reactions, a polycyano-containing bis(diallylammonium) betaine is produced. This crosslinker can be used as a crosslinker for grafting acrylonitrile onto the surface of non-woven fabrics based on seawater uranium-extracted polyethylene or polypropylene. It also introduces more cyano groups, improving grafting efficiency and enhancing the grafted material's hydrophilicity, uranyl anion complexing ability, antibacterial properties, and antifouling properties. It can also be used as a crosslinker in the preparation of electroactive polyolefin materials, imparting hydrophilicity, electrical conductivity, or antibacterial properties to the polyolefin materials.

Description

Technical Field

[0001] The present invention relates to a betaine containing unsaturated ammonium and a preparation method thereof, in particular to a bis(diallylammonium) betaine containing multiple cyano groups in its molecular structure and a preparation method thereof. The betaine is used as a multifunctional crosslinking agent for grafting acrylonitrile on the surface of a polymer material for uranium extraction from seawater, and belongs to the field of functional polymer materials. Technical Background

[0002] Uranium is one of the primary raw materials for green and environmentally friendly nuclear energy. Uranium reserves in vast oceans are enormous, but extracting uranium from seawater is fraught with challenges. Comprehensive evaluation of uranium adsorption materials, including substrate selection, preparation methods, ease of use, cost-effectiveness, safety, environmental protection, and energy-saving recycling, has led to years of experimental and theoretical research demonstrating that amidoxime-modified polymers are preferred adsorbents for the selective extraction of uranyl ions from seawater. The earliest polyamidoximate-based polymers used were amidoxime-modified polyacrylonitrile fibers. However, amidoxime-modified polyacrylonitrile fibers present several insurmountable drawbacks. First, to increase the adsorption capacity of amidoxime-modified polyacrylonitrile fibers, it is desirable to maximize the amidoxime-modified nitrile groups on the polyacrylonitrile fiber surface. However, excessive amidoxime-modified polyacrylonitrile fibers exhibit poor mechanical properties. Second, the amidoxime groups in amidoxime-modified polyacrylonitrile fibers have limited three-dimensional freedom, making it difficult to form stable geometric complexes with uranyl anions in a 2:1 or 4:1 ratio, making them susceptible to absorption by the high Fe content in seawater. 3+ 、Ni 2+ or Cu 2+ ③ The complex adsorption of uranyl ions in seawater and amidoximated polyacrylonitrile fibers with low hydrophilicity is relatively slow, and it takes about 30 days or more to reach saturated adsorption.

[0003] For years, scientists from various countries have been working to identify uranyl ion-absorbing materials and technologies that meet the following requirements: high selectivity for uranyl ion adsorption, rapid equilibrium adsorption rate, high equilibrium adsorption capacity, high hydrophilicity, large surface area in contact with seawater, high mechanical strength, durability, chemical stability in seawater, resistance to microbial adhesion, simple adsorption-desorption process, low recycling cost, easy placement in open seawater, easy retrieval and processing, safe labor, and efficient operation. Research results from scholars in the United States, Japan, China, and other countries have shown that non-woven fabrics based on polyethylene or polypropylene, grafted with acrylonitrile and functional monomers, are the most satisfactory uranium-absorbing materials. First, polyethylene or polypropylene substrates are widely available, with large output, low prices, high chemical stability, and surface grafting polymerization has almost no effect on their own mechanical properties; second, non-woven fabrics have high porosity and large specific surface area, and the shearing, hot pressing, curling, folding, kneading, and weaving processes are simple and convenient, and they are easily adapted to be placed in the shape of nets, ropes, tree branches and leaves, kelp, or seaweed in the open ocean at various depths to absorb and filter seawater. Furthermore, in addition to grafting acrylonitrile, functional monomers are also selected for copolymerization with acrylonitrile. These functional monomers include ① acrylic acid, unsaturated sulfobetaine, or unsaturated phosphoric acid / unsaturated phosphonic acid, which can enhance the complexation effect on uranyl anions; ② unsaturated quaternary ammonium salts, which can not only significantly improve the hydrophilicity of the non-woven fabric surface and achieve water-wetting contact between seawater and the fabric surface, but also attract uranyl anions to the uranium-absorbing material through the electrostatic attraction of its positive charge, thereby achieving rapid ion exchange between the uranium-absorbing material and seawater, and also enhance the uranium-absorbing material's resistance to the attachment and growth of marine microorganisms on its surface; ③ organic amines can improve the hydrophilicity and uranium-absorbing capacity of the uranium-absorbing material.

[0004] Existing methods for grafting acrylonitrile / functional monomers onto the surfaces of non-woven fabrics such as polyethylene or polypropylene include radiation grafting, free radical grafting, plasma grafting, etc. However, these methods all have an insurmountable drawback, namely the homopolymerization of acrylonitrile and functional monomers. The homopolymerization of acrylonitrile or functional monomers not only results in ineffective consumption of monomer raw materials, but also requires a cleaning process prior to the amidoximation process after grafting acrylonitrile and functional monomers onto the surfaces of non-woven fabrics such as polyethylene or polypropylene. To this end, the present invention provides a polycyano group-containing bis(diallylammonium) betaine, which is used as a multifunctional crosslinking agent for grafting acrylonitrile and functional monomers onto the surfaces of non-woven fabrics such as polyethylene or polypropylene, with the aim of improving the grafting efficiency and simultaneously introducing quaternary ammonium cations and sulfobetaine or carboxybetaine. Summary of the Invention

[0005] The present invention provides a bis(diallylammonium) betaine containing a polycyano group, characterized in that the bis(diallylammonium) betaine containing a polycyano group has a structure shown in general formula (I):

[0006]

[0007] Wherein the general formula (I) Refers to C2~C 18 Alkylidene, Q is -SO3 - or -CO2 - , n is selected from a natural number between 1 and 4, R is selected from C1 to C 18 Hydrocarbon, X - Select Cl - Br - or I - .

[0008] The polycyano-containing poly(diallylammonium) betaine of the present invention is prepared from industrial products such as organic polyamines containing multiple N atoms in their molecular structures, glycidyl ammonium, acrylonitrile and propane sultone or gamma-butyrolactone as main raw materials through classic ring-opening reaction, aza-Michael reaction and quaternization reaction.

[0009] The organic polyamine has a structure shown in the general formula (II):

[0010]

[0011] Among them, Refers to C2~C 18 Hydrocarbylene, n is selected from a natural number between 1 and 4. The specific selection of organic polyamines of general formula (II) is mainly preferred in industrial products, for example: ethylenediamine, 1,3-propylenediamine, 1,6-hexanediamine, 1,10-decanediamine, N-(3-aminopropyl)ethylenediamine, N,N'-bis(3-aminopropyl)ethylenediamine, N-(3-aminopropyl)-1,3-propylenediamine, N,N'-bis(3-aminopropyl)1,3-propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropyltriamine, N- (3-aminopropyl)-1,4-butanediamine, N,N'-bis(3-aminopropyl)-1,4-butanediamine, N-(3-aminopropyl)-1,6-hexanediamine, N,N'-bis(3-aminopropyl)-1,6-hexanediamine, N,N'-bis(3-aminopropyl)-1,4-cyclohexanediamine, N,N'-bis(3-aminopropyl)-1,4-cyclohexanediamine or 4-amino-4-(3-aminopropyl)-1,7-heptanediamine.

[0012] The glycidyl ammonium refers to N-glycidyl-N,N-diallyl-N-alkyl ammonium halide having the structure shown in the general formula (III):

[0013]

[0014] The hydrocarbon group refers to R in the general formula (III), and R is selected from C1 to C 18 Hydrocarbon, X- Select Cl - Br - or I - The alkyl group is preferably benzyl, dodecyl or 4-hydroxy-3-formylbenzyl. Existing research results show that quaternary ammonium cations carrying benzyl, dodecyl or 4-hydroxy-3-formylbenzyl groups have high antibacterial activity.

[0015] Professionals are well aware that the nitrogen atoms in the organic polyamine molecules of general formula (II) can be primary or secondary amino groups. Both primary and secondary amino groups can undergo ring-opening reactions with glycidyl compounds. Research has clearly demonstrated the ring-opening reaction mechanism, reaction thermodynamics, reaction kinetics, material ratios, solvent selection, reaction temperature, and time control. The ring-opening reaction between primary amino groups and glycidyl compounds is relatively fast and highly exothermic, so careful attention must be paid to controlling the feed rate and reaction temperature in the early stages of the ring-opening reaction. Secondary amino groups can also undergo ring-opening reactions with glycidyl compounds, but this reaction is somewhat more difficult. In order to efficiently obtain the polycyano-containing bis(diallylammonium) salt of the present invention, it is sufficient to ensure that the molecular structure of the polycyano-containing bis(diallylammonium) salt has two diallylammonium structural units. Therefore, the ring-opening reaction between the secondary amine group in the organic polyamine molecule of general formula (II) and the glycidol compound is minimized, with the purpose of introducing more cyano groups into the polycyano-containing bis(diallylammonium) salt molecule. Therefore, controlling the material ratio, feeding method, feeding rate and reaction temperature is the key to the efficient and selective preparation of the ring-opening reaction product.

[0016] The product, containing multiple secondary amine groups in its molecular structure after the ring-opening reaction, undergoes an aza-Michael addition reaction with acrylonitrile. The reaction mechanism, thermodynamics, kinetics, material ratios, solvent selection, reaction temperature, reaction time, and product yield are clearly understood. Due to steric hindrance, the aza-Michael addition reaction between the secondary amine groups and acrylonitrile is slow, so the temperature is controlled slightly higher. Furthermore, the amount of acrylonitrile used is slightly larger than the theoretical amount, relative to the number of secondary amine groups.

[0017] Professionals are well aware that the tertiary amino group N atom after the aza-Michael addition reaction can, under appropriate conditions, undergo a quaternization reaction with propane sultone or γ-butyrolactone, thereby introducing a betaine structural unit with powerful coordination function and high selectivity for uranyl anions, laying the foundation for the polycyano group-containing bis(diallylammonium) betaines described in the present invention to have richer and more powerful functions. To this end, the present invention preferably uses propane sultone or γ-butyrolactone as the alkylating agent. Existing research results show that after the surface of polymer materials is connected with sulfobetaine or carboxybetaine, the surface hydrophilicity is greatly improved, which can effectively prevent the attachment of marine organisms to the polymer surface.

[0018] In summary, the following reaction formula schematically illustrates the overall process of preparing the polycyano-containing bis(diallylammonium)betaine of general formula (I) of the present invention using organic polyamine, glycidyl ammonium, acrylonitrile, and propane sultone or γ-butyrolactone as main raw materials:

[0019]

[0020] Among them, Refers to C1~C 18 Alkylidene, Q is -SO3 - or -CO2 - , n is selected from a natural number between 1 and 4, R is selected from C1 to C 18 The hydrocarbon group, X - Select Cl - Br - or I - .

[0021] The preparation method of the polycyano-containing bis(diallylammonium)betaine of the present invention comprises the following specific steps: using a solvent to dissolve an organic polyamine, glycidyl ammonium and a polymerization inhibitor respectively, preparing an organic polyamine solution ①, a glycidyl ammonium and a polymerization inhibitor solution ②, regulating the temperature of a tubular reactor at 5 to 25° C., and then continuously adding the solution ① and the solution ② to the tubular reactor in both directions. After 0.5 to 1.0 hours after the addition is completed, the reactant system flows into a reactor, the temperature of the material in the reactor is maintained at 25 to 50° C., and the reaction is stirred for 0.5 to 5 seconds. After the reaction mixture is stirred for 2 hours, the temperature of the reactor is raised to 50-70°C, 1,3-propane sultone or γ-butyrolactone is added to the reactor, and the mixture is stirred for 2-20 hours. The solvent is then partially recovered by rotary evaporation, the temperature of the reactor is lowered to room temperature, and the solid matter is collected. The solid matter is filtered, washed, purified by recrystallization with a small molecule alcohol, and vacuum dried to a constant weight to obtain a polycyano-containing bis(diallylammonium)betaine of the general formula (I).

[0022] The organic polyamine has a structure shown in the general formula (II):

[0023]

[0024] Among them, Refers to C2~C 18 The alkylene group, n is a natural number selected from 1 to 4.

[0025] The solvent is one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, 2-ethoxyethanol acetate, ethyl acetate, methyl acetate, butyl acetate, toluene, acetone, butanone, anisole, chlorobenzene, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, or N,N-dimethylacetamide. The amount of the solvent used is 2 to 10 times the mass of the organic polyamine.

[0026] The glycidyl ammonium refers to N-glycidyl-N,N-diallyl-N-alkylammonium halide of the structure shown in the general formula (III):

[0027]

[0028] The alkyl group refers to R in the general formula (III), and R is selected from C1 to C 18 Hydrocarbon, X - Select Cl - Br - or I - .

[0029] The molar amount of the glycidyl ammonium is 1.0 to 1.2 times the molar amount of -NH2 groups contained in the molecular structure of the organic polyamine.

[0030] The polymerization inhibitor refers to one or more of hydroquinone, p-methoxyphenol, tert-butylhydroquinone, 2,6-dibutylhydroquinone, 2,6-di-tert-butyl-p-cresol or 2,4,6-tri-tert-butylphenol; the amount of the polymerization inhibitor is 0.5-5% of the mass of the glycidyl ammonium.

[0031] The molar amount of acrylonitrile is 0.5 to 1.5 times the molar amount of the NH structural unit contained in the organic polyamine molecular structure.

[0032] The molar amount of 1,3-propane sultone or γ-butyrolactone is 0.5 to 1.5 times the molar amount of nitrogen atoms contained in the organic polyamine.

[0033] The small molecule alcohol refers to one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol. The amount of the small molecule alcohol is 2 to 10 times the mass of the organic polyamine.

[0034] The present invention provides a bis(diallylammonium) betaine containing polycyano groups, which has the following beneficial effects:

[0035] ① It is well known to professionals that the polycyano-containing bis(diallylammonium) betaine of the present invention is used as a crosslinking agent for grafting acrylonitrile onto the surface of polymer materials such as polyethylene or polypropylene, which can effectively prevent the formation of homopolymers of acrylonitrile during the grafting process, improve the grafting efficiency of acrylonitrile, and ensure the utilization rate of acrylonitrile. At the same time, functional groups such as cyano groups, quaternary ammonium cations, sulfobetaine, or carboxybetaine are introduced, resulting in a multi-pronged grafting modification effect on the surface of polymer materials such as polyethylene or polypropylene.

[0036] ② After grafting, the surface of the polymer material, such as polyethylene or polypropylene, significantly enhances its hydrophilicity, facilitating its wet contact with seawater and increasing the equilibrium uranium adsorption rate of the uranium adsorption material. Furthermore, the grafted surface of the polymer material is endowed with antibacterial and antifouling properties, effectively preventing bacteria and microorganisms in seawater from adhering to and growing on the surface of the uranium adsorption material, thereby reducing the labor intensity of recycling the uranium adsorption material.

[0037] ③ The quaternary ammonium salt, sulfobetaine, or carboxybetaine grafted onto the surface of the polymer material such as polyethylene or polypropylene enhances the coordination ability with the uranyl anion and improves the adsorption capacity of the uranium adsorption material.

[0038] ④ The cyano group carried by the polycyano-containing bis(diallylammonium) betaine also has an amidoximation effect, wherein the spacer arm connecting the amidoxime group to the main chain is twice as long as that of polyacrylonitrile amidoxime, and has a high degree of freedom in three-dimensional space, which can effectively increase the probability of forming a stable geometric complex with uranyl anion in a 2:1 or 4:1 ratio.

[0039] ⑤ The polycyano-containing bis(diallylammonium) betaine is easily soluble in water, soluble in small molecule alcohols or a mixed solution of small molecule alcohols and acrylonitrile, so the surface grafting process of the polymer material such as polyethylene or polypropylene can be carried out in the aqueous phase, reducing the amount of VOC generated during the grafting process and realizing the clean production of uranium extraction materials from seawater. DETAILED DESCRIPTION

[0040] The following examples further illustrate the polycyano-containing bis(diallylammonium)betaine and its preparation method, for the purpose of providing a better understanding of the present invention. Therefore, any information not listed in the examples regarding the polycyano-containing bis(diallylammonium)betaine and its preparation method should not be construed as limiting the scope of the present invention.

[0041] Example 1 Preparation of Polycyano-Containing Bis(Diallylammonium) Betaine (1)

[0042] Weigh 6 g (0.100 mol) of ethylenediamine and dissolve it in 50 g of ethanol. Weigh 58 g (0.208 mol) of N-glycidyl-N,N-diallyl-N-benzylammonium chloride and 1.6 g of hydroquinone and dissolve them in 70 g of ethanol. Control the temperature at 10-15 ° C and add them slowly and continuously in two directions into the tubular reactor. After 1 hour of addition, flow into the reactor. Raise the temperature of the liquid in the reactor to 15-25 ° C and stir the reaction for 2 hours. Then add 12 g (0.22 mol) of acrylonitrile to the reactor. 6mol), the temperature of the material in the reactor was raised to 50-70°C, and the reaction was stirred for 6 hours; then 18g (0.148mol) of 1,3-propane sultone was added to the reactor, and the reaction was stirred for 12 hours. Part of the ethanol was recovered by rotary evaporation, and the temperature of the material in the reactor was lowered to room temperature. A white solid material was precipitated, filtered, washed with ethanol, recrystallized with isobutanol, and then sent to a vacuum drying oven to be dried to constant weight, to obtain 89.4g of white crystalline product (1). The product yield was 92.2% based on ethylenediamine. The analytical data of the white crystalline product (1): IR (cm -1 , KBr tablets): 3404 (s, OH), 3031 (w, double bond CH), 2938, 2873 (s, methylene CH), 2248 (s, C≡N), 1647, 1484 (s, benzene ring C=C), 1131, 1108 (m, CO); 1 H-NMR (δ, D2O): 2.29 (m, 4H), 2.86 (t, 4H), 3.28-3.92 (m, 32H), 4.47 (m, 4H), 4.51 (s, 4H), 4.91-5.07 (m, 12H), 7.02-7.22 (m, 10H). Chemical titration analysis of Cl in the white crystalline product (1) - The content is 8.18%, and C 43 H 64 Cl2N 10 The Cl content of the O8S2 molecular formula is 8.36% (calculated value), which is quite consistent. Comprehensively judging that the white crystalline product (1) has the structure of polycyano-containing bis(diallylammonium)sulfobetaine represented by formula (1):

[0043]

[0044] The test results of properties of bis(diallylammonium)sulfobetaine (1) containing polycyano groups show that it is very soluble in water, methanol, ethanol, DMSO or acrylonitrile, but insoluble in toluene, chloroform or ethyl acetate.

[0045] Example 2 Preparation of Polycyano-Containing Bis(Diallylammonium)Sulfobetaine (2)

[0046] According to the preparation method and operation steps of Example 1, ethylenediamine is replaced by triethylenetetramine, and N-glycidyl-N,N-diallyl-N-benzylammonium chloride is replaced by N-glycidyl-N,N-diallyl-N-dodecylammonium bromide to obtain product (2). Similarly, IR spectrum analysis, 1 H-NMR analysis and elemental analysis determined that the product (2) had the structural characteristics of polycyano-containing bis(diallylammonium)sulfobetaine (2) as shown in formula (2):

[0047]

[0048] The property test of bis(diallylammonium)sulfobetaine (2) containing polycyano groups showed that it is easily soluble in water, and its aqueous solution has the foaming characteristics of quaternary ammonium surfactants. It is soluble in methanol, ethanol, acrylonitrile, and DMSO, but insoluble in benzene, toluene, and chloroform.

[0049] Example 3 Preparation of Polycyano-Containing Bis(Diallylammonium)Carboxybetaine (3)

[0050] According to the preparation method and operation steps of Example 1, ethylenediamine is replaced by triethylenetetramine, N-glycidyl-N,N-diallyl-N-benzylammonium chloride is replaced by N-glycidyl-N,N-diallyl-N-dodecylammonium bromide, and propane sultone is replaced by γ-butyrolactone to obtain product (3). Similarly, IR spectrum analysis, 1 H-NMR analysis and elemental analysis determined that the product (3) may have the structural characteristics of polycyano-containing bis(diallylammonium)carboxybetaine (3) of formula (3):

[0051]

[0052] The property test of bis(diallylammonium)sulfobetaine (3) containing polycyano groups showed that it is easily soluble in water and its aqueous solution has the foaming phenomenon of quaternary ammonium surfactants; it is soluble in methanol, ethanol, and acrylonitrile, but insoluble in benzene, toluene, and chloroform.

[0053] Example 4 Preparation of Bis(Diallylammonium)Sulfobetaine (4) Containing Polycyano Groups

[0054] According to the preparation method and operation steps of Example 1, ethylenediamine is replaced with N,N'-bis(3-aminopropyl)-1,4-butanediamine to obtain product (4). Similarly, IR spectrum analysis, 1H-NMR analysis and elemental analysis determined that the product (4) may have the structural characteristics of polycyano-containing bis(diallylammonium)sulfobetaine (4) of formula (4):

[0055]

[0056] The property test of bis(diallylammonium)sulfobetaine (4) containing polycyano groups showed that it is easily soluble in water, soluble in methanol, ethanol, DMSO, and acrylonitrile, but insoluble in benzene, toluene, and chloroform.

[0057] Example 5 Preparation of Bis(Diallylammonium)Sulfobetaine (5) Containing Polycyano Groups

[0058] According to the preparation method and operation steps of Example 1, ethylenediamine is replaced by N,N'-bis(3-aminopropyl)-1,4-butanediamine, and N-glycidyl-N,N-diallyl-N-benzylammonium chloride is replaced by N-glycidyl-N,N-diallyl-N-(4-hydroxy-3-formylbenzyl)ammonium chloride to obtain product (5). Similarly, IR spectrum analysis, 1 H-NMR analysis and elemental analysis determined that the product (5) may have the structural characteristics of bis(diallylammonium)sulfobetaine (5) containing polycyano groups:

[0059]

[0060] The property test of bis(diallylammonium)sulfobetaine (5) containing polycyano groups showed that it is easily soluble in water, soluble in methanol, ethanol, DMSO, and acrylonitrile, but insoluble in benzene, toluene, and chloroform.

[0061] Example 6 Properties of Polycyano-containing Bis(Diallylammonium) Betaines of Examples 1 to 5

[0062] The polycyano group-containing bis(diallylammonium) betaines in Examples 1 to 5 were all readily soluble in water, and aqueous solutions with a mass percentage concentration of 20% were prepared. 2 mL of the aqueous solutions of each concentration in Examples 1 to 5 were mixed with 10 mL of culture medium at dilution ratios of 1:2, 1:5, 1:10, 1:20, 1:50, 1:100, and 1:1000, and 2 drops of the pathogenic bacteria suspension were added. After thorough mixing, the mixture was incubated in a 37° C. incubator for 24 hours. The growth of the pathogenic bacteria was observed, and the minimum inhibitory concentration (MIC) was calculated. The test results are shown in Table 1.

[0063] Table 1 Antibacterial test results

[0064]

Claims

1. A bis(diallylammonium) betaine containing a polycyano group, characterized in that The polycyano-containing bis(diallylammonium) betaine has a structure shown in general formula (I): Wherein the general formula (I) Refers to C2~C 18 Alkylidene, Q is -SO3 - or -CO2 - , n is selected from a natural number between 1 and 4, R is selected from C1 to C 18 Hydrocarbon, X - Select Cl - Br - or I - .

2. A method for preparing a polycyano-containing bis(diallylammonium)betaine according to claim 1, characterized in that The preparation method of the polycyano-containing bis(diallylammonium) betaine is as follows: using a solvent to dissolve an organic polyamine, glycidyl ammonium and a polymerization inhibitor, and respectively preparing an organic polyamine solution ①, a glycidyl ammonium and a polymerization inhibitor solution ②; The temperature of the tubular reactor is controlled at 5-25° C., and then the solution ① and the solution ② are continuously added to the tubular reactor in both directions. 0.5-1.0 hour after the addition is completed, the reactant system flows into the reactor, the temperature of the material in the reactor is maintained at 25-50° C., and the reaction is stirred for 0.5-5 hours; then the temperature of the material in the reactor is lowered to 15-35° C., acrylonitrile is added to the reactor, and the reaction is stirred for 2 hours, and then the temperature of the material in the reactor is raised to 50-70° C., 1,3-propane sultone or γ-butyrolactone is added to the reactor, and the reaction is stirred for 2-20 hours. After that, part of the solvent is recovered by rotary evaporation, the temperature of the material in the reactor is lowered to room temperature, and the solid matter is collected. After filtering, washing, recrystallization with small molecule alcohol, and vacuum drying to constant weight, a polycyano-containing bis(diallylammonium)betaine of general formula (I) is obtained; The organic polyamine has a structure shown in the general formula (II): Among them, Refers to C2~C 18 Hydrocarbylene, n is a natural number selected from 1 to 4; The glycidyl ammonium refers to N-glycidyl-N,N-diallyl-N-alkyl ammonium halide having the structure shown in the general formula (III): R selects C1~C 18 Hydrocarbon, X - Select Cl - Br - or I - ; The molar amount of the glycidyl ammonium is 1.0 to 1.2 times the molar amount of -NH2 groups contained in the molecular structure of the organic polyamine; The polymerization inhibitor refers to one or more of hydroquinone, p-methoxyphenol, tert-butylhydroquinone, 2,6-dibutylhydroquinone, 2,6-di-tert-butyl-p-cresol or 2,4,6-tri-tert-butylphenol; the amount of the polymerization inhibitor is 0.5-5% of the mass of the glycidyl ammonium; The molar amount of acrylonitrile is 0.5 to 1.5 times the molar amount of NH groups contained in the molecular structure of the organic polyamine; The molar amount of 1,3-propane sultone or γ-butyrolactone is 0.5 to 1.5 times the molar amount of nitrogen atoms contained in the organic polyamine.

3. The method for preparing a polycyano-containing bis(diallylammonium)betaine according to claim 2, characterized in that The solvent refers to one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, 2-ethoxyethanol acetate, ethyl acetate, methyl acetate, butyl acetate, toluene, acetone, butanone, anisole, chlorobenzene, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide; the amount of the solvent used is 2 to 10 times the mass of the organic polyamine.

4. The method for preparing a polycyano-containing bis(diallylammonium)betaine according to claim 2, characterized in that The small molecule alcohol refers to one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol. The amount of the small molecule alcohol is 2 to 10 times the mass of the organic polyamine.

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