A bis(diallylammonium) salt and its preparation method

Abstract

The present invention uses tetraglycidyl diamine, diallyl ammonium salt, bis(2-cyanoethyl)amine, etc. as the main raw materials, and through a classical ring-opening reaction, a bis(diallyl ammonium) salt is prepared. It can not only be used as a cross-linking agent for grafting acrylonitrile on the surface of non-woven fabrics based on polyethylene or polypropylene for uranium extraction from seawater, but also introduce more cyano groups, quaternary ammonium cations, amino groups, etc., which is of great significance for improving the grafting efficiency, or improving the hydrophilicity, uranyl anion complexing ability, antibacterial, antifouling and other functions of the grafted materials. The bis(diallyl ammonium) salt can also be used as a cross-linking agent for preparing electroactive polyolefin materials, endowing the polyolefin materials with hydrophilicity, conductivity or antibacterial functions.

Description

Technical Field

[0001] The invention relates to an unsaturated gemini quaternary ammonium salt and a preparation method thereof, in particular to a bis(diallyl ammonium) salt containing multiple cyano groups and multiple amine groups in a molecular structure and a preparation method thereof, which is used as a crosslinking agent for grafting acrylonitrile on the surface of a seawater uranium extraction polymer material, and belongs to the field of functional polymer materials. Technical Background

[0002] Uranium is one of the main raw materials for green and environmentally friendly nuclear energy. The uranium reserves in the vast seawater are very huge, but it is difficult to extract uranium from seawater. Experimental and theoretical studies over the years have shown that amidoxime polymers are the preferred adsorption materials for selectively extracting uranyl ions from seawater, based on comprehensive evaluation of the selection of substrates, preparation methods, ease of use, economic efficiency, safety and environmental protection, and recycling and energy saving of uranium adsorption materials. The earliest polyamidoxime polymer selected was amidoxime polyacrylonitrile fiber, but the amidoxime of polyacrylonitrile fiber has several insurmountable defects. ① In order to improve the adsorption capacity of amidoxime polyacrylonitrile fiber, it is hoped that the nitrile group on the surface of polyacrylonitrile fiber is amidoxime as much as possible. However, the mechanical properties of excessively amidoxime polyacrylonitrile fiber are relatively poor; ② The amidoxime groups contained in amidoxime polyacrylonitrile fiber have small degrees of freedom in three-dimensional space, and it is difficult to form a stable geometric complex with uranyl anions in a 2:1 or 4:1 ratio, and are easily absorbed by high concentrations of Fe in seawater. 3+ 、Ni 2+ Cu 2+ etc.; 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 more than half a century, in order to find uranium adsorption materials and technical processes that meet the following conditions: good adsorption selectivity for uranyl anions, fast equilibrium adsorption rate, large equilibrium adsorption capacity, high hydrophilicity, large specific surface area in contact with seawater, high mechanical strength and durability, high chemical stability in seawater and resistance to the adhesion of microorganisms in seawater, simple adsorption-desorption process, low recycling cost, easy to place in open seawater and easy to retrieve and process, safe labor, and high efficiency in operation, people have been making unremitting efforts. The research results of scholars from the United States, Japan, China and other countries show that non-woven fabrics grafted with acrylonitrile and functional monomers on the surface with polyethylene or polypropylene as the substrate are preferred uranium adsorption materials. Firstly, the polyethylene or polypropylene substrate has a wide source, a large output, a low price, high chemical stability, and surface graft polymerization has almost no impact on its own mechanical properties; secondly, the non-woven fabric has a high porosity and a large specific surface area, and it is simple and convenient to perform processes such as hot pressing, shearing, curling, folding, kneading, and weaving on it, and it is easy to adapt to be placed in open seawater at various depths in the form of netting, rope, branches, kelp, or seaweed to filter seawater. Furthermore, in addition to grafting acrylonitrile, functional monomers are also selected to co-graft 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, realize the water-wetting contact between seawater and the fabric surface, but also attract uranyl anions to aggregate on the uranium adsorption material through the electrostatic attraction of the positive charges it carries, realize the rapid ion exchange between the uranium adsorption material and seawater, and can also enhance the resistance of the uranium adsorption material to the attachment and growth of marine microorganisms on its surface; ③ organic amines, which can improve the hydrophilicity and uranium adsorption capacity of the uranium adsorption material.

[0004] Existing methods for grafting acrylonitrile / functional monomers on the surface of non-woven fabrics such as polyethylene or polypropylene include radiation grafting, free radical grafting, plasma grafting, etc. However, these methods all have insurmountable defects, that is, the homopolymerization problem of acrylonitrile and functional monomers. The homopolymerization phenomenon of acrylonitrile or functional monomers not only causes the ineffective consumption of monomer raw materials, but also brings a necessary cleaning process to the amidoximation process after grafting acrylonitrile and functional monomers on the surface of non-woven fabrics such as polyethylene or polypropylene. Therefore, the present invention provides a bis(diallylammonium) salt containing multiple cyano groups and multiple amino groups, which is used as a cross-linking agent for grafting acrylonitrile and functional monomers on the surface of non-woven fabrics such as polyethylene or polypropylene, aiming to improve the grafting efficiency, ensure the utilization rate of acrylonitrile and functional monomers in the grafting process, and at the same time endow structural units such as multiple cyano groups, multiple quaternary ammonium cations, and multiple organic polyamines. Summary of the Invention

[0005] The present invention provides a bis(diallylammonium) salt containing multiple cyano groups and multiple amino groups, characterized in that the bis(diallylammonium) salt has a structure shown in general formula (Ⅰ) or general formula (Ⅱ):

[0006]

[0007] Among them, R in general formula (I) or general formula (II) is selected from C1-C 18 hydrocarbyl or refers to C2-C 18 alkylene, Q is selected from O or S, n is a natural number between 0 and 2000, X - is selected from Cl - , Br - or I - and R1 is selected from C1-C 18 hydrocarbyl.

[0008] The specific preparation method of the bis(diallylammonium) salt of the present invention comprises the following steps:

[0009] Weigh the solvent, tetraglycidyl diamine, diallylammonium salt and inhibitor respectively and put them into the reaction kettle. Control the temperature of the materials in the reaction kettle at 40-90 °C, stir and react for 2-20 hours under N2 protection, then put bis(2-cyanoethyl)amine into the reaction kettle and continue to stir and react at the same temperature for 2-20 hours. Then, rotary evaporate to remove part of the solvent, lower the temperature of the materials in the reaction kettle to room temperature, filter to obtain a solid product, recrystallize and purify the solid product with a small molecule alcohol, and obtain the bis(diallylammonium) salt with the structure shown in general formula (I) or general formula (II) after vacuum drying.

[0010] The molar ratio of tetraglycidyl diamine / diallylammonium salt / bis(2-cyanoethyl)amine is 1:1-1.2:0.8-1.2.

[0011] The tetraglycidyl diamine has the structure shown in general formula (III):

[0012]

[0013] Among them, in general formula (III) refers to C2-C 18 alkylene, Q is selected from O or S, n is a natural number between 0 and 2000.

[0014] The diallylammonium salt refers to one of N-substituted diallylamine hydrochloride, hydrobromide, or hydroiodide, and has the structure shown in general formula (IV):

[0015]

[0016] Among them, X is selected from one of Cl, Br or I, the substituent refers to R in general formula (IV), and the R is selected from C1-C 18 hydrocarbyl or wherein n is selected from natural numbers between 0 and 2000, and R1 is selected from C1 - C 18 hydrocarbon group.

[0017] 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 - methoxyethyl acetate, 2 - ethoxyethyl acetate, ethyl acetate, methyl acetate, butyl acetate, toluene, acetone, butanone, anisole, chloroform, chlorobenzene, N - methylpyrrolidone, dimethyl sulfoxide, N,N - dimethylformamide or N,N - dimethylacetamide; the dosage of the solvent is 1 - 10 times the mass of the tetraglycidyl diamine.

[0018] The polymerization inhibitor is selected from one or more of hydroquinone, p - methoxyphenol, tert - butylhydroquinone, 2,6 - di - tert - butylhydroquinone, 2,6 - di - tert - butyl - p - cresol, 2,4,6 - tri - tert - butylphenol; the dosage of the polymerization inhibitor is 0.3 - 3% of the mass of the diallyl ammonium salt.

[0019] The small - molecule alcohol refers to one or more of methanol, ethanol, n - propanol, isopropanol, n - butanol, isobutanol, tert - butanol; wherein the dosage of the small - molecule alcohol is 1 - 10 times the mass of the tetraglycidyl diamine.

[0020] The beneficial effects of the bis(diallyl ammonium) salt provided by the present invention are as follows:

[0021] ① The bis(diallyl ammonium) salt described in the present invention is used as a cross - linker for surface grafting of polymer materials such as polyethylene or polypropylene, which can significantly improve the grafting efficiency of acrylonitrile and functional monomers, and effectively reduce the probability of homopolymer formation of acrylonitrile and functional monomers during the grafting process.

[0022] ② The molecular structure of the bis(diallyl ammonium) salt described in the present invention contains multiple cyano groups. After amidoximation, the spacer arm connecting the amidoxime groups in the main chain is twice as long as that of polyacrylonitrile. Therefore, the amidoxime groups have a high degree of freedom in three - dimensional space. Together with multiple tertiary amine groups and two quaternary ammonium cations, it can effectively increase the probability of forming a stable geometric complex with uranyl anions in a ratio of 2:1 or 4:1.

[0023] The raw materials for preparing the bis(diallyl ammonium) salt described in the present invention, including tetraglycidyl diamine, diallyl ammonium salt, bis(2 - cyanoethyl)amine, etc., are all industrial products. The preparation method is simple, and the process is safe and efficient.

[0024] ③ The quaternary ammonium cations in the molecular structure of the bis(diallylammonium) salt of the present invention endow the surface-grafted polymer materials with antibacterial and antifouling properties, etc., which can effectively prevent the attachment and growth of bacteria or microorganisms in seawater on the surface of the uranium absorption material, and reduce the labor intensity of the cyclic use of the uranium absorption material.

[0025] ④ The bis(diallylammonium) salt of the present invention is soluble in water and can also be dissolved in small molecule alcohols or acrylonitrile. Therefore, the surface grafting process of polymer materials such as polyethylene or polypropylene can be carried out in the aqueous phase, reducing the generation amount of VOCs in the grafting process and realizing the clean production of uranium extraction materials from seawater. Detailed implementation mode

[0026] The bis(diallylammonium) salt containing multiple cyano groups and multiple amino groups and its preparation method provided by the present invention are further described through the following examples, aiming to better understand the content of the present invention. Therefore, the bis(diallylammonium) salt containing multiple cyano groups and multiple amino groups and the preparation method not listed in the examples should not be regarded as a limitation to the protection scope of the present invention.

[0027] Example 1 Preparation method of bis(diallylammonium) salt-(1)

[0028] 120 g of an isopropanol solution containing 24.5 g of bis(2-cyanoethyl)amine and 36.6 g of N,N,N',N'-tetraglycidyl isophthalamide was placed in a reaction kettle. Under N2 protection, the temperature of the liquid in the reaction kettle was controlled at 70-90 °C, and after stirring and reacting for 6 hours, the temperature of the liquid in the reaction kettle was lowered to 60-70 °C. Then, 55 g of N-benzyl diallylammonium hydrochloride and 0.6 g of hydroquinone were continuously added, and stirring and reacting were continued for 6 hours. Part of the isopropanol was removed by rotary evaporation. After lowering the temperature of the materials in the reaction kettle, 100 g of chloroform was added, and after standing and filtering, the solid product was separated out, recrystallized with isobutanol, and then sent to a vacuum drying oven to be dried to constant weight to obtain 97.4 g of a light brown crystalline product (1). Based on N,N,N',N'-tetraglycidyl isophthalamide, the product yield was 91.3%.

[0029] Control of the reaction process :

[0030] ⑴ Bis(2-cyanoethyl)amine is a secondary amine. After the ring-opening reaction with N,N,N',N'-tetraglycidyl isophthalamide is completed, the secondary amine N-H in the reaction system has been completely consumed. Sampling and identification analysis of the reaction product system with nitrous acid will not show the positive characteristics of the nitrosamine color change reaction. In the absence of a catalyst, there is almost no side reaction between bis(2-cyanoethyl)amine and N,N,N',N'-tetraglycidyl isophthalamide. The reaction formula -1 between bis(2-cyanoethyl)amine and N,N,N',N'-tetraglycidyl isophthalamide is shown as follows:

[0031]

[0032] ⑵ N-benzyl diallylamine hydrochloride is an unsaturated tertiary amine hydrochloride. There is also a tertiary amine structural unit in the molecular structure of the reaction product of bis(2-cyanoethyl)amine and N,N,N',N'-tetraglycidyl-m-xylenediamine (i.e., cyano-containing glycidyl m-xylenediamine). In order to prevent the metathesis reaction of hydrogen chloride transfer between N-benzyl diallylamine hydrochloride and cyano-containing glycidyl m-xylenediamine, and to ensure the quaternization reaction between N-benzyl diallylamine hydrochloride and cyano-containing glycidyl m-xylenediamine, the feeding method of N-benzyl diallylamine hydrochloride should be an important solution. The reaction formula -2 between N-benzyl diallylamine hydrochloride and cyano-containing glycidyl m-xylenediamine is shown as follows:

[0033]

[0034] Analysis data of the light brown crystalline product (1): IR (cm -1 , KBr tablet): 3342 (s, O-H), 3029 (s, benzene ring C-H), 2923, 2867 (s, methylene C-H), 2250 (s, C≡N), 1648, 1483 (s, benzene ring C=C), 1282, 1108 (s, C-O); Chemical titration analysis shows that the Cl - content in the product is 7.01%, which is basically consistent with the molecular formula C 58 H 82 Cl2N 10 O4; Based on this, it is confirmed that the light brown crystalline product (1) conforms to the structural characteristics of bis(diallylammonium) salt-(1) in Reaction Formula -2. In the structural analysis of the light brown crystalline product (1), it is found that its Cl - content of 7.01% is greater than the theoretical value of 6.73%. The reason may be the mixed precipitation of unreacted excessive N-benzyl diallylamine hydrochloride and bis(diallylammonium) salt-(1).

[0035] The property test results of bis(diallylammonium) salt-(1) show that it is easily soluble in water, soluble in methanol, ethanol, DMSO, acrylonitrile, hardly soluble in methyl ethyl ketone, and insoluble in toluene and chloroform.

[0036] Example 2 Preparation of bis(diallylammonium) salt-(2)

[0037] According to the preparation method and operation steps of Example 1, by replacing N-benzyl diallylamine hydrochloride with N-dodecyl diallylamine hydrobromide, the product-(2) can be prepared. After IR spectral analysis and elemental analysis, it is determined that the product-(2) has the structural characteristics of bis(diallylammonium) salt-(2):

[0038]

[0039] The property test of bis(polyallylammonium) salt-(2) shows that it is easily soluble in water, and its aqueous solution has the foaming phenomenon of ordinary quaternary ammonium salt surfactants; it is soluble in methanol, ethanol, acrylonitrile, DMSO, and insoluble in benzene, toluene, and chloroform.

[0040] Example 3 Preparation method of bis(diallylammonium) salt-(3)

[0041] According to the preparation method and operation steps of Example 1, replacing N,N,N’,N’-tetraglycidyl-m-xylenediamine with 4,4'-bis(N,N-diglycidylamino) diphenyl ether, the product (3) can be obtained. Through IR spectral analysis and elemental analysis, it is determined that the product (3) has the structural characteristics of bis(diallylammonium) salt-(3):

[0042]

[0043] The property test of bis(diallylammonium) salt-(3) shows that it is easily soluble in water, soluble in methanol, ethanol, acrylonitrile, and insoluble in benzene, toluene, and chloroform.

[0044] Example 4 Characteristics of bis(diallylammonium) salts in Examples 1 to 3

[0045] The bis(diallylammonium) salts in Examples 1 to 3 are all easily soluble in water. Aqueous solutions with a mass percentage concentration of 20% of each are prepared. According to the dilution ratios of 1:2, 1:5, 1:10, 1:20, 1:50, 1:100, and 1:1000, 2 mL of the aqueous solutions of bis(diallylammonium) salts in Examples 1 to 3 with different concentrations are each taken and mixed with 10 mL of the culture medium. 2 drops of the pathogenic bacteria suspension are added, and after thorough mixing, they are placed in an incubator at 37°C for 24 hours; observe the growth of the pathogenic bacteria, calculate the minimum inhibitory concentration (MIC), and the test results are shown in Table 1.

[0046] Table 1 Results of the antibacterial experiment

[0047]

Claims

1. A bis(diallylammonium) salt, characterized in that It has the structure shown in general formula (Ⅰ) or general formula (Ⅱ): Among them, R in general formula (I) or general formula (II) is selected from C1-C 18 hydrocarbyl or refers to C2-C 18 alkylene, Q is selected from O or S, n is a natural number between 0 and 2000, and X - is selected from Cl - , Br - or I - one of them, and R1 is selected from C1-C 18 hydrocarbyl.

2. A method for preparing the bis(diallylammonium) salt according to claim 1, characterized in that: The preparation method of the bis(diallylammonium) salt is as described below: Weigh the solvent, tetraglycidyl diamine, diallylammonium salt and inhibitor respectively, put them into the reaction kettle, control the temperature of the materials in the reaction kettle at 40 - 90 °C, stir and react for 2 - 20 hours under N₂ protection, then put bis(2-cyanoethyl)amine into the reaction kettle and continue to stir and react at a constant temperature for 2 - 20 hours. Then, rotary evaporation is used to remove part of the solvent, the temperature of the materials in the reaction kettle is reduced to room temperature, and the solid product is obtained by filtration. The solid product is recrystallized and purified with small molecule alcohol, and after vacuum drying, the bis(diallylammonium) salt with the structure shown in general formula (Ⅰ) or general formula (Ⅱ) is prepared; where the molar ratio of tetraglycidyl diamine / diallylammonium salt / bis(2-cyanoethyl)amine is 1:1 - 1.2:0.8 - 1.0; the dosage of the solvent is 1 - 10 times that of tetraglycidyl diamine; the dosage of the inhibitor is 0.3 - 3% of the mass of the diallylammonium salt; the dosage of the small molecule alcohol is 1 - 10 times the mass of the tetraglycidyl diamine.

3. The preparation method of a bis(diallylammonium) salt according to claim 2, wherein The tetraglycidyl diamine has the structure shown in general formula (Ⅲ): Among them, in general formula (Ⅲ), refers to C2-C 18 alkylene, Q is selected from O or S, and n is a natural number selected from 0 to 2000.

4. The preparation method of a bis(diallylammonium) salt according to claim 2, characterized in that The diallylammonium salt refers to one of N-substituted diallylamine hydrochloride, hydrobromide, or hydroiodide, and has the structure shown in general formula (Ⅳ): Among them, X is selected from one of Cl, Br or I, and the substituent refers to R in the general formula (IV), and R is selected from C1-C 18 hydrocarbyl or wherein n is selected from natural numbers between 0 and 2000, and R1 is selected from C1-C 18 hydrocarbyl.

5. The preparation method of a bis(diallylammonium) salt according to claim 2, characterized in that The solvent is selected from one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethanol acetate, 2-ethoxyethanol acetate, ethyl acetate, methyl acetate, butyl acetate, toluene, acetone, butanone, anisole, chloroform, chlorobenzene, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

6. The preparation method of a bis(diallylammonium) salt according to claim 2, characterized in that The inhibitor is selected from one or more of hydroquinone, p-methoxyphenol, tert-butylhydroquinone, 2,6-dibutylhydroquinone, 2,6-di-tert-butyl-p-cresol, 2,4,6-tri-tert-butylphenol.

7. The preparation method of a bis(diallylammonium) salt 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, tert-butanol.

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