An unsaturated ionic phosphonate composition and a method for its preparation

Abstract

The present application provides an unsaturated ionic phosphonate composition and a preparation method thereof, the composition comprising a diallyl ammonium cationic phosphonate, a diallyl sulfonium zwitterionic phosphonate or a diallyl carboxy ammonium zwitterionic phosphonate, and a gemini quaternary ammonium cationic phosphonate of a bis(diallyl ammonium) type, which is used for surface grafting functionalization of a seawater uranium extraction polymer material, or used as a raw material for preparing an ionomer.

Description

Technical Field

[0001] This invention relates to an unsaturated ionic phosphonate composition, and more particularly to a phosphonate composition containing diallyl ammonium in its molecular structure, for the functionalization of surface grafting of polymer materials for uranium extraction from seawater, belonging 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 ocean are enormous, but extracting uranium from seawater is fraught with difficulties. Based on a comprehensive evaluation of uranium-absorbing materials, considering factors such as substrate selection, functional optimization, performance, preparation methods, cost-effectiveness, ease of use, safety, environmental friendliness, and energy conservation, years of experimental and theoretical research have shown that amylopyramidized polymers are the preferred material for seawater uranium extraction. The earliest selected polyamylopyramidized polymer was amylopyramidized polyacrylonitrile fiber; however, the amylopyramidization of polyacrylonitrile fiber has several insurmountable drawbacks. ① To improve the adsorption capacity of amylopyramidized polyacrylonitrile fiber, it is desirable to amylopyramidize the cyano groups on the surface of the polyacrylonitrile fiber as much as possible; however, excessive amylopyramidization results in poor mechanical properties of the polyacrylonitrile fiber. ② The amylopyramidized groups contained in amylopyramidized polyacrylonitrile fiber have limited freedom in three-dimensional space, making it difficult to form stable geometric complexes with uranyl carbonate anions in a 2:1 or 4:1 ratio, and thus easily attracted by the high concentration of Fe in seawater. 3+ Ni 2+ or Cu 2+ Competition from other sources; ③ The hydrophilicity of the amylopyridine-modified polyacrylonitrile fiber is not high, and its complexation and adsorption with uranyl ions in seawater is relatively slow, requiring about 30 to 50 days to reach saturation adsorption; ④ After being immersed in seawater, the amylopyridine-modified polyacrylonitrile fiber is easily adhered or encapsulated by marine microorganisms, losing its function of adsorbing uranyl ions.

[0003] For a long time, researchers have been tirelessly working to find uranium-absorbing materials and technologies that meet the following criteria: high selectivity for uranium ion adsorption, fast adsorption rate, large saturated adsorption capacity, high hydrophilicity, large specific surface area in contact with seawater, high mechanical strength, high chemical stability, resistance to adhesion of microorganisms in seawater, simple adsorption-desorption process, low recycling cost, durability, easy placement in open seawater, easy recovery and processing, and high operating efficiency. Research findings from scholars in Japan, the United States, China, and other countries indicate that nonwoven fabrics with acrylonitrile and functional monomers grafted onto their surfaces, such as polyethylene or polypropylene polymers, are ideal uranium-absorbing materials. Firstly, polyethylene or polypropylene substrates are widely available, produced in large quantities, inexpensive, and chemically stable, and surface grafting has almost no impact on their mechanical properties. Secondly, nonwoven fabrics have high porosity and a large specific surface area, making it easy to perform processes such as hot pressing, shearing, curling, folding, kneading, and weaving, and suitable for placement in nets, ropes, branches, kelp, or seaweed-like forms in open ocean at various depths to filter seawater. Furthermore, in addition to grafting acrylonitrile, functional monomers are also selected for copolymer grafting with acrylonitrile. These functional monomers include ① acrylic acid, itaconic acid, unsaturated phosphoric acid / unsaturated phosphonic acid, unsaturated sulfobetaine, and unsaturated carboxybetaine, which can enhance the complexation effect on uranyl ions; ② unsaturated quaternary ammonium salts, which can not only significantly improve the hydrophilicity of the nonwoven fabric surface, achieving hydrophilic contact between seawater and the fabric surface, but also attract uranyl carbonate anions to the uranium-absorbing material through the electrostatic attraction of their positive charge, thereby accelerating the ion exchange between the uranium-absorbing material and seawater, and also enhance the resistance of the uranium-absorbing material to the attachment and growth of marine microorganisms on its surface; ③ organic polyamines, which can improve the hydrophilicity and uranium absorption capacity of the uranium-absorbing material. In view of this, how to design a versatile grafting raw material for the optimized preparation of uranium-absorbing materials based on existing research results should be the key to improving the overall performance of uranium-absorbing materials today. Summary of the Invention

[0004] This invention provides an unsaturated ionic phosphonate composition and its preparation method, characterized in that the unsaturated ionic phosphonate composition comprises: ① diallyl ammonium phosphonate, which accounts for 5-95% of the weight of the composition; ② diallyl ammonium zwitterionic phosphonate, which accounts for 0-90% of the weight of the composition; and ③ bis(diallyl ammonium) phosphonate, which accounts for 5-95% of the weight of the composition.

[0005] The diallyl ammonium phosphonate described therein has the structure shown in general formula (I):

[0006]

[0007] In general formula (Ⅰ), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, X - Select Cl -,Br - I - or p-CH3C6H4SO3 - One of them, Y is selected from C1 to C2. 18 hydrocarbon group or Wherein R3 is selected from C1 to C 18 Hydrocarbon group, n is selected from natural numbers between 0 and 2000.

[0008] The diallyl ammonium zwitterionic phosphonate refers to 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonate having the structure shown in general formula (II); or 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonate having the structure shown in general formula (III); or a mixture of general formula (II) and general formula (III), wherein the weight ratio of the mixture is 0.5-1:0.05-1.

[0009]

[0010] In general formula (II) or general formula (III), R1 and R2 are respectively selected from C1 to C2. 18 Hydrocarbon group.

[0011] The bis(diallylammonium)phosphonate has the structure shown in general formula (Ⅳ):

[0012]

[0013] In general formula (Ⅳ), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, X - Select Cl - ,Br - I - or p-CH3C6H4SO3 - One of them, This refers to C2 to C 18 Hydroxyl or Where n is selected from natural numbers between 0 and 2000.

[0014] A significant feature of the unsaturated ionic phosphonate composition of this invention is that the basic materials required for preparing each component of the unsaturated ionic phosphonate are all derived from a single substance, namely 2-hydroxy-3-(N,N-diallylamino)propylphosphonate. In its molecular structure, the N atom of the tertiary amine of diallylamine exhibits moderate nucleophilic substitution reactivity. Through quaternization with a suitable alkylating agent, diallylammonium cationic phosphonate, diallylsulfonium amphoteric phosphonate, or diallyl carboxyammonium amphoteric phosphonate, as well as bis(diallylammonium) type geminal quaternary ammonium cationic phosphonate, are prepared according to this invention. Using a single main raw material to prepare all components of the composition of this invention reduces the variety of required raw materials, lowers equipment investment, coordinates processes, ensures product cost-effectiveness, and simplifies the treatment of waste in the material industrial production process.

[0015] The specific preparation method of the unsaturated ionic phosphonate composition of the present invention includes the following steps:

[0016] Step 1: Preparation of 2-hydroxy-3-(N,N-diallylamino)propylphosphonate

[0017] Solvent and 2,3-epoxypropylphosphonate were weighed into a reaction vessel. The temperature of the material in the reaction vessel was controlled at 5–45°C with stirring. Diallylamine was continuously added to the reaction vessel. Two hours after the addition of diallylamine was completed, the temperature of the material in the reaction vessel was increased by 50–80°C, and the reaction was continued for 2–20 hours to obtain a 2-hydroxy-3-(N,N-diallylamino)propylphosphonate solution as shown in general formula (V), for later use. Reaction formula-1 expresses the preparation reaction process of 2-hydroxy-3-(N,N-diallylamino)propylphosphonate:

[0018]

[0019] In reaction equation -1, R1 and R2 are selected from C1 to C2, respectively. 18 Hydrocarbon group.

[0020] The solvent is selected from one or more of the following: 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 1 to 10 times the total weight of diallylamine and 2,3-epoxypropylphosphonate.

[0021] The 2,3-epoxypropylphosphonate has the structure shown in general formula (VI):

[0022]

[0023] In general formula (VI), R1 and R2 are selected from C1 to C2 respectively. 18 Hydrocarbon group. The molar ratio of the 2,3-epoxypropylphosphonate to diallylamine is 1.0 to 1.2:1.

[0024] Step 2: Preparation of diallyl ammonium phosphonate

[0025] In the 2-hydroxy-3-(N,N-diallylamino)propylphosphonate solution obtained in step one, a monoalkylating agent and a polymerization inhibitor are added. Under N2 protection, the reaction is carried out at a controlled temperature of 10-90°C for 2-20 hours with stirring. The temperature of the reaction product system is then lowered to room temperature, and after separation, purification, and vacuum drying, diallyl ammonium phosphonate of general formula (I) is obtained.

[0026] The diallyl ammonium phosphonate described therein has the structure shown in general formula (I):

[0027]

[0028] In general formula (Ⅰ), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, X - Select Cl - ,Br - I - or p-CH3C6H4SO3 - One of them, Y is selected from C1 to C2. 18 hydrocarbon group or Wherein R3 is selected from C1 to C 18 Hydrocarbon group, n is selected from natural numbers between 0 and 2000.

[0029] The monoalkylating agent has the structure shown in general formula (Ⅶ):

[0030] YX

[0031] General formula (VII)

[0032] In the general formula (Ⅶ), Y is selected from C1 to C2. 18 hydrocarbon group or X is selected from Cl, Br, I, or p-CH3C6H4SO3; wherein R3 is selected from C1 to C6H4SO3. 18 Hydrocarbon group, n is selected from natural numbers between 0 and 2000.

[0033] The amount of the monoalkylating agent used is 1.0 to 1.2 times the molar amount of diallylamine.

[0034] 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 0.3 to 3% of the mass of diallylamine.

[0035] Step 3: Preparation of diallyl ammonium zwitterionic phosphonate

[0036] In the 2-hydroxy-3-(N,N-diallylamino)propylphosphonate solution obtained in step one, 1,3-propanesulfonic acid lactone and a polymerization inhibitor or γ-butyrolactone and a polymerization inhibitor were added. Under N2 protection, the reaction was carried out at a controlled temperature of 30-70°C with stirring for 6-20 hours. The temperature of the reaction product system was then lowered to room temperature, followed by separation, purification, and vacuum drying to obtain 2-hydroxy-3-(N,N-diallyl-N-(3-sulfopropyl)ammonium). 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonate; Reaction formula-2 expresses the preparation reaction process of 2-hydroxy-3-(N,N-diallyl-N-(3-sulfopropyl)ammonium)propylphosphonate as shown in general formula (II) or 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonate as shown in general formula (III):

[0037]

[0038] In reaction equation -2, R1 and R2 are selected from C1 to C2, respectively. 18 Hydrocarbon group.

[0039] According to a weight ratio of 0.5~1:0.05~1, 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonate or 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonate are weighed and mixed together to prepare a mixture of general formula (II) and general formula (III).

[0040] The amount of 1,3-propanesulfonic acid lactone or γ-butyrolactone used is 1.0 to 1.02 times the molar amount of diallylamine.

[0041] 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 0.3 to 3% of the mass of diallylamine.

[0042] Step 4: Preparation of bis(diallylammonium)phosphonate

[0043] A dialkylating agent and a polymerization inhibitor were added to the 2-hydroxy-3-(N,N-diallylamino)propylphosphonate solution obtained in step one. Under N2 protection, the temperature was controlled at 20-90°C, and the reaction was stirred for 2-20 hours. The temperature of the reaction product system was then lowered to room temperature, followed by separation, purification, and vacuum drying to obtain bis(diallylammonium)phosphonate with the structure shown in general formula (IV). Reaction formula-3 expresses the preparation reaction process of bis(diallylammonium)phosphonate:

[0044]

[0045] In reaction formula -3, R1 and R2 are selected from C1 to C2, respectively. 18 hydrocarbon group, X - Select Cl - ,Br - I - or p-CH3C6H4SO3 - One of them, the Select C1 to C 18 Hydroxyl or Where n is selected from natural numbers between 0 and 2000.

[0046] The dialkylating agent has the structure shown in general formula (VIII):

[0047]

[0048] In the general formula (VIII) Select C1 to C 18 Hydroxyl or X is selected from Cl, Br, I or p-CH3C6H4SO3, and n is selected from a natural number between 0 and 2000.

[0049] The amount of the dialkylating agent used is 0.48 to 0.55 times the molar amount of diallylamine.

[0050] 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 0.3 to 3% of the mass of diallylamine.

[0051] Step 5: Preparation of the composition

[0052] The unsaturated ionic phosphonate composition is prepared by weighing the diallyl ammonium phosphonate obtained in step two, the diallyl ammonium zwitterionic phosphonate obtained in step three, and the bis(diallyl ammonium) phosphonate obtained in step four, respectively, according to the proportions of 5-95% of the weight of the composition, 0-90% of the weight of the composition, and 5-95% of the weight of the composition.

[0053] The purpose of this invention is to provide an unsaturated ionic phosphonate composition to meet the grafting raw material requirements for optimizing the preparation of uranium-absorbing materials. Therefore, the selection principle of the alkylating reagent should follow the principles of high grafting efficiency, strong adsorption function of precious metal ions, high antibacterial activity, strong antifouling ability, safe process, readily available raw materials, and low product cost. Thus, this invention first optimized and screened the alkylating reagent. Among the monoalkylating reagents, benzyl chloride, dodecyl bromide, and 5-chloromethylsalicylaldehyde are preferred; among the dialkylating reagents, 1,4-dibromobutane, biphenyl dichlorobenzyl, dibromoneopentyl glycol, or polyethylene glycol bis(p-toluenesulfonate) are preferred.

[0054] This invention optimizes the use of benzyl chloride and dodecyl bromide, which are reacted with 2-hydroxy-3-(N,N-diallylamino)propylphosphonate to prepare 2-hydroxy-3-(N-benzyl chloride-N,N-diallylammonium)propylphosphonate or 2-hydroxy-3-(N-dodecyl bromide-N,N-diallylammonium)propylphosphonate. The specific reason is that existing data report that the two alkyl quaternary ammonium cations have high antibacterial activity; benzyl chloride and dodecyl bromide are both industrial products with large output and low price.

[0055] This invention preferably involves the reaction of 5-chloromethyl salicylic acid aldehyde with 2-hydroxy-3-(N,N-diallylamino)propylphosphonate to prepare 2-hydroxy-3-(N-(3-formyl-4-hydroxybenzyl)-N,N-diallylamyl)propylphosphonate. Its molecular structure contains salicylic acid aldehyde units, which not only possess antibacterial activity but also facilitate the amine oxime reaction after grafting onto polymer surfaces, transforming it into salicylic acid oxime units. Existing data indicate that salicylic acid oxime is a highly selective chelating ligand for uranyl anions.

[0056] In this invention, 1,3-propanesulfonate lactone or γ-butyrolactone are preferably reacted with 2-hydroxy-3-(N,N-diallylamino)propylphosphonate to obtain the 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonate or 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonate described in this invention. Both are zwitterionic monomers. They are mixed with the diallyl ammonium cationic phosphonate and the bis(diallyl ammonium) gemini quaternary ammonium cationic phosphonate to form the composition described in this invention. This composition is used for grafting onto the surface of polymer materials, thereby simultaneously introducing quaternary ammonium cations, sulfonate anions, or carboxylate anions and phosphonates to participate in the complexation competition of carbonate anions in uranyl carbonate anions in seawater, thereby improving the adsorption selectivity and adsorption capacity of the uranium-absorbing material for uranyl anions.

[0057] This invention preferably uses 1,4-dibromobutane, biphenyl dichlorobenzyl, or dibromoneopentyl glycol as dialkylating agents. These are readily available industrial raw materials, inexpensive, and highly reactive for nucleophilic substitution. Under polar solvents and low-temperature conditions, they can react with 2-hydroxy-3-(N,N-diallylamino)propylphosphonate to prepare 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-dialkylphosphono)propyl)ammonium)butane, 4,4'-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-dialkylphosphono)propyl)ammoniummethyl)biphenyl, or 2,2-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-dialkylphosphono)propyl)ammoniummethyl)-1,3-propanediol with high product yields and few side reactions. The aforementioned bis(diallylammonium) phosphonates are used as cationic crosslinking agents. Existing research results indicate that the grafting efficiency of gemini quaternary ammonium crosslinking agents mixed with other monomers on the surface of the aforementioned polymer materials is high, even reaching 100%.

[0058] The beneficial effects of the unsaturated ionic phosphonate composition provided by the present invention are:

[0059] ① The unsaturated ionic phosphonate composition of the present invention is used for surface grafting of polymer materials such as polyethylene or polypropylene. It can also be mixed with monomers such as acrylonitrile and acrylic acid for surface grafting of the polymer materials such as polyethylene or polypropylene. At the same time, it imparts phosphonate esterification, quaternary ammonium cationization, amphoteric ionization, hydrophilicity, antibacterial properties, and antifouling properties to the surface grafted polymer materials, resulting in a multi-beneficial surface grafting modification effect.

[0060] ② The unsaturated ionic phosphonate composition of the present invention has high solubility in water or acrylonitrile, and the surface grafting process of the polymer material can be completed in the aqueous phase, thus avoiding the generation of VOCs during the polymer material grafting process.

[0061] ③ The raw materials required for preparing the unsaturated ionic phosphonate composition of the present invention are all industrial products, which are readily available, simple to prepare, and safe and efficient.

[0062] ④ The unsaturated ionic phosphonate composition of the present invention has a scientifically designed structure, reasonable composition, optimized technology, comprehensive functions, and superior performance. Detailed Implementation

[0063] The following examples further illustrate the unsaturated ionic phosphonate compositions and their preparation methods provided by the present invention, with the aim of providing a better understanding of the invention. Therefore, unsaturated ionic phosphonate compositions and preparation methods not listed in the examples should not be considered as limitations on the scope of protection of the present invention.

[0064] Example 1: Preparation of Unsaturated Ionic Phosphate Composition-1

[0065] Step 1: Preparation of diethyl 2-hydroxy-3-(N,N-diallylamino)propylphosphonate

[0066] 41.3 g of diethyl 2,3-epoxypropylphosphonate, 20 g of isobutanol, and 20 g of tetrahydrofuran were weighed and mixed in a reaction vessel. The temperature of the reaction solution was controlled at 15–25 °C. 20 g of diallylamine was slowly added. Two hours after the addition of diallylamine, the temperature of the reaction solution was increased to 60–70 °C, and the mixture was stirred for 2 hours to obtain a solution of diethyl 2-hydroxy-3-(N,N-diallylamino)propylphosphonate. Chromatographic analysis showed that the effective product was 57.4 g, and the yield of diethyl 2-hydroxy-3-(N,N-diallylamino)propylphosphonate, based on diallylamine, was approximately 91.2%.

[0067] Step 2: Preparation of diethyl 2-hydroxy-3-(N-benzyl-N,N-diallylamyl)propylphosphonate

[0068]

[0069] In a tetrahydrofuran solution of diethyl 2-hydroxy-3-(N,N-diallylamino)propylphosphonate obtained in step one, 30 g of benzyl chloride and 0.5 g of hydroquinone were added. Under N2 protection, the reaction solution temperature was controlled at 60–70 °C, and the reaction was carried out for 12 hours. The temperature of the reaction product system was then lowered to room temperature, allowed to stand, and filtered to obtain the crude product. This crude product was purified by recrystallization from isobutanol and vacuum dried to constant weight, yielding 73.2 g of a white crystalline product, with a yield of 86.1%. The product was analyzed by FT-IR (cm⁻¹). -1 KBr tablets: 3402cm -1 The characteristic absorption peaks for hydroxyl (OH) are 2937 and 2867 cm⁻¹. -1These are characteristic absorption peaks for methyl and methylene groups, at 1645 and 1478 cm⁻¹. -1 The characteristic absorption peak of the benzene ring is at 1256 cm⁻¹. -1 These are characteristic absorption peaks for the P=O double bond, at 1056 and 1012 cm⁻¹. -1 The peak at this location is a characteristic absorption peak of POC. 1 ¹H-NMR (δ, CD₃OD): 1.26 (m, 6H), 2.22 (m, 1H), 3.27 (m, 2H), 3.51 (m, 2H), 3.81 (m, 1H), 3.91 (m, 4H), 4.05 (s, 2H), 4.17 (q, 4H), 4.91–5.10 (m, 6H), 7.02–7.22 (m, 5H); Cl₂ in the product was analyzed by chemical titration. - The content was 8.37%, the phosphorus content was 7.37%, and the carbon content was... 20 H 33 The theoretical chlorine content of ClNO4P (8.48%) and the theoretical phosphorus content (7.41%) are basically consistent. Therefore, the product is confirmed to be diethyl 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonate.

[0070] Step 3: Preparation of diethyl 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonate

[0071]

[0072] In the tetrahydrofuran solution of diethyl 2-hydroxy-3-(N,N-diallylamino)propylphosphonate obtained in step one, 26 g of propanesulfonic acid lactone and 0.5 g of hydroquinone were added. Under N2 protection, the temperature of the reaction solution was controlled at 60-70°C, and the reaction was carried out for 8 hours. The temperature of the material in the reactor was then lowered to room temperature, and the supernatant was separated by standing. Then, anhydrous ethanol was added to the reactor to raise the temperature of the material in the reactor until all the solids were dissolved. The temperature of the material in the reactor was then lowered by 0-5°C, and the mixture was allowed to stand and refrigerated for 10 hours. After filtration, the obtained solid was transferred to a vacuum drying phase and dried at room temperature to constant weight, yielding 72.3 g of a white crystalline product with a yield of 86.7%. Chemical titration analysis showed that the N content of the product was 3.36% and the P content was 7.32%, which is consistent with the results based on the molecular formula C 16 H 32 The theoretical N content of 3.39% and theoretical P content of 7.49% calculated by NO7PS are basically consistent. The spectral analysis data of the product is as follows: 3405 cm⁻¹ -1 The characteristic absorption peaks for the hydroxyl group (OH) are at 2947, 2920, and 2868 cm⁻¹. -1 These are characteristic absorption peaks for methyl and methylene groups.

[0073] 1624, 1438cm -1This is the characteristic absorption peak of CN, at 1255 cm⁻¹. -1 These are characteristic absorption peaks for the P=O double bond, at 1058 and 1018 cm⁻¹. -1 The peak at this location is a characteristic absorption peak of POC. 1 ¹H-NMR (δ, CD₃OD): 1.23 (t, 6H), 1.85 (m, 2H), 2.09 (m, 1H), 3.27 (m, 2H), 3.29 (m, 4H), 3.81 (m, 1H), 3.91 (m, 4H), 4.05 (s, 2H), 4.07 (q, 4H), 4.90–5.12 (m, 6H). This confirms that the product possesses the structure of 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonic acid diethyl ester. Step 4: Preparation of 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-diethylphosphonopropyl)propyl)ammonium)butane.

[0074]

[0075] In a tetrahydrofuran solution of diethyl 2-hydroxy-3-(N,N-diallylamino)propylphosphonate obtained in step one, 22 g of 1,4-dibromobutane, 45 g of isobutanol, and 0.6 g of hydroquinone were added. Under N2 protection, the temperature of the reaction solution was controlled at 60–70 °C, and the reaction was stirred for 24 hours. The temperature of the material in the reactor was then lowered to room temperature, and the supernatant was separated by standing. Then, anhydrous methanol was added to the reactor to raise the temperature of the material in the reactor until all the solids were dissolved. The temperature of the material in the reactor was then lowered by 0–5 °C, and the mixture was allowed to stand and refrigerate for 10 hours. After filtration, the obtained solid was transferred to a vacuum drying phase and dried at room temperature to constant weight, yielding 75.3 g of a white crystalline product with a yield of 93.7%. Chemical titration analysis of the product showed that Br... - The content is 19.83%, and the P content is 7.68%, which is consistent with the molecular formula C. 30 H 60 The calculated Br₂N₂O₈P₂ content is consistent with the theoretical Br content of 20.01% and the theoretical P content of 7.76%. Product spectral analysis data: FT-IR (cm⁻¹) -1 KBr tablets: 3342cm -1 The characteristic absorption peaks for the hydroxyl group (OH) are 2923 and 2867 cm⁻¹. -1 These are characteristic absorption peaks for methyl and methylene groups, at 1624 and 1438 cm⁻¹. -1 This is the characteristic absorption peak of CN, at 1256 cm⁻¹. -1 These are characteristic absorption peaks for the P=O double bond, at 1138 and 1016 cm⁻¹. -1 The peak at this location is a characteristic absorption peak of POC. 1¹H-NMR (δ, CD₃OD): 1.31 (t, 4H), 1.73 (t, 4H), 2.18 (m, 2H), 3.24 (t, 8H), 3.29 (m, 4H), 3.52 (m, 4H), 3.82 (m, 2H), 3.92 (m, 8H), 4.04 (s, 4H), 4.16 (q, 4H), 4.52 (s, 4H), 4.90–5.11 (m, 12H). Based on the above analytical data, the product is confirmed to be 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-diethylphosphonopropyl)propyl)ammonium)butane.

[0076] Step 5: Preparation of Unsaturated Ionic Phosphate Composition-1

[0077] Weigh out 50 g of 2-hydroxy-3-(N-benzyl N,N-diallylammonium)propylphosphonic acid diethyl ester obtained in step two, 10 g of 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonic acid diethyl ester obtained in step three, and 40 g of 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-diethylphosphonopropyl)propyl)ammonium)butane obtained in step four, mix them together and stir well to obtain unsaturated ionic phosphonate composition-1.

[0078] Example 2: Preparation of diallyl ammonium salt composition-2

[0079] Following the preparation method and operating steps of Example 1, benzyl chloride in step two of Example 1 was replaced with dodecyl bromide to prepare diethyl 2-hydroxy-3-(N-dodecyl-N,N-diallylamyl)propylphosphonate, and 1,4-dibromobutane in step four of Example 1 was replaced with biphenyl dichlorobenzyl to prepare 4,4'-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-dialkylphosphonyl)propyl)ammoniummethyl)biphenyl.

[0080] Weigh out 50 g of diethyl 2-hydroxy-3-(N-dodecyl-N,N-diallylammonium)propylphosphonate, 10 g of diethyl 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonate, and 40 g of 4,4'-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-dialkylphosphonopropyl)propyl)ammoniummethyl)biphenyl, mix them together and stir well to obtain the unsaturated ionic phosphonate composition-2.

[0081] Example 3: Preparation of Unsaturated Ionic Phosphate Composition-2

[0082] Following the preparation method and operating steps of Example 1, benzyl chloride in step two of Example 1 was replaced with 5-chloromethylsalicylaldehyde to prepare 2-hydroxy-3-(N-(3-formyl-4-hydroxybenzyl)-N,N-diallylammonium)propylphosphonate, and 1,4-dibromobutane in step four of Example 1 was replaced with dibromoneopentyl glycol to prepare 2,2-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-dialkylphosphonyl)propyl)ammoniummethyl)-1,3-propanediol.

[0083] Weigh out 50 g of 2-hydroxy-3-(N-(3-formyl-4-hydroxybenzyl)-N,N-diallylammonium)propylphosphonate, 40 g of 2,2-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-dialkylphosphonopropyl)ammoniummethyl)-1,3-propanediol, and 10 g of 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonate diethyl ester, mix them together and stir well to obtain the unsaturated ionic phosphonate composition-3.

[0084] Example 4: Preparation of Unsaturated Ionic Phosphate Composition-4

[0085] Following the preparation method and operating steps of Example 1, 1,3-propanesulfonic acid lactone in step two of Example 1 was replaced with γ-butyrolactone to prepare 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonic acid diethyl ester.

[0086] Weigh out 50 g of 2-hydroxy-3-(N-benzyl N,N-diallylammonium)propylphosphonate diethyl ester obtained in step two of Example 1, 40 g of 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(O,O-dialkylphosphonopropyl)propyl)ammonium)butane obtained in step four, and mix them with 10 g of 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonate diethyl ester to obtain unsaturated ionic phosphonate composition-4.

[0087] Example 5: Characteristics of the unsaturated ionic phosphonate composition

[0088] The unsaturated ionic phosphonate compositions in Examples 1-4 are all readily soluble in deionized water and soluble in methanol and acrylonitrile. The unsaturated ionic phosphonate compositions from Examples 1-4 were weighed and dissolved in deionized water to prepare 20% aqueous solutions. These solutions were then diluted with water at ratios of 1:2, 1:5, 1:10, 1:20, 1:50, 1:100, and 1:1000. 2 mL of each solution was mixed with 10 mL of culture medium, and 2 drops of E. coli or S. aureus pathogenic bacterial suspension were added. The mixture was thoroughly mixed and incubated at 37°C for 24 hours. The growth of the pathogenic bacteria was observed, and the minimum inhibitory concentration (MIC) was calculated. The results are shown in Table 1.

[0089] Table 1. Properties of the unsaturated ionic phosphonate compositions in Examples 1-4

[0090]

Claims

1. An unsaturated ionic phosphonate composition, characterized in that... The unsaturated ionic phosphonate composition comprises: ① diallyl ammonium phosphonate, which accounts for 5-95% of the weight of the composition; ② diallyl ammonium zwitterionic phosphonate, which accounts for 10-90% of the weight of the composition; ③ bis(diallyl ammonium)phosphonate, which accounts for 5-95% of the weight of the composition. The diallyl ammonium phosphonate described therein has the structure shown in general formula (I): ； In general formula (Ⅰ), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, X - Select Cl - ,Br - I - or p-CH3C6H4SO3 - One of them, Y is selected from C1~C 18 hydrocarbon group or Wherein R3 is selected from C1~C 18 Hydrocarbon group, where n is a natural number between 0 and 2000; The diallyl ammonium zwitterionic phosphonate refers to: 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonate, having the structure shown in general formula (II); or 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonate, having the structure shown in general formula (III); or a mixture of general formula (II) and general formula (III), wherein the weight ratio of the mixture is 0.5~1:0.05~1; ； In general formula (II) or general formula (III), R1 and R2 are respectively selected from C1 to C2. 18 hydrocarbon group; The bis(diallylammonium)phosphonate has the structure shown in general formula (Ⅳ): ； In general formula (Ⅳ), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, X - Select Cl - ,Br - I - or p-CH3C6H4SO3 - One of them, This refers to C2~C 18 Hydroxyl or , where n is a natural number between 0 and 2000.

2. A method for preparing an unsaturated ionic phosphonate, characterized in that... The preparation method of the unsaturated ionic phosphonate composition is as follows: Step 1: Preparation of general formula (V) 2-hydroxy-3-(N,N-diallylamino)propylphosphonate Weigh the solvent and 2,3-epoxypropylphosphonate into a reaction vessel. Under stirring, control the temperature of the material in the reaction vessel to 5-45℃. Continuously add diallylamine into the reaction vessel. After 2 hours of diallylamine addition, raise the temperature of the material in the reaction vessel by 50-80℃ and react for another 2-20 hours to obtain a 2-hydroxy-3-(N,N-diallylamino)propylphosphonate solution of general formula (V) for later use. ； In general formula (V), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group; Step 2: Preparation of diallyl ammonium phosphonate In the 2-hydroxy-3-(N,N-diallylamino)propylphosphonate solution obtained in step one, a monoalkylating agent and a polymerization inhibitor are added. Under N2 protection, the reaction is carried out at 10~90℃ with stirring for 2~20 hours. The temperature of the reaction product system is then lowered to room temperature, and after separation, purification and vacuum drying, diallyl ammonium phosphonate of general formula (I) is obtained. ； In general formula (Ⅰ), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, X - Select Cl - ,Br - I - or p-CH3C6H4SO3 - One of them, Y is selected from C1~C 18 hydrocarbon group or Wherein R3 is selected from C1~C 18 Hydrocarbon group, where n is a natural number between 0 and 2000; Step 3: Preparation of diallyl ammonium zwitterionic phosphonate In the 2-hydroxy-3-(N,N-diallylamino)propylphosphonate solution obtained in step one, 1,3-propanesulfonic acid lactone and a polymerization inhibitor or γ-butyrolactone and a polymerization inhibitor are added. Under N2 protection, the reaction is carried out at 30~70℃ with stirring for 6~20 hours. The temperature of the reaction product system is then lowered to room temperature, and then separated, purified and vacuum dried to obtain 2-hydroxy-3-(N,N-diallyl-N-(3-sulfonylpropyl)ammonium)propylphosphonate of general formula (II) or 2-hydroxy-3-(N,N-diallyl-N-(3-carboxypropyl)ammonium)propylphosphonate of general formula (III). The amount of 1,3-propanesulfonic acid lactone or γ-butyrolactone used is 1.0 to 1.02 times the molar amount of diallylamine. ； In general formula (II) or general formula (III), R1 and R2 are respectively selected from C1 to C2. 18 hydrocarbon group; According to the weight ratio of 0.5~1:0.05~1, weigh out general formula (II) and general formula (III) respectively and mix them together to obtain the mixture of general formula (II) and general formula (III); Step 4: Preparation of bis(diallylammonium)phosphonate A dialkylating agent and a polymerization inhibitor were added to the 2-hydroxy-3-(N,N-diallylamino)propylphosphonate solution obtained in step one. Under N2 protection, the temperature was controlled at 20~90℃, and the reaction was stirred for 2~20 hours. The temperature of the reaction product system was lowered to room temperature, and then separated, purified, and vacuum dried to obtain bis(diallylamino)phosphonate with the structure shown in general formula (IV). ； In general formula (Ⅳ), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, X - Select Cl - ,Br - I - or p-CH3C6H4SO3 - One of them, the Select C1~C 18 Hydroxyl or , where n is selected from natural numbers between 0 and 2000; Step 5: Preparation of the composition The unsaturated ionic phosphonate composition is prepared by weighing the diallyl ammonium phosphonate obtained in step two, the diallyl ammonium zwitterionic phosphonate obtained in step three, and the bis(diallyl ammonium) phosphonate obtained in step four, respectively, according to the following weight ratios: diallyl ammonium phosphonate accounts for 5-95% of the weight of the composition, diallyl ammonium zwitterionic phosphonate accounts for 10-90% of the weight of the composition, and bis(diallyl ammonium) phosphonate accounts for 5-95% of the weight of the composition.

3. A method for preparing an unsaturated ionic phosphonate composition according to claim 2, characterized in that... The solvent is selected from one or more of the following: 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 solvent used is 1 to 10 times the total weight of diallylamine and 2,3-epoxypropylphosphonate.

4. A method for preparing an unsaturated ionic phosphonate composition according to claim 2, characterized in that... The 2,3-epoxypropylphosphonate has the structure shown in general formula (VI): ； In general formula (VI), R1 and R2 are selected from C1 to C2 respectively. 18 Hydrocarbon group; the molar ratio of the 2,3-epoxypropylphosphonate to diallylamine is 1.0~1.2:

1.

5. A method for preparing an unsaturated ionic phosphonate composition according to claim 2, characterized in that... The monoalkylating agent has the structure shown in general formula (Ⅶ): ； In the general formula (Ⅶ), Y is selected from C1 to C2. 18 hydrocarbon group or X is selected from Cl, Br, I, or p-CH3C6H4SO3; wherein R3 is selected from C1~C 18 The hydrocarbon group, n is selected from natural numbers between 0 and 2000; the amount of the monoalkylating agent is 1.0 to 1.2 times the molar amount of diallylamine.

6. A method for preparing an unsaturated ionic phosphonate composition according to claim 2, characterized in that... 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 0.3-3% of the mass of diallylamine.

7. A method for preparing an unsaturated ionic phosphonate composition according to claim 2, characterized in that... The dialkylating agent has the structure shown in general formula (VIII): ； In the general formula (VIII) Select C1~C 18 Hydroxyl or X is selected from Cl, Br, I or p-CH3C6H4SO3, and n is selected from a natural number between 0 and 2000; the amount of the dialkylating agent is 0.48 to 0.55 times the molar amount of diallylamine.

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