2-hydroxy-3-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium chloride) propyl phosphonate and a process for its preparation

Abstract

The application provides 2-hydroxy-3-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium chloride) propyl phosphonate which can be used as a radical grafting functional monomer on the surface of a high polymer material such as polyolefin, or mixed into copolymerization of acrylate, acrylonitrile or other olefin monomers, and meanwhile, the obtained high polymer material is endowed with phosphonate, quaternary ammonium cation, hydrophilicity, antibacterial property, antifouling property and other functional effects; and the high polymer material can also be used for ring-opening grafting modification of high polymer materials such as starch, cellulose, polyurethane, polyamide and the like which contain amino groups or hydroxyl groups in the structure, and the chemical stability of the new functional high polymer material prepared in an acid-base environment is high.

Description

Technical Field

[0001] The present invention relates to an unsaturated cationic phosphonate and a preparation method thereof. The unsaturated cationic phosphonate specifically refers to 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propyl phosphonate, which is used as a preparation monomer for ionic polymer materials or a functional modifier for polymer materials, belonging to the field of functional polymer materials. Technical Background

[0002] Phosphorus-containing functional polymers not only chelate metal ions, enabling the enrichment and extraction of low-concentration noble and heavy metal ions or rare earth elements, but also possess flame retardancy and bioactivity, making them suitable for flame-retardant polymers, antimicrobial polymers, and biopolymers. Currently, unsaturated phosphoric acid or phosphonic acid and their derivatives are primarily vinyl or allyl phosphoric acid and their derivatives, or vinyl or allyl phosphonic acid and their derivatives, as phosphine-containing functional monomers. These phosphorus-containing monomers have limited functionality and a limited variety. Phosphate esters, phosphonate esters, or quaternary phosphonium salts derived from acrylates or acrylamides as polymerizable monomers are also currently being researched. However, their relatively low chemical stability and high cost limit their practical application.

[0003] Ionomers produced through copolymerization or graft polymerization of quaternary ammonium cationic monomers have been found to possess unique physical, chemical, and biological properties, including hydrophilicity, salt responsiveness, temperature responsiveness, anion exchange, antibacterial and antifouling properties, and biocompatibility. These properties have demonstrated promising applications in rare earth enrichment, extraction, and separation, hydration and antifouling, ion-conducting electrolytes, biomedicine, and water treatment. Based on this, the present invention, based on the research and application of existing phosphorus-containing functional monomers and cationic monomers, designs an unsaturated cationic phosphonate monomer with strong chelating and adsorption capacity for rare earth ions or precious metal ions, high chemical stability in acidic and alkaline environments, high biocidal and antibacterial bioactivity, and high hydrophilicity. To facilitate surface graft modification of polymer materials containing NH or OH groups, a glycidyl group is introduced into the molecular structure of the unsaturated cationic phosphonate monomer, making it particularly suitable for graft modification of surface-aminated aromatic polyamide composite membranes used in seawater desalination. Summary of the Invention

[0004] The present invention provides a 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propyl phosphonate having a chemical structure shown in the general formula (I):

[0005]

[0006] The hydrocarbon group refers to R1 in the general formula (I), and R1 and R2 in the general formula (I) are selected from C1 to C18 hydrocarbyl, R3 is selected from C1-C 18 hydrocarbyl or C1-C 18 hydrocarbyloxy.

[0007] The specific preparation method of the 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium base) propyl phosphonate of general formula (I) is as follows: sodium alcoholate is weighed and added into a reaction kettle containing phosphonate in batches, the temperature of the material in the reaction kettle is controlled at 70-140°C under N2 protection, N-glycidyl-N-hydrocarbyl-N-allyl amine is continuously added into the reaction kettle, after the addition of N-glycidyl-N-hydrocarbyl-N-allyl amine is completed, the reaction is continued for 6-20 hours under insulation and stirring, then the temperature of the reaction product system is lowered to room temperature, solvent is added into the reaction kettle, and sodium salt is recovered by filtration; the obtained filtrate is put into the reaction kettle, epichlorohydrin and a polymerization inhibitor are added, the temperature of the material in the reaction kettle is raised to 30-90°C, and the reaction is continued for 6-60 hours under stirring, after the reaction is completed, the temperature of the reaction product system is lowered to room temperature, and 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium base) propyl phosphonate is prepared by filtration, washing and vacuum drying.

[0008] The amount of the sodium alcoholate is 0.5-5% of the mass of the phosphonate, the amount of the N-glycidyl-N-hydrocarbyl-N-allyl amine is 0.25-2.5 times of the molar amount of the phosphonate, the amount of the solvent is 0.5-5.0 times of the mass of the phosphonate, the amount of the epichlorohydrin is 1.0-2.2 times of the molar amount of the N-glycidyl-N-hydrocarbyl-N-allyl amine, and the amount of the polymerization inhibitor is 0.3-3% of the mass of the N-glycidyl-N-hydrocarbyl-N-allyl amine.

[0009] The sodium alcoholate refers to one of sodium methoxide, sodium ethoxide, sodium propoxide, sodium tert-butoxide and sodium cyclohexoxide.

[0010] The phosphonate has a chemical structure shown in general formula (II):

[0011]

[0012] wherein R2 in general formula (II) is selected from C1-C 18 hydrocarbyl, R3 is selected from C1-C 18 hydrocarbyl or C1-C 18 hydrocarbyloxy.

[0013] The hydrocarbyl in the N-glycidyl-N-hydrocarbyl-N-allyl amine refers to C1-C 18 hydrocarbyl.

[0014] The solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, epichlorohydrin, phosphate ester, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, or N,N-dimethylacetamide.

[0015] The polymerization inhibitor refers to one or more of hydroquinone, p-methoxyphenol, t-butyl hydroquinone, 2,6-di-t-butyl-p-cresol, or 2,4,6-tri-t-butylphenol.

[0016] The 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium) propyl phosphonate provided by the present application has the following advantages:

[0017] ① The 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium) propyl phosphonate provided by the present application can be used as a functional monomer required for graft modification of high molecular materials such as polyolefins, and can also be mixed into copolymerization of acrylate, acrylonitrile or other olefin monomers, while imparting phosphonate, quaternary ammonium cationization, hydrophilicity, antibacterial property, antifouling property and other functional effects to the obtained high molecular materials.

[0018] ② The 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium) propyl phosphonate provided by the present application can be used for ring-opening graft modification of high molecular materials such as starch, cellulose, polyurethane, and polyamide containing amino groups or hydroxyl groups in the structure, and the new functional high molecular materials thus prepared have high chemical stability in acid and alkali environments.

[0019] ③ The 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium) propyl phosphonate provided by the present application has high solubility in water or small molecule alcohols, and the grafting process of the high molecular material can be completed in an aqueous phase, avoiding the generation of VOC in the grafting process of the high molecular material.

[0020] ④ The raw materials required for preparing the 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium) propyl phosphonate provided by the present application are all industrial products, which are easy to obtain, and the preparation method is simple, safe and efficient.

[0021] ⑤ The 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium) propyl phosphonate provided by the present application is used as a phosphonium cation functional monomer, and the structural design is scientific, the functions are comprehensive, the technology is optimized, and the performance is superior. DETAILED DESCRIPTION

[0022] The present application is further illustrated by the following examples of 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbyl-N-allyl ammonium) propyl phosphonate and its preparation method, which aims to better understand the content of the present application.

[0023] Example 1 Preparation of diethyl 2-hydroxy-3-(chlorinated N-glycidyl-N,N- diallyl ammonium) propyl phosphonate

[0024] Diethyl phosphite 60 g was weighed into a reaction kettle, and sodium ethoxide 2.8 g was added in three portions under N2 protection and stirring. The temperature of the material in the reaction kettle was then raised to 90°C, and 40 g of N-glycidyl-N,N-diallyl amine was continuously added into the reaction kettle. After stirring for 8 hours, the temperature of the reaction product system was lowered to room temperature, and tetrahydrofuran 130 g was added. The sodium salt was recovered by filtration, and the obtained filtrate was added with epichlorohydrin 40 g and p-benzenediol 5 g. The temperature was raised to 40-50°C, and the stirring reaction was continued for 24 hours. After the reaction was completed, the temperature of the reaction product system was lowered to 5°C to obtain white solid product. The white solid product was washed or recrystallized with ethanol, and then was sent into a vacuum drying oven for drying until the weight was constant to obtain 89.3 g of pure product. The yield of the product was 81.2% based on N-glycidyl-N,N-diallyl amine. The Cl content of the product was analyzed by chemical titration. - 9.22%, which was consistent with the theoretical Cl content of 9.24% calculated according to the molecular formula C 16 H 31 ClNO5P - ClNO5P -1 The product had infrared spectral data of 3412 cm -1 -1 was a characteristic absorption peak of hydroxyl O-H, 2938, 2924, 2863 cm -1 -1 were characteristic absorption peaks of methyl and methylene, 1642, 1442 cm -1 -1 were characteristic absorption peaks of C-N, 1265 cm -1 -1 were characteristic absorption peaks of P=O double bond, 1132, 1038, 1012 cm 1H-NMR (δ, CD3OD): 1.21 (t, 6H), 1.81 (m, 2H), 2.02 (m, IH), 2.20 (m, IH), 2.32-2.37 (m, 3H), 3.52-3.73 (m, 4H), 3.91 (m, 4H), 4.05 (q, 4H), 4.90 (m, 4H), 5.65 (m, 2H). The product was thus identified as diethyl 2-hydroxy-3-(chloro N-glycidyl-N,N-diallyl ammonio) propyl phosphonate. Reaction Scheme-1 represents the process and procedure for the preparation of diethyl 2-hydroxy-3-(chloro N-glycidyl-N,N-diallyl ammonio) propyl phosphonate:

[0025]

[0026] Example 2 Preparation of diethyl 2-hydroxy-3-(chloro N-glycidyl-N-benzyl-N-allyl ammonio) propyl phosphonate

[0027] Diethyl phosphite 62 g was taken in a reaction vessel, under N2 protection, sodium ethoxide 2.8 g was added under stirring, the temperature of the contents of the reaction vessel was then raised to 90°C, 55 g of N-glycidyl-N-benzyl-N-allyl amine was added continuously to the reaction vessel, the reaction was allowed to proceed under stirring for 8 hours, the temperature of the reaction product system was then lowered to room temperature, tetrahydrofuran 100 g was added, the sodium salt was recovered by filtration, to the filtrate thus obtained, epichlorohydrin 45 g and p-benzenediol 4.8 g were added, the temperature was raised to 40-45°C, the reaction was allowed to proceed under stirring for 36 hours, the reaction was then stopped, the temperature of the reaction product system was lowered to room temperature, the white crystalline product was recovered by filtration, the white crystalline product was washed or recrystallized using ethanol, the product was then taken in a vacuum drying oven and dried to constant weight, pure product 103.7 g was obtained, the yield of the product was 80.8% based on N-glycidyl-N-benzyl-N-allyl amine. The white crystalline product was thus identified as diethyl 2-hydroxy-3-(chloro N-glycidyl-N-benzyl-N-allyl ammonio) propyl phosphonate. Reaction Scheme-2 represents the process and procedure for the preparation of diethyl 2-hydroxy-3-(chloro N-glycidyl-N-benzyl-N-allyl ammonio) propyl phosphonate:

[0028]

[0029] Example 3 Preparation of dimethyl 2-hydroxy-3-(chloro N-glycidyl-N,N-diallyl ammonio) propyl phosphonate

[0030] Take phosphite dimethyl ester 60 grams into the reaction kettle, under N2protection, stirring, add sodium methoxide 2.5 grams, then increase the temperature of the material in the reaction kettle to 90°C, continuously add 40 grams of N-glycidyl-N,N-diallylamine to the reaction kettle, stir for 8 hours, then reduce the temperature of the reaction product system to room temperature, add tetrahydrofuran 120 grams, filter and recover the sodium salt, add epichlorohydrin 40 grams and 4.5 grams of hydroquinone to the obtained filtrate, increase the temperature to 50-55°C, continue to stir for 24 hours, end the reaction, reduce the temperature of the reaction product system to room temperature, filter to obtain white crystalline product, wash or recrystallize the white crystalline product with methanol, then put it into a vacuum drying oven and dry to constant weight to obtain 87.6 grams of pure product, the yield of the product is 90.3% based on N-glycidyl-N,N-diallylamine. The white crystalline product is confirmed to be 2-hydroxy-3-(chlorinated N-glycidyl-N,N-diallyl ammonium) propyl phosphonic acid dimethyl ester through elemental analysis and instrument analysis. Reaction formula-3 represents the preparation method and process of 2-hydroxy-3-(chlorinated N-glycidyl-N,N-diallyl ammonium) propyl phosphonic acid dimethyl ester:

[0031] Example 4 Preparation of 2-hydroxy-3-(chlorinated N-glycidyl-N-dodecyl-N-allyl ammonium) propyl phosphonic acid dimethyl ester

[0032] Take phosphite dimethyl ester 60 grams into the reaction kettle, under N2protection, stirring, add sodium methoxide 2.5 grams, then increase the temperature of the material in the reaction kettle to 90°C, continuously add 40 grams of N-glycidyl-N,N-diallylamine to the reaction kettle, stir for 8 hours, then reduce the temperature of the reaction product system to room temperature, add tetrahydrofuran 120 grams, filter and recover the sodium salt, add epichlorohydrin 40 grams and 4.5 grams of hydroquinone to the obtained filtrate, increase the temperature to 50-55°C, continue to stir for 24 hours, end the reaction, reduce the temperature of the reaction product system to room temperature, filter to obtain white crystalline product, wash or recrystallize the white crystalline product with methanol, then put it into a vacuum drying oven and dry to constant weight to obtain 87.6 grams of pure product, the yield of the product is 90.3% based on N-glycidyl-N,N-diallylamine. The white crystalline product is confirmed to be 2-hydroxy-3-(chlorinated N-glycidyl-N,N-diallyl ammonium) propyl phosphonic acid dimethyl ester through elemental analysis and instrument analysis. Reaction formula-3 represents the preparation method and process of 2-hydroxy-3-(chlorinated N-glycidyl-N,N-diallyl ammonium) propyl phosphonic acid dimethyl ester:

[0033]

[0034] Example 5 Preparation of 2-hydroxy-3-(chlorinated N-glycidyl-N-dodecyl-N-allyl ammonium) propyl phosphonic acid diisooctyl ester

[0035] The phosphorous isooctyl ester 122 g was weighed into a reaction kettle, and under N2protection, sodium tert-butoxide 2.6 g was added with stirring. The temperature of the contents of the reaction kettle was then raised to 90°C, and 40 g of N-glycidyl-N-dodecyl-N-allyl amine was continuously added to the reaction kettle. After stirring for 8 hours, the temperature of the reaction product system was lowered to room temperature, and tetrahydrofuran 150 g was added. The sodium salt was recovered by filtration, and the resulting filtrate was added with epichlorohydrin 60 g and p-benzenediol 4.5 g. The temperature was raised to 50-55°C, and stirring was continued for 48 hours. After the reaction was completed, the temperature of the reaction product system was lowered to room temperature, and the white solid product was obtained by filtration. The white solid product was washed or recrystallized with isopropyl alcohol, and then was placed in a vacuum drying oven for drying to constant weight. The pure product 131.2 g was obtained, and the yield was 62.7% based on N-glycidyl-N-dodecyl-N-allyl amine. The white solid product was confirmed to be 2-hydroxy-3-(chlorinated N-glycidyl-N-dodecyl-N-allyl ammonium) propyl phosphonic acid diisooctyl ester by elemental analysis and instrumental analysis. Reaction Scheme-5 represents the method and process for preparing 2-hydroxy-3-(chlorinated N-glycidyl-N-dodecyl-N-allyl ammonium) propyl phosphonic acid diisooctyl ester:

[0036]

[0037] Example 6 Antimicrobial properties of 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbon-N-allyl ammonium) propyl phosphonic acid esters of Examples 1-5

[0038] The 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbon-N-allyl ammonium) propyl phosphonic acid esters of Examples 1-5 were weighed, dissolved in water, and prepared into an aqueous solution with a mass percentage of 20%. According to the dilution ratios of 1:2, 1:10, 1:50, 1:100, 1:1000, and 1:10000, 2 mL of the aqueous solution of the 2-hydroxy-3-(chlorinated N-glycidyl-N-hydrocarbon-N-allyl ammonium) propyl phosphonic acid esters of Examples 1-5 at different concentrations was mixed with 10 mL of culture medium, 2 drops of pathogenic bacteria suspension was added, and the mixture was thoroughly mixed and then was placed in a 37°C incubator for incubation 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.

[0039] Table 1 Results of the antimicrobial test

[0040]

[0041] As can be seen from the antibacterial experiment of Table 1, the 2-hydroxy-3-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium chloride) propyl phosphonate has high antibacterial activity, which is probably due to the phosphonate unit and the alkylene oxide in the molecular structure of the 2-hydroxy-3-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium chloride) propyl phosphonate having biological activity, and increasing the alkyl group or phosphonate alkyl group connected to the quaternary ammonium N atom, the antibacterial activity seems to be improved.

Claims

1. A 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propylphosphonate, characterized in that: It has the chemical structure shown in the general formula (Ⅰ): The hydrocarbon group refers to R1 in the general formula (I), and R1 and R2 in the general formula (I) are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydrocarbyloxy.

2. A method for preparing the 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propylphosphonate according to claim 1, characterized in that The method is achieved by weighing sodium alcoholate and adding it to a reactor containing phosphate in batches. Under nitrogen protection, the temperature of the materials in the reactor is adjusted to 70-140° C., and N-glycidyl-N-alkyl-N-allylamine is continuously added to the reactor. After the addition of N-glycidyl-N-alkyl-N-allylamine is completed, the reaction is continued with heat preservation and stirring for 6-20 hours. The temperature of the reaction product system is then lowered to room temperature, solvent is added to the reactor, and the sodium salt is filtered and recovered. The obtained filtrate is placed in a reactor, epichlorohydrin and a polymerization inhibitor are added, and the temperature of the materials in the reactor is then raised to 30-90° C. The reaction is continued with stirring for 6-60 hours. After the reaction is completed, the temperature of the reaction product system is lowered to room temperature, and the reaction is filtered, washed, and vacuum dried to obtain 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propylphosphonate. The amount of the sodium alkoxide is 0.5-5% of the mass of the phosphate ester, the amount of the N-glycidyl-N-alkyl-N-allylamine is 0.25-2.5 times the molar amount of the phosphate ester, the amount of the solvent is 0.5-5.0 times the mass of the phosphate ester, the amount of epichlorohydrin is 1.0-2.2 times the molar amount of the N-glycidyl-N-alkyl-N-allylamine, and the amount of the polymerization inhibitor is 0.3-3% of the mass of the N-glycidyl-N-alkyl-N-allylamine; The hydrocarbon group in the N-glycidyl-N-alkyl-N-allylamine refers to C1~C 18 Hydrocarbon group.

3. The method for preparing 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propylphosphonate according to claim 2, characterized in that The sodium alkoxide refers to one of sodium methoxide, sodium ethoxide, sodium propoxide, sodium tert-butoxide, and sodium cyclohexanol.

4. The method for preparing 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propylphosphonate according to claim 2, characterized in that The phosphate ester has a chemical structure shown in general formula (II): Wherein R2 in the general formula (II) is selected from C1~C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydrocarbyloxy.

5. The method for preparing 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propylphosphonate according to claim 2, characterized in that The solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, epichlorohydrin, phosphate, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

6. A method for preparing 2-hydroxy-3-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)propylphosphonate according to claim 2, wherein the polymerization inhibitor is 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.

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