A kind of organic phosphonic acid betaine and preparation method thereof

Abstract

The present invention provides an organic phosphonic acid betaine and a preparation method thereof, specifically an ammonium phosphonic acid betaine containing a glycidyl group. The organic phosphonic acid betaine can be used as a functional monomer for free radical grafting modification of the surface of a polymer material such as polyolefin, or can be mixed with acrylate, acrylonitrile or other olefin monomers for copolymerization to prepare an amphoteric ionomer. The organic phosphonic acid betaine can also be used for ring-opening grafting modification of polymer materials such as starch, cellulose, polyurethane, and polyamide containing amino or hydroxyl groups in their structures. At the same time, the phosphonic acid betaine imparts functional effects such as zwitterionization, hydrophilicity, antibacterial properties, and antifouling properties to the obtained polymer material. The organic phosphonic acid betaine also has high chemical stability in acidic and alkaline water environments.

Description

Technical Field

[0001] The present invention relates to a zwitterionic monomer and a preparation method thereof, and particularly to 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt and a preparation method thereof. The 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt is an unsaturated ammonium phosphine-type betaine containing a glycidyl group in its molecular structure. The 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt can be used for surface grafting modification of polymer materials such as polyolefins, polyesters, and polyethers, and is particularly suitable for multifunctional modification of the surfaces of polymer materials such as cellulose, polyurethane, and polyamide containing OH or NH on the main chain or side chain. The invention belongs to the field of functional polymer materials. Technical Background

[0002] Aromatic polyamide composite membranes are commercially available in a variety of varieties and offer excellent performance. They are widely used in industries such as seawater desalination, brackish water desalination, industrial wastewater treatment, and purified water production. However, key research areas in the field of aromatic polyamide composite membrane technology have long been to improve their ability to prevent marine biofouling, effectively prevent chemical damage to the aromatic polyamide active layer by trace amounts of residual chlorine and chlorine oxides in seawater, and maintain a high degree of hydrophilicity on the membrane surface.

[0003] 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.

[0004] Ionomers produced through copolymerization or graft polymerization of quaternary ammonium cationic monomers or zwitterionic monomers have been found to possess unique physical, chemical, and biological properties such as hydrophilicity, salt responsiveness, temperature responsiveness, anion exchange, antibacterial and antifouling, and biocompatibility. They have shown extremely broad application prospects in the fields of rare earth enrichment, extraction and separation, hydration and anti-pollution, ion-conducting electrolytes, biomedicine, water treatment, etc.

[0005] Based on a comprehensive analysis and evaluation of existing research and application results on antifouling, chlorine-resistant and hydrophilic modification of phosphorus-containing functional monomers, quaternary ammonium cationic monomers, and aromatic polyamide composite membranes, the inventors have created and disclosed an organic phosphonic acid-based betaine that has chelation-adsorption-solidification capabilities for heavy metal ions, high chemical stability in weakly alkaline water environments, high biocidal and antibacterial biological activity, and good hydrophilicity. The organic phosphonic acid-based betaine is suitable for functional modification of polymer surfaces, and is particularly suitable for the antibacterial, antifouling, chlorine-resistant, and hydrophilic modification of polymer materials containing OH or NH in the main chain or side chain. Summary of the Invention

[0006] The present invention provides an organic phosphonic acid betaine, which is specifically prepared by the following steps:

[0007] Step 1, Preparation of 2-(N-alkyl-N-allylamino)ethylphosphonate

[0008] A solvent, N-alkyl-N-allylamine, and vinylphosphonate are weighed into a reaction kettle. Under nitrogen protection, the temperature of the materials in the reaction kettle is controlled at 20-90° C., and the mixture is stirred for 6-20 hours to complete the aza-Michael reaction addition. The solvent, unreacted N-alkyl-N-allylamine, and vinylphosphonate are recovered by vacuum distillation. The high-boiling point substances remaining in the reaction kettle are separated and purified to obtain 2-(N-alkyl-N-allylamino)ethylphosphonate.

[0009] The amount of the N-alkyl-N-allylamine used is 1.0 to 2.2 times the molar amount of the vinyl phosphonate, and the amount of the solvent used is 0.5 to 5.0 times the mass of the vinyl phosphonate.

[0010] The hydrocarbon group in the N-alkyl-N-allylamine refers to C1~C 18 Hydrocarbon group.

[0011] The vinyl phosphonate has a chemical structure shown in general formula (II):

[0012]

[0013] Wherein R2 in the general formula (II) is selected from methoxy, ethoxy, or C1-C 18 One of the hydrocarbon groups, R3 is methyl or ethyl.

[0014] The solvent is selected from one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, acetone, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

[0015] Step 2: Preparation of 2-(chloro-N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonate (trimethylsilyl)

[0016] An organic solvent and the 2-(N-alkyl-N-allylamino)ethylphosphonate prepared in step 1 are weighed into a reactor, the temperature of the materials in the reactor is controlled to 20-60° C., trimethylsilyl bromide is slowly added, and the mixture is stirred for 12-48 hours to complete the substitution reaction. Unreacted trimethylsilyl bromide and the organic solvent are then recovered by distillation, and the organic solvent and epichlorohydrin are added. The temperature of the materials in the reactor is increased to 20-90° C., and the mixture is stirred for 12-48 hours to complete the quaternization reaction. The organic solvent and unreacted epichlorohydrin are recovered by vacuum rotary evaporation, and the residue in the reactor is separated and purified to obtain 2-(chloro-N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonate (trimethylsilyl).

[0017] The amount of trimethylsilyl bromide used is 1 to 5 times the mass of 2-(N-alkyl-N-allylamino)ethylphosphonate, the amount of epichlorohydrin used is 1 to 5 times the mass of 2-(N-alkyl-N-allylamino)ethylphosphonate, and the amount of the organic solvent used is 1 to 5 times the mass of 2-(N-alkyl-N-allylamino)ethylphosphonate.

[0018] The organic solvent refers to one or more of dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxane, acetone, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

[0019] Step 3: Preparation of organic phosphonic acid betaine

[0020] At room temperature, an alcohol solvent, 2-(chloro-N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonate (trimethylsilyl) ester prepared in step 2, a basic ion exchange resin and deionized water are added to a reactor, the temperature of the materials in the reactor is controlled to 20-90° C., and the mixture is stirred for 2-8 hours to complete the hydrolysis reaction. The mother liquor after separation and removal of the ion exchange resin is concentrated by vacuum rotary evaporation. After no alcohol solvent and water flow out, an alcohol solvent is added to the reactor to recrystallize the residual material in the reactor, and the crystals are collected and dried to obtain the organic phosphonic acid betaine.

[0021] The organic phosphonic acid betaine has a chemical structure shown in the general formula (I):

[0022]

[0023] Wherein R1 in the general formula (Ⅰ) is selected from C1~C 18 Hydrocarbon, R2 is selected from hydroxyl or C1~C 18 hydrocarbon group;

[0024] The alkaline ion exchange resin refers to the D301 series macroporous tertiary amine styrene anion exchange resin.

[0025] The alcohol solvent refers to one or more of methanol, ethanol, propanol and butanol.

[0026] The amount of the alkaline ion exchange resin used is 0.2 to 2.0 times the mass of 2-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester, the amount of deionized water used is 0.1 to 1.5 times the mass of 2-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester, and the amount of the alcohol solvent used is 0.5 to 5 times the mass of 2-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester.

[0027] The following reaction formula expresses the preparation method and process of the organic phosphonic acid betaine represented by general formula (I) of the present invention:

[0028]

[0029] Where R1 in the reaction formula is selected from C1~C 18 Hydrocarbon, R2 is selected from methoxy, ethoxy, C1~C 18 One of hydrocarbon group, trimethylsilyl group, or hydroxyl group, and R3 is methyl or ethyl.

[0030] As can be seen from the above reaction formula, the beneficial effects of the organophosphonic acid betaine provided by the present invention are:

[0031] ① The organic phosphonic acid betaine described in the present invention is 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt, which can be used as a zwitterionic olefin monomer to carry out zwitterionic grafting modification on the surface of polymer materials; it can also be mixed with acrylate, acrylonitrile or other olefin monomers to prepare amphoteric ionomers; and it can also utilize the ring-opening reaction of its glycidyl group to carry out grafting modification on polymer materials such as starch, cellulose, polyurethane, and polyamide containing hydroxyl or amino groups in their structures, while simultaneously imparting zwitterionic, hydrophilic, antibacterial, and antifouling properties to the resulting modified polymer material.

[0032] ② The functions and characteristics of the organic phosphonic acid betaine modified polymer material of the present invention are high in chemical stability in acidic or alkaline water environments.

[0033] ③ The raw materials required for preparing the organic phosphonic acid betaine of the present invention are all industrial products, the raw materials are easily available, the preparation method is simple, the product yield in each step is high, and the process is safe and efficient.

[0034] ④ The organic phosphonic acid betaine of the present invention has a scientific structural design, comprehensive functions, optimized technology and superior performance. DETAILED DESCRIPTION

[0035] The organophosphonic acid betaine and its preparation method of the present invention are further illustrated by the following examples, the purpose of which is to better understand the content of the present invention.

[0036] Example 1 Preparation of organic phosphonic acid betaine-1

[0037] Step 1, Preparation of diethyl 2-(N,N-diallylamino)ethylphosphonate

[0038] 30 g of ethanol, 18 g of diallylamine, and 18 g of diethyl vinylphosphonate were weighed into a reactor. The temperature of the materials in the reactor was raised to 45-50° C. and stirred for 16 hours. The ethanol and unreacted diallylamine were then evaporated under reduced pressure. Analysis of the residue revealed a weight of 29.7 g, with a diethyl 2-(N,N-diallylamino)ethylphosphonate content of 94.9%. The calculated yield of diethyl 2-(N,N-diallylamino)ethylphosphonate was 98.4%.

[0039] Step 2: Preparation of 2-(N-glycidyl-N,N-diallylammonium)ethylphosphonate

[0040] 45 g of dichloromethane was added to the reactor to completely dissolve 29.7 g of diethyl 2-(N,N-diallylamino)ethylphosphonate, 31.5 g of trimethylsilyl bromide was slowly added to the reactor at room temperature, and the mixture was stirred for 24 hours. The dichloromethane and unreacted trimethylsilyl bromide were removed by rotary evaporation, and 70 g of epichlorohydrin was added to the reactor. After stirring and mixing, the temperature of the material in the reactor was increased to 50-55° C., and the mixture was stirred for 48 hours to complete the quaternization reaction. The dichloromethane and excess epichlorohydrin were then removed by rotary evaporation, and 35 g of tert-butanol was added to the reactor. The residue in the reactor was recrystallized and dried to constant weight to obtain 2-(chloro-N-glycidyl-N,N-diallylammonium)ethylphosphonic acid di(trimethylsilyl) ester.

[0041] Step 3: Preparation of organic phosphonic acid betaine-1

[0042] At room temperature, 50 grams of tert-butyl alcohol, 2-(N-glycidyl-N,N-diallylammonium)ethylphosphonate prepared in step 2 (trimethylsilyl) ester, and 40 grams of D301 weakly basic ion exchange resin were added to a reactor, 15 grams of deionized water were gradually added, and the mixture was stirred and hydrolyzed for 4 hours. The mother liquor after removing the ion exchange resin was allowed to cool to -20 to -10°C, and filtered to obtain a solid product. The solid product was soaked and washed with tert-butyl alcohol, and then placed in a vacuum drying oven and dried to constant weight to obtain 20.3 grams of organic phosphonic acid betaine-1 product. The product yield was 70.9% based on diethyl vinylphosphonate, and the melting point was 108.5°C (thermal decomposition). The infrared spectrum data of the organic phosphonic acid betaine-1 (KBr tablet) are as follows: 3447 is the characteristic absorption peak of OH, 3029cm -1 Characteristic absorption peaks of C=CH, 2937, 2874 cm -1 Characteristic absorption peaks of methylene, 1642 and 1442 cm -1 It is the characteristic absorption peak of C=C or CN, 1252cm -1 Characteristic absorption peaks of P=O double bond, 1128, 1041, 997 cm -1 The characteristic absorption peaks of COC and PO are at 1 H-NMR (δ, D2O): 1.82 (t, 2H), 2.26 (s, 1H), 2.32 (t, 2H), 3.16 (m, 1H), 3.63-3.93 (m, 8H), 4.90-5.05 (m, 6H), which confirmed that the product was 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt of formula (1). The structural characteristics are as follows:

[0043]

[0044] Formula (1): 2-(N-glycidyl-N,N-diallylammonium)ethylphosphonic acid inner salt

[0045] Example 2 Preparation of organic phosphonic acid betaine-2

[0046] According to the preparation method and steps of Example 1, the diallylamine is replaced with N-benzyl-N-allylamine to obtain organophosphonic acid betaine-2. Structural analysis and characterization confirm that the organophosphonic acid betaine-2 has the structural characteristics of 2-(N-glycidyl-N-benzyl-N-allylammonium)ethylphosphonate of formula (2):

[0047]

[0048] Formula (2): 2-(N-glycidyl-N-benzyl-N-allylammonium)ethylphosphonic acid inner salt.

[0049] Example 3 Preparation of organic phosphonic acid betaine-3

[0050] According to the preparation method and steps of Example 1, the diallylamine is replaced with N-benzyl-N-allylamine, and the vinyl diethyl phosphate is replaced with vinyl methyl phosphonate ethyl ester to obtain organophosphonic acid betaine-3. Structural analysis and characterization confirmed that the organophosphonic acid betaine-3 has the structural characteristics of 2-(N-glycidyl-N-benzyl-N-allylammonium)ethylphosphonate of formula (3):

[0051]

[0052] Formula (3): 2-(N-glycidyl-N-benzyl-N-allylammonium)ethylmethylphosphinic acid inner salt.

[0053] Example 4 Antibacterial properties of organophosphonic acid betaines of Examples 1 to 3

[0054] The organophosphonic acid betaines in Examples 1 to 3 are all soluble in water, and aqueous solutions with a mass percentage concentration of 20% were prepared. According to the dilution ratios of 1:2, 1:10, 1:50, 1:100, 1:1000, and 1:10000, 2 mL of the glycidyl-containing organophosphonic acid betaine aqueous solutions of Examples 1 to 3 of different concentrations were mixed with 10 mL of culture medium, 2 drops of pathogenic bacteria suspension were added, and after thorough mixing, the mixture was placed in an incubator at 37° C. and cultured 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.

[0055] Table 1 Antibacterial test results

[0056]

Claims

1. An organic phosphonic acid betaine, characterized in that It has the chemical structure shown in the general formula (Ⅰ): Wherein R1 in the general formula (Ⅰ) is selected from C1~C 18 Hydrocarbon, R2 is selected from hydroxyl or C1~C 18 Hydrocarbon group.

2. A method for preparing an organic phosphonic acid betaine according to claim 1, characterized in that Prepared by the following steps: Step 1, Preparation of 2-(N-alkyl-N-allylamino)ethylphosphonate A solvent, N-alkyl-N-allylamine, and vinylphosphonate are weighed into a reaction kettle. Under nitrogen protection, the temperature of the materials in the reaction kettle is controlled at 20-90° C., and the mixture is stirred for 6-20 hours to complete the aza-Michael reaction addition. The solvent, unreacted N-alkyl-N-allylamine, and vinylphosphonate are recovered by vacuum distillation. The high-boiling point substances remaining in the reaction kettle are separated and purified to obtain 2-(N-alkyl-N-allylamino)ethylphosphonate. The amount of the N-alkyl-N-allylamine is 1.0 to 2.2 times the molar amount of the vinyl phosphonate, and the amount of the solvent is 0.5 to 5.0 times the mass of the vinyl phosphonate; The hydrocarbon group in the N-alkyl-N-allylamine refers to C1~C 18 hydrocarbon group; The vinyl phosphonate has a chemical structure shown in general formula (II): Wherein R2 in the general formula (II) is selected from methoxy, ethoxy, or C1-C 18 One of the hydrocarbon groups, R3 is methyl or ethyl; Step 2: Preparation of 2-(chloro-N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonate (trimethylsilyl) An organic solvent and the 2-(N-alkyl-N-allylamino)ethylphosphonate prepared in step 1 are weighed into a reactor, the temperature of the materials in the reactor is controlled to 20-60° C., trimethylsilyl bromide is slowly added, and the mixture is stirred for 12-48 hours to complete the substitution reaction. Unreacted trimethylsilyl bromide and organic solvent are then recovered by distillation, and the organic solvent and epichlorohydrin are added. The temperature of the materials in the reactor is increased to 20-90° C., and the mixture is stirred for 12-48 hours to complete the quaternization reaction. The organic solvent and unreacted epichlorohydrin are recovered by vacuum rotary evaporation, and the residue in the reactor is separated and purified to obtain 2-(chloro-N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonate (trimethylsilyl); The amount of trimethylsilyl bromide used is 1 to 5 times the mass of 2-(N-alkyl-N-allylamino)ethylphosphonate, the amount of epichlorohydrin used is 1 to 5 times the mass of 2-(N-alkyl-N-allylamino)ethylphosphonate, and the amount of the organic solvent used is 1 to 5 times the mass of 2-(N-alkyl-N-allylamino)ethylphosphonate; Step 3: Preparation of organic phosphonic acid betaine At room temperature, an alcohol solvent, 2-(chloro-N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonate (trimethylsilyl) ester prepared in step 2, a basic ion exchange resin, and deionized water are added to a reactor. The temperature of the materials in the reactor is controlled to 20-90° C., and the mixture is stirred for 2-8 hours to complete the hydrolysis reaction. The mother liquor after separation and removal of the ion exchange resin is concentrated by vacuum rotary evaporation. After no alcohol solvent and water flow out, an alcohol solvent is added to the reactor to recrystallize the residual material in the reactor. The crystals are collected and dried to obtain the organic phosphonic acid betaine described in general formula (I); The amount of the alkaline ion exchange resin used is 0.2 to 2.0 times the mass of 2-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester, the amount of deionized water used is 0.1 to 1.5 times the mass of 2-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester, and the amount of the alcohol solvent used is 0.5 to 5 times the mass of 2-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester.

3. A method for preparing organic phosphonic acid betaine 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, acetone, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

4. A method for preparing organic phosphonic acid betaine according to claim 2, characterized in that The organic solvent refers to one or more of dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxane, acetone, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

5. A method for preparing organic phosphonic acid betaine according to claim 2, characterized in that The alkaline ion exchange resin refers to the D301 series macroporous tertiary amine styrene anion exchange resin.

6. A method for preparing organic phosphonic acid betaine according to claim 2, characterized in that The alcohol solvent refers to one or more of methanol, ethanol, propanol and butanol.

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