Organic phosphonic acid betaine and preparation method thereof

Abstract

The invention provides organic phosphonic acid betaine and a preparation method thereof, and particularly relates to glycidyl-containing ammonium-phosphine type betaine, the organic phosphonic acid betaine can be used as a functional monomer for surface free radical grafting modification of high polymer materials such as polyolefin, or can be used as a functional monomer for copolymerization of acrylic ester, acrylonitrile or other olefin monomers, or can be used as a functional monomer for surface free radical grafting modification of high polymer materials such as polyolefin, or can be used as a functional monomer for surface free radical grafting modification of high polymer materials such as polyolefin. The amphiprotic ionomer can also be used for ring-opening grafting modification of starch, cellulose, polyurethane, polyamide and other high polymer materials containing amino or hydroxyl in the structure, and meanwhile, the obtained high polymer materials are endowed with the functional effects of amphiprotic ionization, hydrophilicity, antibacterial property, antifouling property and the like of phosphonic acid betaine. And the chemical stability in an acid-base water environment is high.

Description

Technical Field

[0001] The invention relates to a zwitterionic monomer and a preparation method thereof, in particular 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 belongs to an unsaturated ammonium phosphine type betaine containing a glycidyl group in a molecular structure, can be used for surface grafting modification of polymer materials such as polyolefins, polyesters, polyethers, etc., is particularly suitable for multifunctional modification of the surface of polymer materials such as cellulose, polyurethane, polyamide, etc. containing OH or NH on the main chain or side chain, and belongs to the field of functional polymer materials. Technical Background

[0002] Aromatic polyamide composite membranes are commercially available in a variety of varieties and with excellent performance, and have been widely used in seawater desalination, brackish water desalination, industrial wastewater treatment, pure water production and other industries. However, the anti-marine biofouling performance in the field of seawater desalination, the function of effectively preventing the residual trace chlorine and chlorine oxides in seawater from chemically damaging the aromatic polyamide active layer, and maintaining high hydrophilicity on the membrane surface have always been important research topics in the field of aromatic polyamide composite membrane technology.

[0003] Phosphorus-containing functional polymer materials not only have the chelation effect on metal ions, can achieve the enrichment and extraction separation of low-concentration noble and heavy metal ions or rare earth elements, but also have flame retardant and biological activity functions, and are used as flame retardant polymer materials, antibacterial polymer materials, biopolymer materials, etc. At present, unsaturated phosphoric acid or unsaturated phosphonic acid and its derivatives are mainly vinyl or allyl phosphoric acid and its derivatives, or vinyl or allyl phosphonic acid and its derivatives as phosphine-containing functional monomers. Such phosphorus-containing monomers have a single function and few varieties; and phosphates, phosphonates or quaternary phosphonium salts derived from acrylates or acrylamides as polymerizable monomers are also the research objects of phosphorus-containing functional monomers. However, such phosphorus-containing functional monomers have relatively low chemical stability and high prices, which are limited in practical applications.

[0004] Ionomers made 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, and water treatment.

[0005] Based on comprehensive analysis and evaluation of existing research and application results of phosphorus-containing functional monomers, quaternary ammonium cationic monomers, and antifouling, chlorine-resistant and hydrophilic modification of aromatic polyamide composite membranes, the inventors have created and disclosed an organic phosphonic acid-based betaine with chelating-adsorption-solidification ability for heavy metal ions, high chemical stability in weakly alkaline water environment, high biocidal and antibacterial biological activity, and good hydrophilicity. The organic phosphonic acid-based betaine is suitable for functional modification of the surface of polymer materials, especially for the needs of 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] Weighing a solvent, N-alkyl-N-allylamine, and vinylphosphonate into a reaction kettle, and under N2 protection, adjusting the temperature of the materials in the reaction kettle to 20-90° C., stirring for 6-20 hours to complete the aza-Michael reaction addition, and respectively recovering the solvent, unreacted N-alkyl-N-allylamine, and vinylphosphonate by negative pressure distillation, and separating and purifying the high-boiling point substances remaining in the reaction kettle 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 alkyl group in the N-alkyl-N-allylamine refers to C1~C 18 Hydrocarbon.

[0011] The vinyl phosphonate has a chemical structure shown in the 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 selected from 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)ethylphosphonic acid (trimethylsilyl) ester

[0016] An organic solvent and 2-(N-alkyl-N-allylamino)ethylphosphonate prepared in step 1 are weighed into a reaction kettle, the material temperature in the reaction kettle is controlled to 20-60° C., trimethylsilyl bromide is slowly added, and the reaction is stirred for 12-48 hours to complete the substitution reaction, and then unreacted trimethylsilyl bromide and organic solvent are recovered by distillation, and then an organic solvent and epichlorohydrin are added, the material temperature in the reaction kettle is increased to 20-90° C., and the reaction is stirred for 12-48 hours to complete the quaternization reaction, and the organic solvent and unreacted epichlorohydrin are recovered by negative pressure rotary evaporation, and the residue in the reaction kettle is separated and purified to obtain 2-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester.

[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)ethylphosphonic acid (trimethylsilyl) ester prepared in step 2, an alkaline ion exchange resin and deionized water are added to a reactor, the material temperature in the reactor is controlled to 20 to 90° C., and the reaction is stirred for 2 to 8 hours to complete the hydrolysis reaction. The mother liquor after separation and removal of the ion exchange resin is concentrated by negative pressure 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;

[0024] The alkaline ion exchange resin refers to the D301 series macroporous tertiary amine type 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 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 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 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 the general formula (I) of the present invention:

[0028]

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

[0030] It can be seen from the above reaction formula that the beneficial effects of the organic phosphonic 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; 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, polyamide, etc. containing hydroxyl or amino groups in the structure, and at the same time, give the obtained modified polymer material the organic phosphonic acid betaine zwitterionic, hydrophilic, antibacterial, antifouling and other functions.

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

[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 yield of the product in each step is high, and the process is safe and efficient.

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

[0035] The organic phosphonic acid betaine and the preparation method thereof of the present invention are further described by the following examples, the purpose of which is to provide a better understanding 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] Weigh 30 grams of ethanol, 18 grams of diallylamine and 18 grams of diethyl vinylphosphonate in a reactor, raise the temperature of the materials in the reactor to 45-50°C, stir and react for 16 hours, then evaporate the ethanol and unreacted diallylamine under vacuum. After analysis, the residue weighs 29.7 grams, and the content of diethyl 2-(N,N-diallylamino)ethylphosphonate is 94.9%. The yield of diethyl 2-(N,N-diallylamino)ethylphosphonate is calculated to be 98.4%.

[0039] Step 2: Preparation of 2-(N-glycidyl chloride-N,N-diallylammonium)ethylphosphonic acid bis(trimethylsilyl) ester

[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, stirred for reaction for 24 hours, dichloromethane and unreacted trimethylsilyl bromide were evaporated, 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 reaction was stirred for 48 hours to complete the quaternization reaction, followed by rotary evaporation to remove dichloromethane and excess epichlorohydrin, 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-(chlorinated 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 chloride-N,N-diallylammonium)ethylphosphonic acid di(trimethylsilyl) ester obtained in step 2, and 40 grams of D301 weakly alkaline ion exchange resin are added to a reaction kettle, 15 grams of deionized water are gradually added, and the mixture is stirred and hydrolyzed for 4 hours. The mother liquor after the ion exchange resin is removed is allowed to stand and cool to -20 to -10°C, and a solid product is obtained by filtration. The solid product is soaked and washed with tert-butyl alcohol, and then sent to a vacuum drying oven and dried to constant weight to obtain 20.3 grams of organic phosphonic acid betaine-1 product. The product yield is 70.9% based on diethyl vinylphosphonate, and the melting point is 108.5°C (thermal decomposition). The infrared spectrum data of the organic phosphonic acid betaine-1 (KBr tablet): 3447 is the characteristic absorption peak of OH, 3029cm -1 Characteristic absorption peaks of C=CH, 2937, 2874cm -1 Characteristic absorption peaks of methylene, 1642, 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 confirms that the product is the structural characteristics of 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt of formula (1):

[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 organic phosphonic acid betaine-2. Structural analysis and characterization confirm that the organic phosphonic 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 organic phosphonic acid betaine-3. Through structural analysis and characterization, it is confirmed that the organic phosphonic acid betaine-3 has the structural characteristics of 2-(N-glycidyl-N-benzyl-N-allylammonium) ethyl phosphonate of formula (3):

[0051]

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

[0053] Example 4 Antibacterial properties of organic phosphonic acid betaine 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% are 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 are mixed with 10 mL of culture medium, 2 drops of pathogenic bacteria suspension are added, and after sufficient mixing, the mixture is placed in a 37° C. incubator and cultured for 24 hours; the growth of pathogenic bacteria is observed, and the minimum inhibitory concentration (MIC) is 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.

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 Weighing a solvent, N-alkyl-N-allylamine, and vinylphosphonate into a reaction kettle, and under N2 protection, adjusting the temperature of the materials in the reaction kettle to 20-90° C., stirring for 6-20 hours to complete the aza-Michael reaction addition, and respectively recovering the solvent, unreacted N-alkyl-N-allylamine, and vinylphosphonate by negative pressure distillation, and separating and purifying the high-boiling point substances remaining in the reaction kettle to obtain 2-(N-alkyl-N-allylamino)ethylphosphonate; 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; The alkyl group in the N-alkyl-N-allylamine refers to C1~C 18 Hydrocarbon; The vinyl phosphonate has a chemical structure shown in the 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 selected from methyl or ethyl; Step 2: Preparation of 2-(chloro-N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester Weigh an organic solvent and the 2-(N-alkyl-N-allylamino)ethylphosphonate prepared in step 1 into a reactor, control the temperature of the material in the reactor to 20-60° C., slowly add trimethylsilyl bromide, stir for 12-48 hours to complete the substitution reaction, then distill and recover the unreacted trimethylsilyl bromide and organic solvent, then add the organic solvent and epichlorohydrin, increase the temperature of the material in the reactor to 20-90° C., stir for 12-48 hours to complete the quaternization reaction, recover the organic solvent and unreacted epichlorohydrin by negative pressure rotary evaporation, separate and purify the residue in the reactor to obtain 2-(chlorinated N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid (trimethylsilyl) ester; 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)ethylphosphonic acid (trimethylsilyl) ester prepared in step 2, a basic ion exchange resin and deionized water are added to a reactor together, the temperature of the materials in the reactor is controlled to 20 to 90° C., and the reaction is stirred for 2 to 8 hours to complete the hydrolysis reaction. The mother liquor after separation and removal of the ion exchange resin is concentrated by negative pressure 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 described in general formula (I); The amount of the alkaline ion exchange resin 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 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 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 type 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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