A kind of 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate and preparation method thereof

Abstract

The invention provides a 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate, which can be used as a free radical grafting functional monomer on the surface of a polymer material such as polyolefin, or mixed into the copolymerization of acrylate, acrylonitrile or other olefin monomers, and at the same time impart functional effects such as zwitterionization, hydrophilicity, antibacterial property, antifouling property, etc. to the obtained polymer material; and can also be used for the ring-opening grafting modification of polymer materials such as starch, cellulose, polyurethane, polyamide, polyester, polyolefin or polyether containing amino groups or hydroxyls in the structure, and the prepared new functional polymer material has high chemical stability in acidic and alkaline environments.

Description

Technical Field

[0001] The invention relates to a zwitterionic monomer and a preparation method thereof, and in particular to a 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate and a preparation method thereof. The 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate is used for grafting modification of polymer materials or as a zwitterionic monomer for preparing ionomers, and belongs to the field of functional polymer materials. Technical Background

[0002] Reverse osmosis, nanofiltration and microfiltration membranes made of metaphenylenediamine and trimesoyl chloride as monomers deposited on the surface of the support membrane are currently commonly used commercial varieties of polyamide composite membranes. They have good separation performance, high mechanical strength and a wide temperature and pH tolerance range. They are widely used in seawater desalination, brackish water desalination, industrial sewage treatment, pure water production and other industries. However, the thorny problem in seawater desalination is the biological contamination of the membrane by marine organisms and the chemical degradation of the aromatic polyamide layer of the membrane by active chlorine. The marine biological contamination of the membrane refers to the adhesion, growth and reproduction of seawater microorganisms on the surface of the composite membrane to form an extremely stubborn biological layer, which is difficult to clean manually and seriously affects the working efficiency of the composite membrane; in order to solve the biological contamination of aromatic polyamide composite membranes by microorganisms during seawater desalination or sewage treatment, seawater must be pre-treated and inactivated by chlorine. However, due to the chemical destruction of the aromatic polyamide active layer by trace amounts of chlorine and chlorine oxides remaining in seawater, the performance and life of the aromatic polyamide composite membrane are greatly shortened. Therefore, how to effectively control and reduce the pollution of aromatic polyamide composite membranes while ensuring the chemical stability of aromatic polyamide composite membranes has always been an important research topic in the field of aromatic polyamide composite membrane technology.

[0003] Over the years, researchers from many countries have developed a variety of membrane-making strategies and modification methods. Among them, it was found that grafting sulfonate betaine on the aromatic polyamide layer is effective in improving the membrane's anti-fouling ability. On the one hand, sulfonate betaine has excellent hydrophilicity, which improves the permeability of the membrane and promotes the transmission of water molecules through the membrane; at the same time, a thick layer of sulfonate betaine combines a large number of water molecules on the membrane surface to form a hydration layer, which prevents the adhesion or deposition of microorganisms or inorganic salts on the membrane surface, ensuring the membrane's anti-fouling ability. There are also many ways to improve the chlorine resistance of aromatic polyamide composite membranes. Among them, the more convenient and effective method is to graft chlorine-blocking structures or chlorine-consuming units on the surface of the composite membrane.

[0004] Although the surface modification of aromatic polyamide composite membranes requires additional membrane preparation steps and the operation process is prolonged, the membrane surface grafting method has almost no significant effect on the structure of the original aromatic polyamide active separation layer, and the interception performance of the membrane remains basically unchanged. However, if the material selection for membrane surface grafting is inappropriate, the membrane mesh will be clogged, the mass transfer resistance of the membrane will often increase, and the membrane water flux will be reduced. Accordingly, in combination with the purpose and requirements of the surface modification of aromatic polyamide composite membranes, the inventors designed 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate, which can react with the aromatic polyamide composite membrane containing amino groups on the surface under mild conditions to perform a ring-opening reaction, and graft unsaturated sulfobetaine on the surface of the aromatic polyamide composite membrane in a monolayer manner and with a high-density effect, laying a material foundation for simultaneously improving the hydrophilicity, antibacterial and antifouling properties, and chlorine resistance of the aromatic polyamide composite membrane surface. Summary of the invention

[0005] The present invention provides a 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate having a chemical structure shown in the general formula (I):

[0006]

[0007] Wherein R in the general formula (Ⅰ) is selected from C1 to C 18 Hydrocarbon.

[0008] The specific preparation method of the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate described in the present invention is as follows: respectively weigh a solvent, N-glycidyl-N-alkyl-N-allylamine, 1,3-propanesultone and a polymerization inhibitor in a reaction kettle, and under N2 protection, adjust the temperature of the materials in the reaction kettle to 30-90°C, stir and react for 6-60 hours, then reduce the temperature of the reaction product system to room temperature, filter, wash and dry to obtain the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate.

[0009] The amount of the solvent is 0 to 5.0 times the sum of the masses of N-glycidyl-N-alkyl-N-allylamine and 1,3-propane sultone, the amount of 1,3-propane sultone is 1.0 to 1.5 times the molar amount of N-glycidyl-N-alkyl-N-allylamine, and the amount of the inhibitor is 0.3 to 3% of the mass of N-glycidyl-N-alkyl-N-allylamine.

[0010] The solvent is selected from one or more of N-glycidyl-N-alkyl-N-allylamine, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, acetone, butanone, acetonitrile, chloroform, 1,2-dichloroethane, carbon tetrachloride, toluene, chlorobenzene, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.

[0011] The hydrocarbon group in the N-glycidyl-N-alkyl-N-allylamine refers to a C1-C 18 Hydrocarbon.

[0012] 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.

[0013] The beneficial effects of the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate provided by the present invention are:

[0014] ① The 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate provided by the present invention can be used as a free radical grafting functional monomer on the surface of polymer materials such as polyolefins, and can also be mixed into the copolymerization of acrylate, acrylonitrile or other olefin monomers, while giving the resulting polymer material functional effects such as zwitterionization, hydrophilicity, and antibacterial properties.

[0015] ② The 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate provided by the present invention can be used for the ring-opening grafting modification of starch, cellulose, polyurethane, polyamide, polyester, polyolefin or polyether containing amino groups or hydroxyl groups in the polymer chain structure. The new functional polymer material prepared thereby has high chemical stability in acidic and alkaline environments.

[0016] ③ The 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate of the present invention has high solubility in water or small molecule alcohols, and the grafting process of the polymer material can be completed in the aqueous phase, thereby avoiding the generation of VOCs in the grafting process of the polymer material.

[0017] ④ The raw materials required for preparing the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate of the present invention are all industrial products, the raw materials are easily available, the preparation method is simple, and the process is safe and efficient.

[0018] ⑤ The 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate described in the present invention is used as a zwitterionic functional monomer, which has a scientific structure, comprehensive functions, optimized technology and superior performance. DETAILED DESCRIPTION

[0019] The following examples further illustrate the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate and its preparation method provided by the present invention, the purpose of which is to better understand the content of the present invention.

[0020] Example 1 Preparation of 3-(N-glycidyl-N,N-diallylammonium)propyl 1-sulfonate

[0021] Weigh 60 grams of tetrahydrofuran, 43 grams of N-glycidyl-N,N-diallylamine, 40 grams of 1,3-propanesultone and 0.83 grams of 2,6-di-tert-butyl-p-cresol into a reactor. Under N2 protection, control the temperature of the materials in the reactor to 60-65°C, stir and react for 24 hours, terminate the reaction, lower the temperature of the reaction product system to 5°C, filter to obtain a white crystalline product, wash the product with ethanol, recrystallize it with ethanol, send it into a vacuum drying oven, and dry it to constant weight to obtain 73.9 grams of pure product, with a melting point of 155.3-156.5°C. Based on N-glycidyl-N,N-diallylamine, the product yield is 96.1%. The infrared spectrum data of the product (KBr tablet): 3012cm -1 Characteristic absorption peaks of C=CH, 2965, 2937, 2838cm -1 The characteristic absorption peak of methylene and methine is 1634cm -1 It is the characteristic absorption peak of C=C, 1464cm -1 It is the characteristic absorption peak of CN, 1047cm -1 Characteristic absorption peaks of S=O, 1012, 975cm -1 The center is the characteristic absorption peak of COC ring; 1 H-NMR (δ, CD3OD):

[0022] 2.27 (m, 2H), 2.72 (d, 2H), 3.10 (m, 1H), 3.22-3.24 (m, 4H), 3.41 (t, 2H), 3.91 (m, 4H), 5.41 (m, 4H), 5.72 (m, 2H), thus confirming that the product is 3-(N-glycidyl-N,N-diallylammonium)propyl-1-sulfonate,

[0023]

[0024] Comparative Example 1 Preparation of 3-(N-glycidyl-N,N-diallylammonium)propyl 1-sulfonate

[0025] Weigh 100 grams of N-glycidyl-N,N-diallylamine, 40 grams of 1,3-propane sultone and 1.5 grams of 2,6-di-tert-butyl-p-cresol into a reactor, and under N2 protection, control the temperature of the materials in the reactor to 60-65°C, stir and react for 24 hours, terminate the reaction, lower the temperature of the reaction product system to 5°C, filter to obtain a white crystalline product, wash the product with ethanol, recrystallize it with ethanol, send it into a vacuum drying oven, and dry it to constant weight to obtain 88.3 grams of pure product, with a melting point of 154.5-156.5°C, and a product yield of 97.9% based on 1,3-propane sultone. After analysis and characterization, it is confirmed that the product is 3-(N-glycidyl-N,N-diallylammonium)propyl-1-sulfonate.

[0026] Example 2 Preparation of 3-(N-glycidyl-N-benzyl-N-allylammonium)propyl-1-sulfonate

[0027] Weigh 60 grams of butanone, 70 grams of N-glycidyl-N-benzyl-N-allylamine, 40 grams of 1,3-propane sultone and 1.5 grams of 2,6-di-tert-butyl-p-cresol into a reactor. Under N2 protection, control the temperature of the materials in the reactor to 60-65°C, stir and react for 24 hours, terminate the reaction, lower the temperature of the reaction product system to 5°C, filter to obtain a white crystalline product, wash the product with ethanol, recrystallize it with isopropanol, send it to a vacuum drying oven, dry it to constant weight, and obtain 100.6 grams of pure product with a melting point of 151.5-154.5°C. The product yield is 94.5% based on 1,3-propane sultone. After analysis and characterization, it is confirmed that the product is 3-(N-glycidyl-N-benzyl-N-allylammonium)propyl-1-sulfonate.

[0028]

[0029] Comparative Example 2 Preparation of 3-(N-glycidyl-N-benzyl-N-allylammonium)propyl-1-sulfonate

[0030] Weigh 60 grams of 1,4-dioxane, 70 grams of N-glycidyl-N-benzyl-N-allylamine, 40 grams of 1,3-propane sultone and 1.3 grams of 2,6-di-tert-butyl-p-cresol into a reactor. Under N2 protection, control the temperature of the materials in the reactor to 60-65°C, stir and react for 24 hours, terminate the reaction, lower the temperature of the reaction product system to 5°C, filter to obtain a white crystalline product, wash the product with ethanol, recrystallize it with isopropanol, send it to a vacuum drying oven, dry it to constant weight, and obtain 101.3 grams of pure product, with a melting point of 153.3-154.5°C, and a product yield of 95.2% based on 1,3-propane sultone. After analysis and characterization, it is confirmed that the product is 3-(N-glycidyl-N-benzyl-N-allylammonium)propyl-1-sulfonate.

[0031] Example 3 Preparation of 3-(N-glycidyl-N-dodecyl-N-allylammonium)propyl-1-sulfonate

[0032] Weigh 98 grams of toluene, 100 grams of N-glycidyl-N-dodecyl-N-allylamine, 40 grams of 1,3-propane sultone and 2.1 grams of 2,6-di-tert-butyl-p-cresol and put them into a reactor. Under N2 protection, control the temperature of the materials in the reactor to 60-65°C, stir and react for 24 hours, end the reaction, lower the temperature of the reaction product system to 5°C, filter to obtain a white solid product, wash the product with ethanol, then recrystallize it with isopropanol, send it into a vacuum drying oven, dry it to constant weight, and obtain 125.6 grams of pure product, with a melting point of 91.0-94.5°C, and a product yield of 95.2% based on 1,3-propane sultone. After analysis and characterization, it was confirmed that the product was 3-(N-glycidyl-N-dodecyl-N-allylammonium)propyl-1-sulfonate.

[0033]

[0034] Comparative Example 3 Preparation of 3-(N-glycidyl-N-dodecyl-N-allylammonium)propyl-1-sulfonate

[0035] Weigh 100 g of ether, 100 g of N-glycidyl-N-dodecyl-N-allylamine, 40 g of 1,3-propane sultone and 2.1 g of 2,6-di-tert-butyl-p-cresol and put them into a reactor. Under N2 protection, reflux for 24 hours to terminate the reaction. Lower the temperature of the reaction product system to 5°C, filter to obtain a white solid product, wash the product with ethanol, recrystallize it with isopropanol, send it into a vacuum drying oven, and dry it to constant weight to obtain 127.2 g of pure product with a melting point of 92.3-94.5°C. The product yield is 96.4% based on 1,3-propane sultone. After analysis and characterization, it is confirmed that the product is 3-(N-glycidyl-N-dodecyl-N-allylammonium)propyl-1-sulfonate.

[0036] Example 4 Properties of 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate in Examples 1 to 3

[0037] Prepare a 20% mass percentage concentration of 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate aqueous solution in Examples 1 to 3, according to a dilution ratio of 1:2, 1:10, 1:50, 1:100, 1:1000, and 1:10000, take 2 mL of 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate aqueous solution in Examples 1 to 3 of different concentrations and mix with 10 mL of culture medium, add 2 drops of pathogenic bacteria suspension, mix thoroughly, and culture in a 37°C incubator for 24 hours; observe the growth of pathogenic bacteria, calculate the minimum inhibitory concentration (MIC), and the test results are shown in Table 1.

[0038] Table 1 Antibacterial test results

[0039]

[0040] It can be seen from the antibacterial experiment in Table 1 that the antibacterial activity of the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate of the present invention is high, and the antibacterial activity seems to be improved by increasing the alkyl group connected to the quaternary ammonium N atom.

Claims

1. A 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate, characterized in that It has the chemical structure shown in the general formula (Ⅰ): Wherein R in the general formula (Ⅰ) is selected from C1~C 18 Hydrocarbon.

2. A method for preparing the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate according to claim 1, characterized in that The preparation method of the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate is achieved by the following method: respectively weighing a solvent, N-glycidyl-N-alkyl-N-allylamine, 1,3-propanesultone and a polymerization inhibitor in a reaction kettle, and under N2 protection, adjusting the temperature of the materials in the reaction kettle to 30-90°C, stirring the reaction for 6-60 hours, and then lowering the temperature of the reaction product system to room temperature, filtering, washing and drying to obtain the 3-(N-glycidyl-N-alkyl-N-allylammonium)propyl-1-sulfonate; The alkyl group in the N-glycidyl-N-alkyl-N-allylamine refers to C1~C 18 Hydrocarbon; The amount of the solvent is 0 to 5.0 times the sum of the mass of N-glycidyl-N-alkyl-N-allylamine and 1,3-propane sultone, the amount of 1,3-propane sultone is 1.0 to 1.5 times the molar amount of N-glycidyl-N-alkyl-N-allylamine, and the amount of the polymerization inhibitor is 0.3 to 3% of the mass of N-glycidyl-N-alkyl-N-allylamine; The solvent is selected from one or more of N-glycidyl-N-alkyl-N-allylamine, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, acetone, butanone, acetonitrile, chloroform, 1,2-dichloroethane, carbon tetrachloride, toluene, chlorobenzene, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide; 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.

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