Water-soluble quaternary ammonium salt antibacterial agent and preparation method thereof

Abstract

The invention discloses a preparation method of a water-soluble quaternary ammonium salt antibacterial agent. The water-soluble quaternary ammonium salt antibacterial agent is prepared by taking aryl sulfonyl chloride, linear fatty amine with tertiary amino at the tail end and sultone as raw materials. The preparation method comprises the following steps: under the condition that alkali is used as an acid-binding agent, preparing an aryl sulfonamide compound by using aryl sulfonyl chloride and linear fatty amine with tertiary amino at the tail end as raw materials, and carrying out heating reflux reaction on tertiary amino functional groups in the sulfonamide compound and sultone to generate the water-soluble quaternary ammonium salt; the obtained target product quaternary ammonium salt is high in purity and excellent in yield, the structural formula of the quaternary ammonium salt does not contain a long alkane chain, the obtained product has good antibacterial ability and good water solubility, the hydrophilic performance of the fabric is not affected after antibacterial finishing, and it is ensured that the fabric has good antibacterial property and wearing comfort.

Description

Technical Field

[0001] The invention relates to the technical field of chemical product preparation, in particular to a water-soluble quaternary ammonium salt antibacterial agent and a preparation method thereof. Background Art

[0002] With the improvement of living standards, people's requirements for quality of life are constantly increasing, especially the awareness of health is constantly increasing. Textiles with antibacterial function can effectively reduce or avoid harmful bacteria, fungi, viruses and other pathogenic microorganisms directly contacting human skin and causing diseases. Therefore, textiles with antibacterial function are becoming more and more popular.

[0003] Most of the existing antibacterial textiles are obtained by treating fabrics with antibacterial agents or antimicrobial agents. Organic antibacterial agents are widely used due to their advantages such as fast sterilization speed and high antibacterial efficacy. However, the hydrophilicity of fabrics treated with existing antibacterial agents is significantly reduced, resulting in reduced moisture absorption and air permeability of the textiles, affecting the comfort of use. Summary of the invention

[0004] The invention provides a method for preparing a water-soluble quaternary ammonium salt antibacterial agent, thereby solving the problems of poor hydrophilicity and insufficient air permeability of textiles treated with the existing antibacterial agent.

[0005] In order to solve the above technical problems, the present invention provides a water-soluble quaternary ammonium salt antibacterial agent, including a compound of the following structural formula:

[0006]

[0007] Wherein, Ar is at least one of phenyl, p-tolyl, 2-tolyl, 3-tolyl, 4-ethylphenyl, 4-butylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 2,4,6-trimethylphenyl, 2,5-xylyl, 2,4-xylyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2,4,6-triisopropylphenyl, 2-naphthyl, 2-nitrophenyl, 3-nitrophenyl, and 4-nitrophenyl;

[0008] R is C 1 ~C 4 A straight chain alkyl group;

[0009] m is an integer from 1 to 5;

[0010] n is an integer from 0 to 12.

[0011] In order to solve the above technical problems, the present invention also provides a method for preparing a water-soluble quaternary ammonium salt antibacterial agent, comprising the following steps:

[0012] (1) using arylsulfonyl chloride and terminal tertiary amino linear fatty amine as raw materials, reacting in an aqueous phase under the action of an inorganic base, separating the reaction solution into layers after the reaction, removing the aqueous layer, washing, and drying to obtain an arylsulfonamide compound;

[0013] The reaction process is as follows:

[0014]

[0015] (2) heating the aromatic sulfonamide compound obtained in step (1) and sultone under reflux in an organic solvent, cooling and crystallizing after the reaction, filtering, washing and drying to obtain the water-soluble quaternary ammonium salt antibacterial agent;

[0016] The reaction process is as follows:

[0017]

[0018] In a preferred embodiment of the present invention, in step (1), the molar ratio of the terminal tertiary amino linear fatty amine, the aryl sulfonyl chloride and the inorganic base is 1:1-1.4:1-1.5.

[0019] In a preferred embodiment of the present invention, the inorganic base includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, iron hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, strontium carbonate or lithium carbonate.

[0020] In a preferred embodiment of the present invention, the reaction temperature in step (1) is 0-60°C.

[0021] In a preferred embodiment of the present invention, in step (2), the molar ratio of the aromatic sulfonamide compound to the sultone is 1:1 to 1.2.

[0022] In a preferred embodiment of the present invention, the structural formula of the sultone is Here, m is an integer from 1 to 5.

[0023] In a preferred embodiment of the present invention, the reaction temperature in step (2) is 50-120°C.

[0024] In a preferred embodiment of the present invention, in step (2), the organic solvent is at least one of acetonitrile, ethyl acetate, propyl acetate, butyl acetate or acetone.

[0025] The invention has the beneficial effects that: the method for preparing a water-soluble quaternary ammonium salt antibacterial agent comprises the following steps: firstly, in an aqueous phase, under the action of an inorganic base, using aryl sulfonyl chloride and a terminal tertiary amino straight-chain fatty amine as raw materials to synthesize an aryl sulfonamide compound, and then reacting the aryl sulfonamide compound with sultone to generate a water-soluble quaternary ammonium salt; the target product quaternary ammonium salt obtained by the invention has high purity and excellent yield, and its structural formula does not contain a long alkane chain; the obtained product has not only good antibacterial ability, but also good water solubility, and does not affect the hydrophilicity of fabrics after antibacterial finishing. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the NMR spectrum of the water-soluble quaternary ammonium salt (1) prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0027] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making a clearer and more definite definition of the protection scope of the present invention.

[0028] The present invention discloses a water-soluble quaternary ammonium salt antibacterial agent, the structural formula of which is as follows:

[0029]

[0030] In the formula, Ar is at least one of phenyl, p-tolyl, 2-tolyl, 3-tolyl, 4-ethylphenyl, 4-butylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 2,4,6-trimethylphenyl, 2,5-xylyl, 2,4-xylyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2,4,6-triisopropylphenyl, 2-naphthyl, 2-nitrophenyl, 3-nitrophenyl, and 4-nitrophenyl; R is C 1 ~C 4 m is an integer from 1 to 5; n is an integer from 0 to 12.

[0031] The preparation method of the above-mentioned water-soluble quaternary ammonium salt antibacterial agent specifically comprises the following steps:

[0032] (1) adding a terminal tertiary amino linear fatty amine, an aryl sulfonyl chloride and an inorganic base in a molar ratio of 1:1 to 1.4:1 to 1.5 to a reaction bottle containing water, reacting at 0 to 60° C., separating the reaction solution after the reaction, removing the water layer, washing and drying to obtain an aryl sulfonamide compound;

[0033] (2) Add the aromatic sulfonamide compound and sultone prepared in step (1) to a reaction flask at a molar ratio of 1:1 to 1.2, heat and reflux in an organic solvent such as acetonitrile, ethyl acetate, propyl acetate, butyl acetate or acetone at 50 to 120° C. for reaction, cool and crystallize, filter, wash and dry after the reaction to obtain the water-soluble quaternary ammonium salt antibacterial agent.

[0034] The reaction formula of the above reaction is as follows:

[0035]

[0036] The inorganic base includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, iron hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, strontium carbonate or lithium carbonate. The inorganic base is used as an acid-binding agent. In the aqueous phase, under the action of the inorganic base, the aryl sulfonyl chloride and the terminal tertiary amino straight-chain fatty amine synthesize the aryl aryl sulfonamide compound.

[0037] The structural formula of the sultone is The value of m is 1, 2, 3, 4 or 5.

[0038] The structural formula of the straight-chain fatty amine with a tertiary amino group at the end is:

[0039]

[0040] Wherein, n is an integer from 0 to 12; R 2 C 1 ~C 4 of a straight chain alkyl group.

[0041] The process of the present invention is described in detail below through specific embodiments.

[0042] Example 1

[0043] Synthesis of Water-Soluble Quaternary Ammonium Salt (1)

[0044]

[0045] Add 44 g of N,N-dimethylethylenediamine and 300 ml of water to the reaction flask, cool with ice water, control the temperature of the reaction solution to 10-20°C, and simultaneously add dropwise 98 g of benzenesulfonyl chloride and 300 ml of 2N sodium hydroxide aqueous solution; after the addition is complete, maintain the stirring reaction at 10-20°C for 2 hours, let the mixture stand for stratification, remove the upper aqueous phase, wash with cold water 3 times, and vacuum dry to obtain 109 g of an oily product, N-(2-(dimethylamino)ethyl)benzenesulfonamide, with a yield of 96%; 1H (NMR, CDCl3): δ7.66 (m, 2H), 7.39 (m, 1H), 7.35 (m, 2H), 2.85 (t, 2H), 2.16 (t, 2H), 1.96 (s, 6H).

[0046] To the reaction flask, 22.8 g of N-(2-(dimethylamino)ethyl)benzenesulfonamide, 15 g of 1,3-propanesultone and 100 ml of ethyl acetate were added, heated to reflux for 2 hours, cooled to crystallize, filtered, washed with ethyl acetate, and vacuum dried to obtain 32.7 g of a solid product with a yield of 98%; 1H (NMR, d6-DMSO): δ8.11 (s, 1H), 7.89 (m, 2H), 7.68 (m, 2H), 3.43 (m, 4H), 3.37 (m, 2H), 3.08 (s, 6H), 2.53 (m, 2H), 1.99 (m, 2H).

[0047] Example 2

[0048] Synthesis of Water-Soluble Quaternary Ammonium Salt (2)

[0049]

[0050] Add 44 g of N,N-dimethylethylenediamine, 45 g of potassium carbonate and 400 ml of water to the reaction flask, stir thoroughly to dissolve, heat to 40°C, control the temperature at 40-50°C, and add 100 g of p-toluenesulfonyl chloride in batches within 1 hour under vigorous stirring; after the addition is completed, maintain 40-50°C and continue to stir vigorously for 1 hour, cool with ice water, filter with suction, wash with ice water, and vacuum dry to obtain a solid product N-(2-(dimethyl Amino)ethyl)-4-methylbenzenesulfonamide 114 g, yield 94%; 1H (NMR, CDCl3): δ7.78 (d, J=7.8 Hz, 2H), 7.32 (d, J=7.8 Hz, 2H), 2.98-2.96 (m, 2H), 2.45 (s, 3H), 2.6-2.33 (m, 2H), 2.8 (s, 6H), 1., 5 (br, 1H).

[0051] To the reaction flask, 12.1 g of N-(2-(dimethylamino)ethyl)-4-methylbenzenesulfonamide, 8.2 g of 1,4-butanesulfonate and 50 ml of butyl acetate were added, heated to reflux for 3 hours, cooled to 0°C for crystallization, quickly filtered, washed with ethyl acetate, and vacuum dried to obtain 18 g of a solid product with a yield of 95%; 1H (NMR, d6-DMSO): δ8.12 (s, 1H), 7.78 (d, J = 7.8 Hz, 2H), 7.33 (d, J = 7.8 Hz, 2H), 3.43 (m, 4H), 3.37 (m, 2H), 3.09 (s, 6H), 2.53 (m, 2H), 2.45 (s, 3H), 1.99 (m, 4H).

[0052] Example 3

[0053] Synthesis of Water-Soluble Quaternary Ammonium Salt (3)

[0054]

[0055] Add 51 g of 3-N,N-dimethylaminopropylamine and 250 ml of water to the reaction flask, cool with ice salt to -5°C, add 300 ml of 2N potassium hydroxide aqueous solution, control the reaction solution to -5-0°C, and add 108 g of 4-fluorobenzenesulfonyl chloride dropwise over 2 hours; after the addition is completed, maintain -5-0°C and continue to react with vigorous stirring for 1 hour, cool with ice water, filter with suction, wash with ice water, and dry in vacuo to obtain 120 g of solid product N-(3-(dimethylamino)propyl)-4-fluorobenzenesulfonamide, with a yield of 92%; 1H (NMR, CDCl3): δ7.89 (m, 2H), 7.44 (s, 1H), 7.42 (m, 2H), 2.92 (t, 2H), 2.31 (t, 2H), 2.16 (s, 6H), 1.66 (m, 2H).

[0056] To the reaction flask, 13 g of N-(3-(dimethylamino)propyl)-4-fluorobenzenesulfonamide, 7.3 g of 1,3-propanesultone and 50 ml of acetone were added, heated to reflux for 2 hours, cooled to -5°C for crystallization, filtered, cooled with ice water, washed with petroleum ether, and dried in vacuo to obtain 18.3 g of a solid product with a yield of 96%; 1H (NMR, d6-DMSO): δ8.14 (s, 1H), 7.86 (m, 2H), 7.39 (m, 2H), 3.43 (m, 4H), 3.37 (m, 2H), 3.09 (s, 6H), 2.53 (m, 4H), 1.99 (m, 2H).

[0057] Example 4

[0058] Synthesis of Water-Soluble Quaternary Ammonium Salt (4)

[0059]

[0060] 51 g of 3-N,N-dimethylaminopropylamine, 82 g of potassium carbonate and 600 ml of water were added to the reaction flask, stirred thoroughly to dissolve, cooled with ice water, controlled at about 0°C, and under vigorous stirring, 114 g of p-methoxybenzenesulfonyl chloride was added in batches within 1 hour; after the addition was completed, the reaction was continued with vigorous stirring at room temperature for 2 hours, filtered, washed with ice water, and dried in vacuo to obtain 129 g of a solid product, N-(3-(dimethylamino)propyl)-4-methoxybenzenesulfonamide, with a yield of 95%; 1H (NMR, d6-DMSO): δ8.22 (s, 1H), 7.74 (d, J = 9.2 Hz, 2H), 7.14 (d, J = 9.2 Hz, 2H), 3.92 (s, 3H), 2.91 (t, 2H), 2.32 (t, 2H), 2.18 (s, 6H), 1.66 (m, 2H).

[0061] To the reaction flask, 13.6 g of N-(3-(dimethylamino)propyl)-4-methoxybenzenesulfonamide, 7.3 g of 1,3-propanesultone and 50 ml of ethyl acetate were added, heated to reflux for 2 hours, cooled to 0°C for crystallization, quickly filtered, cooled with ice water, washed with petroleum ether, and dried in vacuo to obtain 18.6 g of a solid product with a yield of 94%; 1H (NMR, d6-DMSO): δ8.10 (s, 1H), 7.75 (d, J = 9.2 Hz, 2H), 7.12 (d, J = 9.2 Hz, 2H), 3.92 (s, 3H), 3.43 (m, 4H), 3.37 (m, 2H), 3.09 (s, 6H), 2.53 (m, 4H), 1.99 (m, 2H).

[0062] (I) Antibacterial performance testing

[0063] The antibacterial rate of the water-soluble quaternary ammonium salt antibacterial agent with a mass concentration of 0.3% was tested using Staphylococcus aureus. The test results are shown in Table 1 below.

[0064] Table 1

[0065]

[0066] The above experimental results show that the tested quaternary ammonium salt has a significant inhibitory effect on the growth of Staphylococcus aureus.

[0067] (II) Hydrophilicity test

[0068] The antibacterial agents prepared in Examples 1-4 were used to perform antibacterial finishing on polyester fabrics, and the hydrophilic properties of the fabrics after antibacterial finishing were tested. Fabrics without antibacterial finishing were used as Comparative Example 1.

[0069] The antibacterial agent prepared in the above Examples 1-4 was dissolved in water to prepare 40 g / L of antibacterial agent finishing liquid, and then the polyester fabric was subjected to double dipping and double padding finishing with a padding rate of 85%, pre-baked at 100°C for 2 min, baked at 150°C for 2 min, washed with water, and dried to obtain a silicone quaternary ammonium salt antibacterial agent-finished polyester fabric.

[0070] The stiffness of polyester fabric is measured with reference to the standard GB / T18318.1-2009.

[0071] The hydrophilicity and water droplet absorption time of polyester fabrics were tested with reference to the dripping method of AATCC 79-2000. With reference to the GB / T 8629-2017 method, the polyester fabrics were washed 50 times and the stiffness and water droplet absorption time were tested.

[0072] The test results are shown in Table 2 below.

[0073] Table 2

[0074]

[0075] It can be seen from the test results in Table 2 that, compared with Comparative Examples 1 and 2, the water-soluble quaternary ammonium salt antibacterial agent prepared by the present invention has good hydrophilic properties, and the polyester fabric treated therewith has good stiffness and water absorption time, and has excellent hydrophilic properties.

[0076] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A water-soluble quaternary ammonium salt antibacterial agent, characterized in that: Including compounds with the following structural formula: Wherein, Ar is at least one of phenyl, p-tolyl, 2-tolyl, 3-tolyl, 4-ethylphenyl, 4-butylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 2,4,6-trimethylphenyl, 2,5-xylyl, 2,4-xylyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2,4,6-triisopropylphenyl, 2-naphthyl, 2-nitrophenyl, 3-nitrophenyl, and 4-nitrophenyl; R is a C1-C4 straight chain alkyl group; m is an integer from 1 to 5; n is an integer from 0 to 12.

2. A method for preparing a water-soluble quaternary ammonium salt antibacterial agent as claimed in claim 1, characterized in that: The steps include: (1) using arylsulfonyl chloride and terminal tertiary amino linear fatty amine as raw materials, reacting in an aqueous phase under the action of an inorganic base, separating the reaction solution into layers after the reaction, removing the aqueous layer, washing, and drying to obtain an arylsulfonamide compound; The reaction process is as follows: (2) heating the aromatic sulfonamide compound obtained in step (1) and sultone under reflux in an organic solvent, cooling and crystallizing after the reaction, filtering, washing and drying to obtain the water-soluble quaternary ammonium salt antibacterial agent; The reaction process is as follows:

3. A method for preparing a water-soluble quaternary ammonium salt antibacterial agent according to claim 2, characterized in that: In step (1), the molar ratio of the terminal tertiary amino linear fatty amine, aryl sulfonyl chloride and inorganic base is 1:1-1.4:1-1.

5.

4. A method for preparing a water-soluble quaternary ammonium salt antibacterial agent according to claim 2, characterized in that: The inorganic base includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, iron hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, strontium carbonate or lithium carbonate.

5. A method for preparing a water-soluble quaternary ammonium salt antibacterial agent according to claim 2, characterized in that: The reaction temperature in step (1) is 0-60°C.

6. A method for preparing a water-soluble quaternary ammonium salt antibacterial agent according to claim 2, characterized in that: In step (2), the molar ratio of the aromatic sulfonamide compound to the sultone is 1:1 to 1.

2.

7. A method for preparing a water-soluble quaternary ammonium salt antibacterial agent according to claim 6, characterized in that: The structural formula of the sultone is Here, m is an integer from 1 to 5.

8. A method for preparing a water-soluble quaternary ammonium salt antibacterial agent according to claim 2, characterized in that: The reaction temperature in step (2) is 50-120°C.

9. A method for preparing a water-soluble quaternary ammonium salt antibacterial agent according to claim 2, characterized in that: In step (2), the organic solvent is at least one of acetonitrile, ethyl acetate, propyl acetate, butyl acetate or acetone.

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