Bacteriostatic and mite-repelling liquid and preparation method thereof

Abstract

The application discloses a kind of bacteriostatic mite repellent liquid and preparation method thereof, it is related to bacteriostatic mite repellent liquid technical field.The bacteriostatic mite repellent liquid is prepared, 3-chloro-1-propane mercaptan, triphenyl phosphorus is reacted to obtain functionalized quaternary phosphonium salt;Polyvinyl alcohol is sequentially reacted with glycidyl methacrylate, functionalized quaternary phosphonium salt to obtain modified polyvinyl alcohol;Nano zinc oxide is sequentially reacted with γ-aminopropyl triethoxysilane, tannic acid to obtain modified nano zinc oxide;Modified polyvinyl alcohol, modified nano zinc oxide, hexyl salicylate, diisopropyl sebacate, polyether polyol, glycine, diethylene glycol monobutyl ether, benzalkonium chloride and deionized water are mixed to obtain the bacteriostatic mite repellent liquid.The bacteriostatic mite repellent liquid prepared by the application has excellent bacteriostatic and mite repellent performance.

Description

Technical Field

[0001] This invention relates to the field of antibacterial and mite-repellent liquid technology, specifically to an antibacterial and mite-repellent liquid and its preparation method. Background Technology

[0002] With the continuous improvement of public health awareness, consumers are increasingly demanding higher hygiene standards for everyday home and intimate apparel fabrics. Antibacterial and mite-repellent functional additives have become a core necessity in the textile finishing industry. Currently, in the domestic market, antibacterial and mite-repellent agents, long-lasting antibacterial finishing agents, and related products have formed a complete supply chain system, widely used in the post-processing of various textile products such as bedding, clothing, and home furnishings. However, most common antibacterial and mite-repellent products on the market suffer from problems such as limited functionality, insufficient washability, and strong irritation. Most products focus only on antibacterial or mite-repellent properties, failing to simultaneously achieve long-lasting bacterial inhibition and active mite repellency, thus failing to meet the complex hygiene and protection needs of the home environment. Some traditional formulations contain highly irritating chemical components, which can easily cause skin redness, itching, and other discomfort in infants and people with sensitive skin, contradicting the current trend of healthy textile development. This invention designs and develops an antibacterial and mite-repellent liquid with both high-efficiency antibacterial and mite-repellent capabilities to solve the problems existing in the prior art. Summary of the Invention

[0003] The purpose of this invention is to provide an antibacterial and mite-repellent liquid and its preparation method. The antibacterial and mite-repellent liquid prepared by the method provided by this invention has both excellent antibacterial and mite-repellent properties, thereby solving one or more problems existing in the prior art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: An antibacterial and anti-mite liquid, by weight, mainly comprises: 3-5 parts modified polyvinyl alcohol, 1-2 parts modified nano zinc oxide, 4-5 parts hexyl salicylate, 2-3 parts diisopropyl sebacate, 2-3 parts polyether polyol, 0.5-1 part glycine, 5-6 parts diethylene glycol monobutyl ether, 1-1.2 parts benzalkonium chloride, and 150-200 parts deionized water.

[0005] Furthermore, the modified polyvinyl alcohol is prepared by reacting polyvinyl alcohol sequentially with glycidyl methacrylate and a functionalized quaternary phosphonium salt.

[0006] Furthermore, the functionalized quaternary phosphorus salt is prepared by reacting 3-chloro-1-propanethiol and triphenylphosphine.

[0007] Furthermore, the modified nano zinc oxide is prepared by reacting nano zinc oxide sequentially with γ-aminopropyltriethoxysilane and tannic acid.

[0008] A method for preparing an antibacterial and mite-repellent liquid, the method comprising the following preparation steps: (1) Dissolve 3-chloro-1-propanethiol and triphenylphosphine in a molar ratio of 1:(1.1~1.2) in N,N-dimethylformamide at 7~8 times the mass of triphenylphosphine. Under nitrogen protection, stir and react at 90~100℃ for 36~48h. Cool to room temperature, filter, wash with ethyl acetate, and vacuum dry at 50~60℃ for 20~24h to obtain functionalized quaternary phosphonium salt; (2) Mix pre-modified polyvinyl alcohol and dimethyl sulfoxide at a mass ratio of 1:(20~24), stir at room temperature for 10~20 min, add 0.1~0.2 times the mass of functionalized quaternary phosphonium salt of pre-modified polyvinyl alcohol, add 0.01~0.02 times the mass of triethylamine of pre-modified polyvinyl alcohol, heat to 75~85℃ and stir for 10~12 h, cool to room temperature, precipitate in 4~6 times the volume of dimethyl sulfoxide in acetone, filter, wash with acetone, and vacuum dry at 40~50℃ for 16~20 h to obtain modified polyvinyl alcohol; (3) Mix pre-modified nano zinc oxide and tannic acid aqueous solution at a mass ratio of 1:(50~60), stir at 40~50℃ for 10~12h, centrifuge, and vacuum dry at 50~60℃ for 15~18h to obtain modified nano zinc oxide; (4) By mass, mix 3-5 parts of modified polyvinyl alcohol, 1-2 parts of modified nano zinc oxide, 4-5 parts of hexyl salicylate, 2-3 parts of diisopropyl sebacate, 2-3 parts of polyether polyol, 0.5-1 parts of glycine, 5-6 parts of diethylene glycol monobutyl ether, 1-1.2 parts of benzalkonium chloride, and 150-200 parts of deionized water to prepare an antibacterial and mite-repellent liquid.

[0009] Further, the preparation method of the pre-modified polyvinyl alcohol in step (2) is as follows: polyvinyl alcohol and dimethyl sulfoxide are mixed at a mass ratio of 1:(20~24), stirred at room temperature for 10~20 min, 0.01~0.05 times the mass of polyvinyl alcohol of p-diaminopyridine is added, stirred at room temperature for 5~10 min, 0.06~0.18 times the mass of polyvinyl alcohol of glycidyl methacrylate is added and mixed evenly, heated to 50~80℃ and reacted for 7~8 h, cooled to room temperature, precipitated in 4~6 times the volume of dimethyl sulfoxide in acetone, filtered, washed with acetone, and vacuum dried at 40~50℃ for 16~20 h to obtain pre-modified polyvinyl alcohol.

[0010] Furthermore, the degree of alcoholysis of the polyvinyl alcohol is 88%.

[0011] Further, the preparation method of the pre-modified nano zinc oxide in step (3) is as follows: mix nano zinc oxide and anhydrous ethanol at a mass ratio of 1:(100~120), ultrasonically disperse for 20~30 min, add 0.3~0.5 times the mass of nano zinc oxide of γ-aminopropyltriethoxysilane and 8~10 times the mass of nano zinc oxide of deionized water, heat to 70~80℃ and stir for 10~12 h, centrifuge, wash with anhydrous ethanol, vacuum dry at 70~80℃ for 10~12 h to obtain pre-modified nano zinc oxide.

[0012] Furthermore, the particle size of the nano zinc oxide is 20~50nm.

[0013] Further, the method for preparing the tannic acid aqueous solution in step (3) is as follows: tannic acid and deionized water are mixed evenly to prepare a 3wt%~5wt% tannic acid aqueous solution.

[0014] Further, the molecular weight of the polyether polyol in step (4) is 200~1000.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: First, a functionalized quaternary phosphonium salt is prepared by reacting 3-chloro-1-propanethiol and triphenylphosphine, and a thiol group is introduced onto the functionalized quaternary phosphonium salt. Then, a hydroxyl group on polyvinyl alcohol is reacted with an epoxy group on glycidyl methacrylate to prepare pre-modified polyvinyl alcohol, and a methacrylate group is introduced onto the side chain of the pre-modified polyvinyl alcohol molecule. Then, a thiol-alkene click reaction is carried out with the thiol group on the functionalized quaternary phosphonium salt to prepare modified polyvinyl alcohol. The quaternary phosphonium salt is grafted onto the side chain of the modified polyvinyl alcohol molecule to enhance the antibacterial ability of the antibacterial and anti-mite liquid.

[0016] Secondly, modified nano-zinc oxide was prepared by reacting nano-zinc oxide sequentially with γ-aminopropyltriethoxysilane and tannic acid. Nano-zinc oxide is an inorganic antibacterial agent, and tannic acid is a natural water-soluble phenolic acid antibacterial agent. By loading tannic acid onto nano-zinc oxide, an organic-inorganic composite antibacterial system was formed, which not only improved the antibacterial ability of nano-zinc oxide, but also improved the dispersibility and stability of nano-zinc oxide in water, and avoided the aggregation and sedimentation of nano-zinc oxide particles.

[0017] Finally, modified polyvinyl alcohol, modified nano zinc oxide, hexyl salicylate, diisopropyl sebacate, polyether polyol, glycine, diethylene glycol monobutyl ether, benzalkonium chloride, and deionized water were mixed to prepare an antibacterial and mite-repellent liquid. Hexyl salicylate belongs to the aromatic carboxylic acid ester class of mite repellents, while diisopropyl sebacate belongs to the fatty acid ester class of mite repellents. Hexyl salicylate, as the core mite-repellent active ingredient, directly interferes with the nerve and metabolic pathways of mites to achieve repellency. Diisopropyl sebacate, as a penetration enhancer, helps the active ingredient penetrate the mite epidermis. The synergistic effect of the two gives the antibacterial and mite-repellent liquid excellent mite-repellent ability. Benzalkonium chloride, a quaternary ammonium salt cationic bactericide, can further enhance the antibacterial performance of the antibacterial and mite-repellent liquid. Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0019] Raw material information: Polyvinyl alcohol: degree of alcoholysis 88%, purchased from Wen'an County Juke Technology Co., Ltd.; Nano zinc oxide: 20nm particle size, 99% effective ingredient content, purchased from Shandong Xuchen Chemical Technology Co., Ltd. Polyether polyol: model PPG-600, purchased from Sanda Chemical Co., Ltd.; Polyester-cotton fabric: blend ratio 65 / 35, weight 246.2 g / m² 2 Purchased from Zhejiang Xinjian Textile Co., Ltd.

[0020] Example 1: A method for preparing an antibacterial and mite-repellent liquid, the method comprising the following preparation steps: (1) 3-chloro-1-propanethiol and triphenylphosphine were dissolved in N,N-dimethylformamide at a molar ratio of 1:1.1. The mixture was stirred at 90°C for 48 h under nitrogen protection, cooled to room temperature, filtered, washed with ethyl acetate, and dried under vacuum at 50°C for 24 h to obtain the functionalized quaternary phosphonium salt. (2) Mix polyvinyl alcohol and dimethyl sulfoxide at a mass ratio of 1:20, stir at room temperature for 10 min, add 0.03 times the mass of polyvinyl alcohol of p-diaminopyridine, stir at room temperature for 5 min, add 0.14 times the mass of polyvinyl alcohol of glycidyl methacrylate and mix evenly, heat to 70℃ and react for 7 h, cool to room temperature, precipitate in acetone with a volume of 4 times that of dimethyl sulfoxide, filter, wash with acetone, and vacuum dry at 40℃ for 20 h to obtain pre-modified polyvinyl alcohol; mix pre-modified polyvinyl alcohol and dimethyl sulfoxide at a mass ratio of 1:20, stir at room temperature for 10 min, add 0.1 times the mass of pre-modified polyvinyl alcohol of functionalized quaternary phosphonium salt, add 0.01 times the mass of pre-modified polyvinyl alcohol of triethylamine, heat to 75℃ and stir for 12 h, cool to room temperature, precipitate in acetone with a volume of 4 times that of dimethyl sulfoxide, filter, wash with acetone, and vacuum dry at 40℃ for 20 h to obtain modified polyvinyl alcohol; (3) Mix nano zinc oxide and anhydrous ethanol at a mass ratio of 1:100, ultrasonically disperse for 20 min, add 0.3 times the mass of nano zinc oxide γ-aminopropyltriethoxysilane and 8 times the mass of nano zinc oxide deionized water, heat to 70℃ and stir for 12 h, centrifuge, wash with anhydrous ethanol, and vacuum dry at 70℃ for 12 h to obtain pre-modified nano zinc oxide; mix tannic acid and deionized water evenly to prepare a 3wt% tannic acid aqueous solution; mix pre-modified nano zinc oxide and tannic acid aqueous solution at a mass ratio of 1:50, stir at 40℃ for 12 h, centrifuge, and vacuum dry at 50℃ for 18 h to obtain modified nano zinc oxide; (4) By mass, 3 parts modified polyvinyl alcohol, 1 part modified nano zinc oxide, 4 parts hexyl salicylate, 2 parts diisopropyl sebacate, 2 parts polyether polyol, 0.5 parts glycine, 5 parts diethylene glycol monobutyl ether, 1 part benzalkonium chloride and 150 parts deionized water are mixed to prepare an antibacterial and mite-repellent liquid.

[0021] Example 2: A method for preparing an antibacterial and mite-repellent liquid, the method comprising the following preparation steps: (1) 3-chloro-1-propanethiol and triphenylphosphine were dissolved in N,N-dimethylformamide at a molar ratio of 1:1.1. The mixture was stirred at 95°C for 42 h under nitrogen protection, cooled to room temperature, filtered, washed with ethyl acetate, and dried under vacuum at 55°C for 22 h to obtain the functionalized quaternary phosphonium salt. (2) Mix polyvinyl alcohol and dimethyl sulfoxide at a mass ratio of 1:22, stir at room temperature for 15 min, add 0.03 times the mass of polyvinyl alcohol of p-diaminopyridine, stir at room temperature for 7 min, add 0.14 times the mass of polyvinyl alcohol of glycidyl methacrylate and mix evenly, heat to 70℃ and react for 7 h, cool to room temperature, precipitate in acetone with a volume of 5 times that of dimethyl sulfoxide, filter, wash with acetone, and vacuum dry at 45℃ for 18 h to obtain pre-modified polyvinyl alcohol; mix pre-modified polyvinyl alcohol and dimethyl sulfoxide at a mass ratio of 1:22, stir at room temperature for 15 min, add 0.15 times the mass of pre-modified polyvinyl alcohol of functionalized quaternary phosphonium salt, add 0.015 times the mass of pre-modified polyvinyl alcohol of triethylamine, heat to 80℃ and stir for 11 h, cool to room temperature, precipitate in acetone with a volume of 5 times that of dimethyl sulfoxide, filter, acetone, and vacuum dry at 45℃ for 18 h to obtain modified polyvinyl alcohol; (3) Mix nano zinc oxide and anhydrous ethanol at a mass ratio of 1:110, ultrasonically disperse for 25 min, add 0.4 times the mass of nano zinc oxide γ-aminopropyltriethoxysilane and 9 times the mass of nano zinc oxide deionized water, heat to 75℃ and stir for 11 h, centrifuge, wash with anhydrous ethanol, and vacuum dry at 75℃ for 11 h to obtain pre-modified nano zinc oxide; mix tannic acid and deionized water evenly to prepare a 4wt% tannic acid aqueous solution; mix pre-modified nano zinc oxide and tannic acid aqueous solution at a mass ratio of 1:55, stir at 45℃ for 11 h, centrifuge, and vacuum dry at 55℃ for 17 h to obtain modified nano zinc oxide; (4) By mass, 4 parts modified polyvinyl alcohol, 1.5 parts modified nano zinc oxide, 4.5 parts hexyl salicylate, 2.5 parts diisopropyl sebacate, 2.5 parts polyether polyol, 0.7 parts glycine, 5.5 parts diethylene glycol monobutyl ether, 1.1 parts benzalkonium chloride and 175 parts deionized water are mixed to prepare an antibacterial and mite-repellent liquid.

[0022] Example 3: A method for preparing an antibacterial and mite-repellent liquid, the method comprising the following preparation steps: (1) 3-chloro-1-propanethiol and triphenylphosphine were dissolved in N,N-dimethylformamide at a molar ratio of 1:1.2, and the mixture was stirred at 100°C for 36 h under nitrogen protection. After cooling to room temperature, the mixture was filtered, washed with ethyl acetate, and dried under vacuum at 60°C for 20 h to obtain the functionalized quaternary phosphonium salt. (2) Mix polyvinyl alcohol and dimethyl sulfoxide at a mass ratio of 1:24, stir at room temperature for 20 min, add 0.03 times the mass of polyvinyl alcohol of p-diaminopyridine, stir at room temperature for 10 min, add 0.14 times the mass of polyvinyl alcohol of glycidyl methacrylate and mix evenly, heat to 70℃ and react for 7 h, cool to room temperature, precipitate in 6 times the volume of dimethyl sulfoxide in acetone, filter, wash with acetone, and vacuum dry at 50℃ for 16 h to obtain pre-modified polyvinyl alcohol; mix pre-modified polyvinyl alcohol and dimethyl sulfoxide at a mass ratio of 1:24, stir at room temperature for 20 min, add 0.2 times the mass of pre-modified polyvinyl alcohol of functionalized quaternary phosphonium salt, add 0.02 times the mass of pre-modified polyvinyl alcohol of triethylamine, heat to 85℃ and stir for 10 h, cool to room temperature, precipitate in 6 times the volume of dimethyl sulfoxide in acetone, filter, wash with acetone, and vacuum dry at 50℃ for 16 h to obtain modified polyvinyl alcohol; (3) Mix nano zinc oxide and anhydrous ethanol at a mass ratio of 1:120, ultrasonically disperse for 30 min, add 0.5 times the mass of nano zinc oxide γ-aminopropyltriethoxysilane and 10 times the mass of nano zinc oxide deionized water, heat to 80℃ and stir for 10 h, centrifuge, wash with anhydrous ethanol, and vacuum dry at 80℃ for 10 h to obtain pre-modified nano zinc oxide; mix tannic acid and deionized water evenly to prepare a 5 wt% tannic acid aqueous solution; mix pre-modified nano zinc oxide and tannic acid aqueous solution at a mass ratio of 1:60, stir at 50℃ for 10 h, centrifuge, and vacuum dry at 60℃ for 15 h to obtain modified nano zinc oxide; (4) By mass, 5 parts of modified polyvinyl alcohol, 2 parts of modified nano zinc oxide, 5 parts of hexyl salicylate, 3 parts of diisopropyl sebacate, 3 parts of polyether polyol, 1 part of glycine, 6 parts of diethylene glycol monobutyl ether, 1.2 parts of benzalkonium chloride and 200 parts of deionized water are mixed to prepare an antibacterial and anti-mite liquid.

[0023] Comparative Example 1: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 1 and Example 2 is that the step (2) of "adding 0.03 times the mass of polyvinyl alcohol with p-diaminopyridine" is changed to "adding 0.01 times the mass of polyvinyl alcohol with p-diaminopyridine".

[0024] Comparative Example 2: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 2 and Example 2 is that the step (2) of "adding 0.03 times the mass of polyvinyl alcohol with p-diaminopyridine" is changed to "adding 0.02 times the mass of polyvinyl alcohol with p-diaminopyridine".

[0025] Comparative Example 3: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 3 and Example 2 is that the step (2) of "adding 0.03 times the mass of polyvinyl alcohol to p-diaminopyridine" is changed to "adding 0.04 times the mass of polyvinyl alcohol to p-diaminopyridine".

[0026] Comparative Example 4: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 4 and Example 2 is that the step (2) of "adding 0.03 times the mass of polyvinyl alcohol with p-diaminopyridine" is changed to "adding 0.05 times the mass of polyvinyl alcohol with p-diaminopyridine".

[0027] Comparative Example 5: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 5 and Example 2 is that the step (2) of "adding 0.14 times the mass of polyvinyl alcohol glycidyl methacrylate" is changed to "adding 0.06 times the mass of polyvinyl alcohol glycidyl methacrylate".

[0028] Comparative Example 6: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 6 and Example 2 is that the step (2) of "adding 0.14 times the mass of polyvinyl alcohol glycidyl methacrylate" is changed to "adding 0.10 times the mass of polyvinyl alcohol glycidyl methacrylate".

[0029] Comparative Example 7: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 7 and Example 2 is that the step (2) of "adding 0.14 times the mass of polyvinyl alcohol glycidyl methacrylate" is changed to "adding 0.18 times the mass of polyvinyl alcohol glycidyl methacrylate".

[0030] Comparative Example 8: The difference between the preparation method of the antibacterial and mite-repellent liquid in Comparative Example 8 and Example 2 is that the "heating to 70°C and reacting for 7 hours" in step (2) is changed to "heating to 50°C and reacting for 7 hours".

[0031] Comparative Example 9: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 9 and Example 2 is that the "heating to 70°C and reacting for 7 hours" in step (2) is changed to "heating to 60°C and reacting for 7 hours".

[0032] Comparative Example 10: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 10 and Example 2 is that the "heating to 70°C and reacting for 7 hours" in step (2) is changed to "heating to 80°C and reacting for 7 hours".

[0033] Comparative Example 11: The preparation method of the antibacterial and anti-mite liquid in Comparative Example 11 differs from that in Example 2 in that steps (1) and (2) are omitted, and "modified polyvinyl alcohol" in step (4) is replaced with "polyvinyl alcohol".

[0034] Comparative Example 12: The preparation method of the antibacterial and anti-mite liquid in Comparative Example 12 differs from that in Example 2 in that step (3) is omitted, and "modified nano zinc oxide" in step (4) is replaced with "nano zinc oxide".

[0035] Comparative Example 13: The preparation method of the antibacterial and anti-mite liquid in Comparative Example 13 differs from that in Example 2 in that step (3) is not performed, and in step (4), "modified nano zinc oxide" is not added.

[0036] Comparative Example 14: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 14 and Example 2 is that "benzalkonium chloride" is not added in step (4).

[0037] Comparative Example 15: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 15 and Example 2 is that "hexyl salicylate" is not added in step (4).

[0038] Comparative Example 16: The difference between the preparation method of the antibacterial and anti-mite liquid in Comparative Example 16 and Example 2 is that "diisopropyl sebacate" is not added in step (4).

[0039] Comparative Example 17: The preparation method of the antibacterial and anti-mite liquid in Comparative Example 17 differs from that in Example 2 in that, in step (4), "hexyl salicylate" and "diisopropyl sebacate" are not added.

[0040] Test Example 1: The effects of reaction conditions (catalyst dosage, glycidyl methacrylate (GMA) dosage, and reaction temperature) on glycidyl methacrylate-modified polyvinyl alcohol (PVA).

[0041] Test samples: Example 2 and Comparative Examples 1-10; Test method: The prepared samples were dissolved in heavy water and scanned by 1H NMR using an AMX600M NMR spectrometer. The characteristic peaks of vinyl hydrogen were represented at δ = 5.6 ppm and δ = 6.0 ppm, and the peak of methyl proton in the unreacted acetyl group on the pre-modified polyvinyl alcohol chain was represented at δ = 2.0 ppm. The degree of substitution (DS) of glycidyl methacrylate on polyvinyl alcohol was calculated using the following formula. ; Among them, A 5.6 +A 6.0 Characteristic peaks representing hydrogen atoms grafted onto double bonds in pre-modified polyvinyl alcohol; A 2.0 This indicates the methyl proton peak in the unreacted acetyl group on the pre-modified polyvinyl alcohol chain. The results are shown in Table 1. in conclusion: As shown in Table 1, the experimental data reveals that different degrees of substitution in pre-modified polyvinyl alcohol (PVA) can be obtained by adjusting the amount of catalyst, glycidyl methacrylate (GMA), and reaction temperature. When the amount of catalyst is 0.03 times the mass of PVA, the amount of GMA is 0.14 times the mass of PVA, and the reaction temperature is 70°C, a pre-modified PVA with a substitution degree of 7.5% can be obtained. Further increasing the amount of catalyst does not significantly change the substitution degree. Further increasing the reaction temperature slightly decreases the substitution degree. Further increasing the amount of GMA slightly increases the substitution degree. To save resources and energy, this invention preferably uses an amount of catalyst of 0.03 times the mass of PVA, an amount of GMA of 0.14 times the mass of PVA, and a reaction temperature of 70°C.

[0042] Test Example 2: Antibacterial performance testing: Test samples: Examples 1-3 and Comparative Examples 11-14; Test method: The prepared antibacterial and anti-mite liquid was diluted with water to twice the mass of the original antibacterial and anti-mite liquid to obtain the finishing solution; the polyester-cotton fabric was soaked in the finishing solution at a bath ratio of 1:20, and the polyester-cotton fabric was dipped and rubbed twice with a padding machine with a padding rate of 80%; dried at 80℃ for 6 hours and baked at 150℃ for 5 minutes to obtain the test sample. The antimicrobial test was conducted according to GB / T 20944.3 "Evaluation of antimicrobial properties of textiles - Part 3: Shaking method". The polyester-cotton fabric without antimicrobial treatment was used as the control sample. The antimicrobial rate was calculated as (WQ) / W×100%. Where Q is the number of colonies in the petri dish of the test sample after 24 hours of shaking contact, and W is the number of colonies in the petri dish of the control sample after 24 hours of shaking contact. The test bacteria was Escherichia coli. The results are shown in Table 2. in conclusion: As can be seen from the experimental data in Table 2, the antibacterial rates of Examples 1-3 are significantly better than those of Comparative Examples 11-14, indicating that grafting quaternary phosphonium salts onto polyvinyl alcohol, adding nano zinc oxide, loading tannic acid onto the surface of nano zinc oxide, and adding benzalkonium chloride can all enhance the antibacterial and mite-repellent properties of the solution to a certain extent.

[0043] Tests on mite-repellent performance: Test samples: Examples 1-3 and Comparative Examples 15-17; Test method: The prepared antibacterial and anti-mite liquid was diluted with water to twice the mass of the original antibacterial and anti-mite liquid to obtain the finishing solution; the polyester-cotton fabric was soaked in the finishing solution at a bath ratio of 1:20, and the polyester-cotton fabric was dipped and rubbed twice with a padding machine with a padding rate of 80%; dried at 80℃ for 6 hours and baked at 150℃ for 5 minutes to obtain the test sample. According to GB / T24253, the repellency rate of the test sample against mites was tested. The mites were house dust mites, and untreated polyester-cotton fabric was used as a control. Seven petri dishes were fixed in a petal shape on an adhesive plate. 2000 mites were placed in the central dish, and the test sample and control sample were placed alternately in the outer six dishes, each with 0.05g of mite feed added. The dishes were incubated in a constant temperature and humidity incubator at 25℃ and 75% relative humidity for 24 hours. The number of surviving mites was counted. The repellency rate was calculated using the following formula: ; The test results are shown in Table 3; in conclusion: As shown in Table 3, the repulsion rate of mites in Examples 1-3 was significantly better than that in Comparative Examples 15-17, indicating that both hexyl salicylate and diisopropyl sebacate have the ability to repel mites and can significantly improve the mite-repelling ability of the antibacterial and mite-repelling liquid.

[0044] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An antibacterial and mite-repellent liquid, characterized in that, By weight, it mainly includes: 3-5 parts modified polyvinyl alcohol, 1-2 parts modified nano zinc oxide, 4-5 parts hexyl salicylate, 2-3 parts diisopropyl sebacate, 2-3 parts polyether polyol, 0.5-1 part glycine, 5-6 parts diethylene glycol monobutyl ether, 1-1.2 parts benzalkonium chloride, and 150-200 parts deionized water.

2. The antibacterial and mite-repellent liquid according to claim 1, characterized in that, The modified polyvinyl alcohol is prepared by reacting polyvinyl alcohol with glycidyl methacrylate and functionalized quaternary phosphonium salt in sequence.

3. The antibacterial and mite-repellent liquid according to claim 2, characterized in that, The functionalized quaternary phosphorus salt is prepared by reacting 3-chloro-1-propanethiol and triphenylphosphine.

4. The antibacterial and mite-repellent liquid according to claim 1, characterized in that, The modified nano zinc oxide is prepared by reacting nano zinc oxide sequentially with γ-aminopropyltriethoxysilane and tannic acid.

5. A method for preparing an antibacterial and anti-mite liquid, characterized in that, The preparation method of the antibacterial and mite-repellent liquid includes the following preparation steps: (1) Dissolve 3-chloro-1-propanethiol and triphenylphosphine in N,N-dimethylformamide at a molar ratio of 1:(1.1~1.2), stir and react at 90~100℃ for 36~48h under nitrogen protection, cool to room temperature, filter, wash and dry to obtain functionalized quaternary phosphonium salt; (2) Mix pre-modified polyvinyl alcohol and dimethyl sulfoxide, stir at room temperature for 10-20 min, add 0.1-0.2 times the mass of pre-modified polyvinyl alcohol functionalized quaternary phosphonium salt, add 0.01-0.02 times the mass of pre-modified polyvinyl alcohol triethylamine, heat to 75-85℃ and stir for 10-12 h, cool to room temperature, precipitate in acetone, filter, wash, dry, and obtain modified polyvinyl alcohol; (3) Mix pre-modified nano zinc oxide and tannic acid aqueous solution at a mass ratio of 1:(50~60), stir at 40~50℃ for 10~12h, centrifuge, and dry to obtain modified nano zinc oxide; (4) By mass, mix 3-5 parts of modified polyvinyl alcohol, 1-2 parts of modified nano zinc oxide, 4-5 parts of hexyl salicylate, 2-3 parts of diisopropyl sebacate, 2-3 parts of polyether polyol, 0.5-1 parts of glycine, 5-6 parts of diethylene glycol monobutyl ether, 1-1.2 parts of benzalkonium chloride, and 150-200 parts of deionized water to prepare an antibacterial and mite-repellent liquid.

6. The method for preparing the antibacterial and anti-mite liquid according to claim 5, characterized in that, The preparation method of the pre-modified polyvinyl alcohol in step (2) is as follows: polyvinyl alcohol and dimethyl sulfoxide are mixed and stirred at room temperature. 0.01 to 0.05 times the mass of polyvinyl alcohol and p-diaminopyridine are added and stirred at room temperature. 0.06 to 0.18 times the mass of polyvinyl alcohol and glycidyl methacrylate are added and mixed evenly. The mixture is heated to 50 to 80°C and reacted for 7 to 8 hours. The mixture is cooled to room temperature, precipitated in acetone, filtered, washed, and dried to obtain the pre-modified polyvinyl alcohol.

7. The method for preparing the antibacterial and anti-mite liquid according to claim 6, characterized in that, The degree of alcoholysis of the polyvinyl alcohol is 88%.

8. The method for preparing the antibacterial and anti-mite liquid according to claim 5, characterized in that, The preparation method of the pre-modified nano zinc oxide in step (3) is as follows: mix nano zinc oxide and anhydrous ethanol, disperse by ultrasonication, add 0.3 to 0.5 times the mass of nano zinc oxide in γ-aminopropyltriethoxysilane, add deionized water, heat to 70 to 80°C and stir for 10 to 12 hours, centrifuge, wash, dry, and obtain pre-modified nano zinc oxide.

9. The method for preparing the antibacterial and anti-mite liquid according to claim 8, characterized in that, The particle size of the nano zinc oxide is 20~50nm.

10. The method for preparing the antibacterial and anti-mite liquid according to claim 5, characterized in that, The method for preparing the tannic acid aqueous solution in step (3) is as follows: mix tannic acid and deionized water evenly to prepare a 3wt%~5wt% tannic acid aqueous solution.

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