Spinning oil agent for antibacterial chinlon and preparation method of spinning oil agent

Abstract

The invention provides spinning oil for antibacterial chinlon and a preparation method, and the spinning oil for antibacterial chinlon comprises the following components in parts by weight: 60-65 parts of a smoothing agent, 12-16 parts of an emulsifier, 5-10 parts of an antistatic agent and 4-6 parts of modified nano titanium dioxide, the modified nano titanium dioxide is prepared by reacting with alkylchlorosilane to carry out alkyl grafting and then carrying out epoxy modification, the smoothing agent comprises the following components in parts by weight: 67-73 parts of mineral oil, 11-15 parts of pentaerythritol oleate and 0.1-0.2 part of a polyurea-based compound, the molecular formula of the polyurea-based compound is H-[R1-NHCONH-R2] n-OH, R1 and R1 are C12-C15, and n is equal to 5-8. According to the invention, the surface of nano titanium dioxide is subjected to alkyl grafting modification, so that the hydrophobicity and the compatibility with an oil agent are improved; and then epoxy modification is carried out to introduce an epoxy group to the surface, and the epoxy group and an amide group of chinlon can form a hydrogen bond to improve the binding strength of the nano titanium dioxide and the chinlon fiber, so that the chinlon fiber is endowed with certain antibacterial ability.

Description

Technical Field

[0001] The present invention relates to the technical field of spinning oils, and in particular to an antibacterial spinning oil for nylon and a preparation method thereof. Background Art

[0002] As the first industrialized synthetic fiber, nylon (also known as nylon) was mass-produced by DuPont in 1935. Its molecular structure is composed of repeating -[NH-(CH2)5-CO]- units. The polarity of the amide bonds it contains makes it have good hygroscopicity. The flexibility of the fatty chains makes the elastic recovery rate exceed 90%, and it has good elasticity and resilience. The hydrogen bond network formed by a large number of amide bonds gives it high strength and toughness. Because it can take into account strength, elasticity and modification flexibility, it has become a benchmark for synthetic fibers that balance performance and function expansion. It is widely used in civilian textiles such as sportswear and home textiles, as well as industrial textiles in the medical field, automotive industry, etc., with a global production capacity exceeding 8 million tons in 2023.

[0003] Antibacterial nylon is gaining increasing attention due to its ability to inhibit bacterial regeneration. Its main production methods include: 1) coating the nylon surface with antibacterial materials, which usually have poor water washability and affect their effectiveness; 2) preparing the product by melting a mixture of inorganic antibacterial agents and nylon chips. The addition of inorganic antibacterial metals increases the friction coefficient, making it very easy for abnormal phenomena such as lint and broken ends to occur during the spinning process.

[0004] Spinning oil is an intermediate medium in the process of converting textile raw materials into textiles. The formula design of spinning oil directly affects production cost control, spinning efficiency and finished product quality. However, the mechanical strength of the oil film of existing nylon spinning oils is insufficient, resulting in an increased breakage rate during high-speed spinning. The antibacterial performance does not meet medical application standards, which limits its application in high-value-added scenarios such as medical dressings and antibacterial surgical gowns. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide an antibacterial spinning oil for nylon and a preparation method. Modified titanium dioxide is added to the spinning oil to improve compatibility, while solving the technical problems of high friction coefficient and poor antibacterial property during the spinning process.

[0006] To solve the above problems, the present invention provides an antibacterial nylon spinning oil, which comprises the following components, calculated by weight: 60-65 parts of a smoothing agent, 12-16 parts of an emulsifier, 5-10 parts of an antistatic agent, and 4-6 parts of modified nano-titanium dioxide, wherein the modified nano-titanium dioxide is prepared by reacting with an alkylchlorosilane for alkyl grafting and then epoxy-modified. The smoothing agent comprises, by weight, 67-73 parts of mineral oil, 11-15 parts of pentaerythritol oleate, and 0.1-0.2 parts of a polyurea-based compound, wherein the molecular formula of the polyurea-based compound is H-[R1-NHCONH-R2] n -OH, where R1, R2 are C 12 -C 15 , n=5-8.

[0007] The present application increases the hydrophobicity of nano-titanium dioxide by performing alkyl grafting modification on the surface, thereby improving its compatibility with the oil so that it can be better dispersed in the oil; then epoxy modification is performed, and the epoxy groups introduced on the surface, the hydroxyl groups obtained by the ring opening of the epoxy groups can form hydrogen bonds with the amide groups of nylon, thereby improving the bonding strength between nano-titanium dioxide and nylon fibers, improving the wetting performance of the spinning oil on the fiber surface and giving the nylon fibers a certain antibacterial ability; at the same time, by using a mineral oil that is inexpensive, has good smoothness at low temperatures and good sizing performance as the base oil, a small amount of pentaerythritol tetraester is added to improve the heat resistance of the oil, and the four ester groups contained in the molecule make its adsorption force with the fiber stronger, and a small amount of polyurea-based compound not only has thermal stability that meets the requirements of high-speed spinning, but also provides hydrogen bond donors through double NH and can form an intermolecular hydrogen bond network with the ester group, thereby improving the solubility of pentaerythritol ester while improving the oil film strength and wear resistance.

[0008] Preferably, the preparation method of the modified nano-titanium dioxide comprises: adding 1.0 g of nano-titanium dioxide powder, 10-13 ml of octamethylcyclotetrasiloxane and 10-12 ml of toluene to a reaction container, ultrasonically dispersing the mixture under nitrogen protection for 40-45 min until uniform dispersion, heating the mixture to 52-60° C. and purging the mixture with nitrogen for 20-45 min; adding 0.1-0.7 g of alkylchlorosilane dropwise under heating to 64-70° C. and stirring the mixture for 6-8 h; then adding 9-13 mL of glacial ethanol to terminate the reaction, separating the solid product, washing the solid product 2-4 times with anhydrous ethanol at a ratio of 1 g / 2-3 ml, and vacuum drying the solid product at 40-50° C. for 8-15 h to obtain an intermediate product.

[0009] Preferably, the alkylchlorosilane is one of dodecyltrichlorosilane, tetradecyltrichlorosilane, or hexadecyltrichlorosilane, and the weight ratio of the alkylchlorosilane to the nano-titanium dioxide powder is 3-7g:10g. This configuration can ensure that the grafting rate of the alkyl graft modification is 35-45%, ensuring good compatibility with the oil and a large antibacterial agent loading. At the same time, the epoxy modification leaves certain reaction sites, thereby strengthening the bonding ability with the fiber. Preferably, the weight ratio of the alkylchlorosilane to the nano-titanium dioxide powder is 3-5g:10g.

[0010] Preferably, the nano-titanium dioxide powder has a particle size of 40-50 nm. This particle size range ensures that anatase TiO2 has excellent photocatalytic activity, forming cavities under ultraviolet light. These cavities react with surface-adsorbed H2O / O2 to generate highly oxidizing reactive oxygen species, thereby destroying bacterial cell membrane lipids and sterilizing them. It also prevents deposition and clogging of the spinneret micropores during the spinning process.

[0011] Preferably, the preparation method of the modified nano-titanium dioxide further includes: adding 6-10g of the intermediate product and 15-25g of γ-glycidyloxypropyltrimethoxysilane to 120-150ml of 85%-90wt% ethanol aqueous solution, reacting at 65-72°C under nitrogen protection for 4-6h, separating the solid product, washing it with anhydrous ethanol at a ratio of 1g / 2-4ml for 2-4 times, and vacuum drying it at 42-48°C for 8-12h to obtain the product.

[0012] The lubricant comprises, by weight, 67-73 parts of mineral oil, 11-15 parts of pentaerythritol oleate, 2-3 parts of modified nano-silica, and 0.1-0.2 parts of a polyurea-based compound. The modified nano-silica described herein can improve the stability of the lubricant. After being dispersed in the lubricant, it can act as "micro-balls" at the fiber contact interface, converting sliding friction into rolling friction. It can also fill surface pits to reduce roughness, thereby reducing the coefficient of friction. Furthermore, the hydroxyl groups (-OH) on the surface of the nano-silica interact with polar groups such as ester groups in the lubricant, further enhancing the strength of the oil film.

[0013] As an example of the present invention, the modified nano-silica is prepared by the following method: nano-silica is dissolved in ethanol at a ratio of 1 g / 100 ml and then ultrasonically dispersed for 30 minutes to obtain solution one; a silane coupling agent is dissolved in ethanol at a ratio of 1 g:10 ml, 3 ml of distilled water is slowly added under stirring at 60 rpm, the pH value is adjusted to 4.5, and the solution is allowed to stand for 6 hours to obtain solution two; solution one is slowly added to solution two and stirred at 60 rpm for 3 hours, the solid product is separated, washed twice with anhydrous ethanol at a ratio of 1 g / 2 ml, and vacuum dried at 45°C for 12 hours.

[0014] Preferably, the emulsifier is composed of 4-7 parts of trioctylamine and 15-20 parts of any one selected from fatty acid polyoxyethylene esters, fatty alcohol polyoxyethylene ethers, castor oil polyoxyethylene ethers, sorbitan fatty acid ester polyoxyethylene ethers, and sorbitan fatty acid esters.

[0015] This application uses trioctylamine as part of the emulsifier. It has a boiling point of 365-370°C and contains three long octyl chains. It has strong hydrophobicity and can effectively reduce the surface tension of the oil. It has good compatibility with the oil and no risk of volatilization, which can improve the emulsification stability. In addition, trioctylamine can capture the hydrogen of the amide nitrogen atom to generate nucleophilic amide anion and attack the epoxy ring to open the ring, thereby catalyzing the bonding of modified nano-titanium dioxide containing epoxy groups with the amide group of nylon fiber, thereby improving the water washing resistance.

[0016] Preferably, the antistatic agent is any one of tridecyl isomeric ether phosphate, lauryl potassium phosphate, and diethanolamine salt of alkyl phosphate. Anionic antistatic agents such as phosphate salts can form ion-pair complexes with the weakly basic nitrogen atoms contained in trioctylamine. Their amphiphilic properties significantly reduce the oil-water interfacial tension. The trioctylamine cations form a conductive path with the anionic antistatic agent, thereby enhancing the antistatic ability of the spinning oil in low-humidity environments.

[0017] The present invention also provides a method for preparing an antibacterial nylon spinning oil, comprising the following steps: weighing each component by weight, first stirring and dispersing a portion of the emulsifier and modified nano zinc oxide particles to uniformly form a mixed dispersion, then adding a smoothing agent, an antistatic agent and trioctylamine in sequence, and then reacting at a temperature of 40-45°C and a stirring rate of 50-70 r / min for 2-3 hours to obtain the obtained product.

[0018] Compared with the prior art, the antibacterial nylon spinning oil and preparation method described in the embodiments of the present invention have the following beneficial effects: 1) Alkyl grafting modification of the surface of nano-titanium dioxide can increase its hydrophobicity, thereby improving its compatibility with the oil so that it can be better dispersed in the oil; 2) Nano-titanium dioxide is further epoxy-modified to introduce epoxy groups on its surface. The hydroxyl groups obtained by ring-opening the epoxy groups can form hydrogen bonds with the amide groups of nylon, thereby improving the bonding strength between nano-titanium dioxide and nylon fibers, improving the wetting performance of the spinning oil on the fiber surface and giving nylon fibers a certain antibacterial ability. Combined with the existing antibacterial nylon preparation process It can take into account both antibacterial properties and water washability; 3) modified nano-silica can act as "micro-balls" at the fiber contact interface, converting sliding friction into rolling friction, and at the same time can fill surface pits to reduce roughness, thereby reducing the friction coefficient; at the same time, it interacts with polar groups in the oil to improve the oil film strength; 4) the smoothing agent improves the heat resistance of the oil by adding a small amount of pentaerythritol tetraester to the mineral oil, and a small amount of polyurea-based compound double NH provides hydrogen bond donors and ester groups to form an intermolecular hydrogen bond network, which not only improves the solubility of pentaerythritol ester, but also helps to improve the oil film strength and wear resistance of the oil. DETAILED DESCRIPTION

[0019] To make the above-mentioned objects, features and advantages of the present invention more clearly understood, the following describes in detail the specific embodiments of the present invention. The technical features of the embodiments of the present invention may be combined with each other without conflict.

[0020] Nylon is a chemical synthetic fiber, scientifically known as polyamide fiber (PA). Its molecular main chain contains repeated amide groups. It is widely used in clothing, home textiles, industry and other fields due to its excellent wear resistance, high strength and good elastic recovery, and has become one of the indispensable important fiber materials in the modern textile industry. Traditional nylon fibers are prone to breeding bacteria during use, which not only produces odor, but also causes skin allergies, infections and other problems, especially in application scenarios such as sportswear, underwear, bedding, etc. that are in close contact with the human body. It is more prominent. The commonly used method is to attach inorganic antibacterial agents to the fiber surface by impregnation, coating, etc., but there are usually problems such as easy shedding of antibacterial agents and poor durability. As an intermediate medium in the process of converting textile raw materials into textiles, the attachment rate of spinning oil on the fiber is about 0.3%-0.5%, but it plays an important role in the process of fiber production, spinning and weaving. How to use spinning oil to solve the high friction coefficient in the spinning process and make nylon have certain antibacterial properties is obviously of great significance. To this end, the applicant proposes the following technical solution: Experimental Example: Effect of Nano-Titanium Dioxide Modification on the Physical and Chemical Properties of Oils This application uses alkyl chlorosilane to perform alkyl grafting modification on nano-titanium dioxide, and then performs epoxy modification to improve the ability of the hydroxyl groups obtained by ring-opening the epoxy groups of nylon fibers to form hydrogen bonds with the amide groups of nylon, thereby improving the bonding strength between nano-titanium dioxide and nylon fibers, thereby improving its water resistance. The applicant found that the carbon chain length of the alkyl chlorosilane is related to the compatibility of the final modified nano-titanium dioxide with the oil agent and the efficiency of the subsequent epoxy modification reaction. For this reason, the applicant modified the nano-titanium dioxide according to the alkyl chlorosilane in Table 1 on the basis of Example 1, and tested the physical properties of the prepared oil agent and its configured emulsion under the same conditions. The test indicators include: Zeta potential (electrophoretic light scattering instrument, model Nano ZS90); oil film strength (using a four-ball friction instrument), friction coefficient (using a Changzhou Second Textile Machinery Plant Y151 yarn friction coefficient tester). The specific detection method is existing technology and will not be repeated here.

[0021] As shown in Table 1, as the carbon chain length of the alkylchlorosilane increases, the absolute value of the zeta potential of the final spinning oil first increases and then decreases. Among them, the oil corresponding to the modified nano-titanium dioxide prepared with dodecyltrichlorosilane, tetradecyltrichlorosilane, or hexadecyltrichlorosilane has good stability and is not prone to precipitation or stratification. The oil film strength shows a positive correlation with the carbon chain length of the alkylchlorosilane, while the dynamic friction coefficient shows a trend of first decreasing and then increasing with the increase of the carbon chain length of the alkylchlorosilane. In summary, when the carbon chain length of the alkylchlorosilane is 12-16, the final oil has good oil film strength and low dynamic friction coefficient while maintaining dispersion stability. Among them, tetradecyltrichlorosilane has the best performance. The possible reasons are: when the carbon chain of the alkylchlorosilane is too short, it affects the compatibility with the oil, resulting in poor stability, while when the carbon chain is too long, the steric hindrance is too large, which affects the epoxy modification reaction and has an adverse effect on the oil film strength and dynamic friction coefficient of the final oil.

[0022] Since the polar Si-OH groups on the surface of nano-titanium dioxide can undergo an alkyl grafting reaction with alkylchlorosilanes, and also undergo a condensation reaction with the siloxane groups of γ-glycidyloxypropyltrimethoxysilane, the epoxy groups are retained on the surface of the nano-titanium dioxide. This not only enhances the compatibility of nano-titanium dioxide with the oil, but also provides the possibility for subsequent hydrogen bonding with the amide groups of nylon fibers. Obviously, the dosage ratio of nano-titanium dioxide and alkylchlorosilane will affect the grafting rate, thereby changing the ratio of alkyl and epoxy groups and ultimately affecting the dispersibility and oil film strength. For this reason, based on Example 3, nano-titanium dioxide was modified according to the dosage ratios in Table 2. The prepared oil and its configured emulsion were tested for physical properties under the same conditions. The antibacterial rate of Escherichia coli was carried out in accordance with QB / T2738-2012.

[0023] As can be seen from Table 2, the oil film strength gradually increases with the increase of the dosage of tetradecyltrichlorosilane, while the antibacterial performance gradually decreases. When the mass ratio of tetradecyltrichlorosilane to TiO2 is 0.3-0.5, the spinning oil prepared by modified nano-silica has good oil film strength and the antibacterial rate is also maintained at a high level. The experiment found that when the mass ratio of tetradecyltrichlorosilane to TiO2 is too high, the high hydrophobicity may hinder the emulsification balance of water in the oil, and it is very easy to stratify when there is water in the oil.

[0024] Example 1 An antibacterial nylon spinning oil, comprising the following components by weight: 60 parts of a smoothing agent, 15 parts of an emulsifier, 5 parts of an antistatic agent, and 4 parts of modified nano-titanium dioxide; The lubricant comprises 70 parts by weight of mineral oil, 15 parts of pentaerythritol oleate, and 0.1 parts of a polyurea compound, wherein the molecular formula of the polyurea compound is (H-[C 12 -NHCONH-C 12 ]5-OH), the emulsifier includes 18 parts of fatty acid polyoxyethylene ester and 7 parts of trioctylamine in parts by weight, and the antistatic agent is isomeric tridecyl alcohol ether phosphate; The modified nano titanium dioxide is prepared by the following method: 1.0 g of nano-titanium dioxide powder, 12 ml of octamethylcyclotetrasiloxane, and 12 ml of toluene were added to a three-necked flask, and ultrasonicated for 45 min under nitrogen protection until uniformly dispersed. The temperature was raised to 60°C, and nitrogen was purged for 30 min to remove trace moisture. 0.4 g of dodecyltrichlorosilane was added dropwise under heating to 70°C, and stirred for 6 h. 10 mL of glacial ethanol was added to terminate the reaction. After separating the solid product, it was washed three times with anhydrous ethanol at a ratio of 1 g / 3 ml, and dried in vacuo at 45°C for 12 h to obtain an intermediate product. 8 g of the intermediate product and 25 g of γ-glycidyloxypropyltrimethoxysilane were added to 150 ml of a 90 wt% ethanol aqueous solution, and the mixture was reacted at 70° C. for 5 h under nitrogen protection. After separation, the solid product was washed three times with anhydrous ethanol at a ratio of 1 g / 3 ml, and dried in vacuo at 45° C. for 12 h to obtain modified nano-titanium dioxide.

[0025] The method for preparing the antibacterial nylon spinning oil comprises the following steps: Weigh each component by weight, first stir and disperse fatty acid polyoxyethylene ester and modified nano titanium dioxide particles evenly to form a mixed dispersion; then add a smoothing agent, an antistatic agent, and trioctylamine in sequence, then heat to 45°C and stir at 50 rpm for 2 hours to obtain the dispersion.

[0026] Example 2 An antibacterial nylon spinning oil comprises the following components in parts by weight: 65 parts of a smoothing agent, 12 parts of an emulsifier, 8 parts of an antistatic agent, and 6 parts of modified nano-titanium dioxide; The lubricant comprises 67 parts of mineral oil, 13 parts of pentaerythritol oleate, and 0.2 parts of a polyurea compound by weight, wherein the molecular formula of the polyurea compound is (H-[C 13 -NHCONH-C 13 ]8-OH), the emulsifier includes 15 parts of fatty alcohol polyoxyethylene ether and 4 parts of trioctylamine in parts by weight, and the antistatic agent is potassium lauryl phosphate; The modified nano titanium dioxide is prepared by the following method: 1.0 g of nano-titanium dioxide powder, 10 ml of octamethylcyclotetrasiloxane, and 10 ml of toluene were added to a three-necked flask, and ultrasonicated for 40 min under nitrogen protection until uniform dispersion was achieved. The temperature was raised to 55°C and purged with nitrogen for 45 min to remove trace moisture. 0.5 g of hexadecyltrichlorosilane was added dropwise under heating to 68°C, and stirred for 7 h. 13 mL of glacial ethanol was added to terminate the reaction. The solid product was separated and washed twice with anhydrous ethanol at a ratio of 1 g / 2.5 ml, and dried in vacuo at 40°C for 15 h to obtain an intermediate product. 6 g of the intermediate product and 20 g of γ-glycidyloxypropyltrimethoxysilane were added to 140 ml of a 90 wt% ethanol aqueous solution, and the mixture was reacted at 72° C. for 4 h under nitrogen protection. After separation, the solid product was washed four times with anhydrous ethanol at a ratio of 1 g / 2 ml, and vacuum dried at 42° C. for 10 h to obtain modified nano-titanium dioxide.

[0027] The method for preparing the antibacterial nylon spinning oil comprises the following steps: Weigh each component by weight, first stir and disperse fatty acid polyoxyethylene ester and modified nano titanium dioxide particles evenly to form a mixed dispersion; then add a smoothing agent, an antistatic agent, and trioctylamine in sequence, then heat to 40°C and stir at 70 rpm for 2.5 hours to obtain the dispersion.

[0028] Example 3 An antibacterial nylon spinning oil comprises the following components in parts by weight: 62 parts of a smoothing agent, 16 parts of an emulsifier, 10 parts of an antistatic agent, and 5 parts of modified nano-titanium dioxide; The lubricant comprises, by weight, 73 parts of mineral oil, 11 parts of pentaerythritol oleate, 2 parts of modified nano-silicon dioxide, and 0.15 parts of a polyurea-based compound, wherein the molecular formula of the polyurea-based compound is (H-[C 15 -NHCONH-C 15 ]7-OH), the emulsifier includes 20 parts of castor oil polyoxyethylene ether and 6 parts of trioctylamine in parts by weight, and the antistatic agent is alkyl phosphate diethanolamine salt; The preparation method of the modified nano-silica comprises the following steps: dissolving nano-silica in ethanol at a ratio of 1 g / 100 ml and then ultrasonically dispersing the solution for 30 minutes to obtain a first solution; dissolving a silane coupling agent in ethanol at a ratio of 1 g:10 ml, slowly adding 3 ml of distilled water under stirring at 60 rpm, adjusting the pH value to 4.5, and then standing for 6 hours to obtain a second solution; slowly adding the first solution to the second solution and stirring at 60 rpm for 3 hours, separating the solid product, washing it twice with anhydrous ethanol at a ratio of 1 g / 2 ml, and vacuum drying it at 45° C. for 12 hours to obtain the product.

[0029] The modified nano titanium dioxide is prepared by the following method: 1.0 g of nano-titanium dioxide powder, 13 ml of octamethylcyclotetrasiloxane, and 11 ml of toluene were added to a three-necked flask and ultrasonically dispersed under nitrogen for 43 min. The temperature was raised to 52°C and purged with nitrogen for 20 min to remove trace moisture. 0.3 g of tetradecyltrichlorosilane was added dropwise under heating to 64°C and stirred for 8 h. 9 mL of glacial ethanol was added to terminate the reaction. The solid product was separated and washed four times with anhydrous ethanol at a ratio of 1 g / 2 ml, and dried under vacuum at 50°C for 8 h to obtain an intermediate product. 10 g of the intermediate product and 15 g of γ-glycidyloxypropyltrimethoxysilane were added to 120 ml of 85 wt% ethanol aqueous solution, and the mixture was reacted at 65° C. for 6 h under nitrogen protection. After separation, the solid product was washed twice with anhydrous ethanol at a ratio of 1 g / 4 ml, and vacuum dried at 48° C. for 8 h to obtain modified nano-titanium dioxide.

[0030] The method for preparing the antibacterial nylon spinning oil comprises the following steps: Weigh each component by weight, first stir and disperse fatty acid polyoxyethylene ester and modified nano titanium dioxide particles evenly to form a mixed dispersion; then add a smoothing agent, an antistatic agent, and trioctylamine in sequence, then heat to 42°C and stir at 60 rpm for 3 hours to obtain the dispersion.

[0031] Comparative Example 1 This comparative example uses nano-titanium dioxide as the antibacterial component, and the rest is based on Example 1, specifically: An antibacterial nylon spinning oil, comprising the following components by weight: 60 parts of a smoothing agent, 15 parts of an emulsifier, 5 parts of an antistatic agent, and 4 parts of nano-titanium dioxide; The lubricant comprises 70 parts by weight of mineral oil, 15 parts of pentaerythritol oleate, and 0.1 parts of a polyurea compound, wherein the molecular formula of the polyurea compound is (H-[C 12 -NHCONH-C 12 ]5-OH), the emulsifier includes 18 parts of fatty acid polyoxyethylene ester and 7 parts of trioctylamine in parts by weight, and the antistatic agent is isomeric tridecyl alcohol ether phosphate.

[0032] The method for preparing the antibacterial nylon spinning oil comprises the following steps: Weigh each component by weight, first stir and disperse fatty acid polyoxyethylene ester and nano-titanium dioxide particles evenly to form a mixed dispersion; then add a smoothing agent, an antistatic agent, and trioctylamine in sequence, then heat to 45°C and stir at 50 rpm for 2 hours to obtain the dispersion.

[0033] Comparative Example 2 This comparative example adjusts the process sequence of modified nano-titanium dioxide, and the rest refers to Example 1, specifically: An antibacterial nylon spinning oil, comprising the following components by weight: 60 parts of a smoothing agent, 15 parts of an emulsifier, 5 parts of an antistatic agent, and 4 parts of modified nano-titanium dioxide; The lubricant comprises 70 parts by weight of mineral oil, 15 parts of pentaerythritol oleate, and 0.1 parts of a polyurea compound, wherein the molecular formula of the polyurea compound is (H-[C 12 -NHCONH-C 12 ]5-OH), the emulsifier includes 18 parts of fatty acid polyoxyethylene ester and 7 parts of trioctylamine in parts by weight, and the antistatic agent is isomeric tridecyl alcohol ether phosphate.

[0034] 1.0 g of nano-titanium dioxide powder and 3.1 g of γ-glycidyloxypropyltrimethoxysilane were added to 18 ml of 90 wt% ethanol aqueous solution, and the mixture was reacted at 70°C for 5 h under nitrogen protection. The solid product was separated and washed three times with anhydrous ethanol at a ratio of 1 g / 3 ml, and dried in vacuo at 45°C for 12 h to obtain an intermediate product. 1 g of the intermediate product, 12 ml of octamethylcyclotetrasiloxane and 12 ml of toluene were added to a three-necked flask, and the mixture was ultrasonically treated for 45 min under nitrogen protection until uniform dispersion. The temperature was raised to 60°C, and nitrogen was purged for 30 min to remove trace moisture. 0.4 g of dodecyltrichlorosilane was added dropwise under heating to 70°C and stirred for 6 h. 10 mL of icy ethanol was added to terminate the reaction. After separating the solid product, it was washed three times with anhydrous ethanol at a ratio of 1 g / 3 ml, and dried in vacuo at 45°C for 12 h to obtain modified nano-titanium dioxide.

[0035] The method for preparing the antibacterial nylon spinning oil comprises the following steps: Weigh each component by weight, first stir and disperse fatty acid polyoxyethylene ester and nano-titanium dioxide particles evenly to form a mixed dispersion; then add a smoothing agent, an antistatic agent, and trioctylamine in sequence, then heat to 45°C and stir at 50 rpm for 2 hours to obtain the dispersion.

[0036] The antibacterial nylon spinning oils prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests, and their oil film strength (referring to GB / T3142-82), wetting performance (referring to GB / T11983-2008), and dynamic friction coefficient were tested respectively. At the same time, the antibacterial performance of the fabrics prepared using the spinning oils was tested for washability, wherein the washability test was conducted in accordance with GB / T8629-2017, and the antibacterial performance test was conducted using Escherichia coli as the test bacteria in accordance with GB / T20944.3-2008. The results are shown in Table 3.

[0037] As shown in Table 3, compared with Comparative Example 1, Examples 1-3 can increase the hydrophobicity of nano-titanium dioxide by alkyl grafting modification on the surface, thereby improving the compatibility with the oil agent so as to better disperse in the oil agent; and then perform epoxy modification, the epoxy groups introduced on the surface, the hydroxyl groups obtained by the ring opening of the epoxy groups can form hydrogen bonds with the amide groups of nylon, thereby improving the bonding strength between nano-titanium dioxide and nylon fiber, improving the wetting performance of the spinning oil on the fiber surface and giving the nylon fiber a certain antibacterial ability. Finally, the antibacterial performance retention rate of the fabric after 10 washings is greater than 95%, which is much higher than that of Comparative Example 1; due to the addition of the spinning oil The oil content is typically no more than 1%, while the modified nano-titanium dioxide accounts for approximately 5% of the oil, resulting in an extremely low content of antimicrobial components ultimately attached to the fabric, thus limiting the final antimicrobial performance. However, this is compatible with the preparation of traditional antimicrobial nylon, thus achieving a balance between antimicrobial performance and durability. Compared to Examples 1-2, the addition of modified nano-silica in Example 3 of this application acts as "micro-balls" at the fiber contact interface, transforming sliding friction into rolling friction while filling surface pits to reduce roughness and, consequently, the coefficient of kinetic friction. The surface hydroxyl groups interact with the polar groups in the oil to enhance the oil film strength. Compared to Comparative Example 2, this application first performs alkyl grafting modification on the nano-titanium dioxide. The alkyl chain is an inert group that does not interfere with the subsequent epoxy grafting and improves the dispersibility of TiO2 in organic solvents, facilitating the uniformity of the second epoxy modification step. If epoxy modification is performed first, the highly reactive epoxy groups will undergo ring-opening side reactions during the alkylation process, resulting in significant loss of epoxy groups and adversely affecting the physical and chemical properties of the oil.

[0038] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope defined by the claims.

Claims

1. An antibacterial nylon spinning oil, characterized in that: The invention comprises the following components in parts by weight: 60-65 parts of a smoothing agent, 12-16 parts of an emulsifier, 5-10 parts of an antistatic agent, and 4-6 parts of modified nano-titanium dioxide, wherein the modified nano-titanium dioxide is prepared by reacting with an alkylchlorosilane for alkyl grafting and then epoxy-modified. The smoothing agent comprises 67-73 parts of a mineral oil, 11-15 parts of pentaerythritol oleate, and 0.1-0.2 parts of a polyurea-based compound, wherein the molecular formula of the polyurea-based compound is H-[R1-NHCONH-R2] n -OH, where R1, R2 are C 12 -C 15 , n=5-8.

2. The antibacterial nylon spinning oil according to claim 1, characterized in that: The preparation method of the modified nano-titanium dioxide comprises: adding 1.0 g of nano-titanium dioxide powder, 10-13 ml of octamethylcyclotetrasiloxane and 10-12 ml of toluene to a reaction container, performing ultrasonic treatment for 40-45 minutes under nitrogen protection until uniform dispersion, heating to 52-60° C. and purging with nitrogen for 20-45 minutes; adding 0.1-0.7 g of alkylchlorosilane dropwise under the condition of heating to 64-70° C. and stirring for reaction for 6-8 hours; then adding 9-13 ml of glacial ethanol to terminate the reaction, separating the solid product, washing it 2-4 times with anhydrous ethanol at a ratio of 1 g / 2-3 ml, and vacuum drying it at 40-50° C. for 8-15 hours to obtain an intermediate product.

3. The antibacterial nylon spinning oil according to claim 2, characterized in that: The alkylchlorosilane is one of dodecyltrichlorosilane, tetradecyltrichlorosilane or hexadecyltrichlorosilane, and the weight ratio of the alkylchlorosilane to the nano titanium dioxide powder is 1-7g:10g.

4. The antibacterial nylon spinning oil according to claim 2, characterized in that: The particle size of the nano titanium dioxide powder is 40-50 nm.

5. The antibacterial nylon spinning oil according to claim 2, characterized in that: The preparation method of the modified nano-titanium dioxide further includes: adding 6-10g of the intermediate product and 15-25g of γ-glycidyloxypropyltrimethoxysilane to 120-150ml of 85%-90wt% ethanol aqueous solution, reacting at 65-72°C under nitrogen protection for 4-6h, separating the solid product, washing it 2-4 times with anhydrous ethanol at a ratio of 1g / 2-4ml, and vacuum drying it at 42-48°C for 8-12h to obtain the product.

6. The antibacterial nylon spinning oil according to claim 1, characterized in that: The smoothing agent comprises, by weight, 67-73 parts of mineral oil, 11-15 parts of pentaerythritol oleate, 2-3 parts of modified nano-silicon dioxide, and 0.1-0.2 parts of a polyurea-based compound.

7. The antibacterial nylon spinning oil according to claim 1, characterized in that: The emulsifier is composed of 4-7 parts of trioctylamine and 15-20 parts of any one selected from fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, and sorbitan fatty acid ester.

8. The antibacterial nylon spinning oil according to claim 1, characterized in that: The antistatic agent is any one of isomeric tridecyl alcohol ether phosphate, lauryl phosphate potassium salt, and alkyl phosphate diethanolamine salt.

9. The method for preparing the antibacterial nylon spinning oil according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: weighing each component by weight, stirring and dispersing a portion of the emulsifier and modified nano zinc oxide particles to form a mixed dispersion, then sequentially adding a smoothing agent, an antistatic agent and trioctylamine, and then reacting at a temperature of 40-45° C. and a stirring rate of 50-70 r / min for 2-3 hours to obtain the obtained product.

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