Layered composite fabric based on waterproof and weather-resistant coating, preparation method and application

Abstract

The invention relates to the technical field of layered composite fabrics, in particular to a layered composite fabric based on a waterproof and weather-resistant coating, a preparation method and application. The layered composite fabric comprises an outer-layer fabric and an inner-layer fabric, the inner-layer fabric is a bamboo cotton fabric, the outer-layer fabric is a nylon fabric with a waterproof and weather-resistant coating, and the nylon fabric with the waterproof and weather-resistant coating is prepared by dipping a bio-based nylon fabric in a composite finishing agent and curing the bio-based nylon fabric. The composite finishing agent is prepared by the following steps: carrying out a reaction on diisocyanate, polyether polyol, bio-based polyester polyol and hydroxyl-terminated polydimethylsiloxane in N, N-dimethylacetamide, so as to prepare a polyurethane prepolymer solution; n-octadecyl diethanolamine is added for a chain extension reaction; n-butyl bromide is added, and quaternization reaction is carried out; and finally, adding the composite weather-resistant auxiliary agent, and stirring to obtain the composite finishing agent.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of layered composite fabric, in particular to a layered composite fabric based on waterproof and weather-resistant coating, a preparation method and application. BACKGROUND

[0002] With the development of economy, people have higher and higher functional requirements for clothing. Among them, outdoor sports clothing inevitably faces the climate environment of sunlight, precipitation, snowfall, etc. In order to protect the safety and comfort of the athletes, the waterproof performance and weather resistance of the fabric have higher requirements.

[0003] Chinese patent CN118418563B discloses a nylon bio-based composite double-layer fabric, a preparation method thereof and a waterproof and moisture-permeable fabric. In the preparation of the base material nylon bio-based polyurethane liquefied resin, the bio-based nylon 510 master batch is processed into a film after melting and liquefaction. After the organic combination of nylon bio-based and related materials, the fabric has excellent weather resistance. The addition of a fluorine-free waterproof additive based on natural palm oil and its derivatives improves the waterproofness of the fabric. However, the waterproof performance and weather resistance of the fabric are limited and need to be improved.

[0004] In addition, when in a complex outdoor environment, the antibacterial performance of the fabric also needs to be improved to further protect the safety of the athletes. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a layered composite fabric based on waterproof and weather-resistant coating to solve the problem that the waterproof performance, weather resistance and antibacterial performance of the fabric in the prior art need to be improved.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows: A preparation method of a layered composite fabric based on waterproof and weather-resistant coating, comprising the following steps: Step one, the bio-based nylon fabric is immersed in a composite finishing agent for treatment, and after immersion, it is solidified, washed, and dried to obtain a nylon fabric with a waterproof and weather-resistant coating; The composite finishing agent is prepared by the following steps: S1, diisocyanate, polyether polyol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane are added to N,N-dimethylacetamide, reacted, and after the reaction is completed, a polyurethane prepolymer solution is obtained; S2, N-octadecyl diethanolamine is added to the polyurethane prepolymer solution, reacted, and after the reaction is completed, bromo-n-butane is added dropwise, and after the dropwise addition is completed, the reaction is continued, and after the reaction is completed, a polyurethane mixture is obtained; S3, adding a composite weather-resistant additive to the polyurethane mixed solution, stirring, to obtain a composite finishing agent; Step two, the nylon fabric with waterproof and weather-resistant coating is used as the outer layer fabric, and the bamboo-cotton fabric is used as the inner layer fabric, and the outer layer fabric and the inner layer fabric are compounded to obtain a layered composite fabric based on the waterproof and weather-resistant coating.

[0007] Preferably, in the step one, the mass ratio of the bio-based nylon fabric to the composite finishing agent is 1:(15-25), the dipping treatment is carried out at room temperature, two-dip-two-rolling is adopted, the liquid rate is 90%, and the curing conditions are first heating and curing at a temperature of 80-90℃ for 3-5min, and then heating and curing at a temperature of 140-150℃ for 3-5min.

[0008] Preferably, the bio-based nylon fabric is prepared by the following steps: The bio-based nylon is melted, the melt is spun through a spinneret, side-blowing air cooling is carried out, drawing and winding are carried out, and a bio-based nylon fiber is obtained. The melting temperature is 270-280℃, the pressure of the spinneret is 15-18MPa, the wind speed of the side-blowing air is 0.38m / s, the temperature of the side-blowing air is 15-20℃, the oiling rate is 1.6%-1.8%, the drawing multiple is 1-1.2 times, and the winding speed is 4800-5000m / min. The bio-based nylon fiber is spun into a bio-based nylon yarn, the bio-based nylon yarn is spun into a fabric through a knitting process, and a bio-based nylon fabric is obtained. The gram weight of the bio-based nylon fabric is 200g / m 2 .

[0009] Preferably, in the step one, when preparing the composite finishing agent, in S1, the molar ratio of the diisocyanate, the polyether polyol, the bio-based polyester polyol, and the hydroxyl-terminated polydimethylsiloxane is (1.5-2.5):(0.4-0.6):(0.4-0.6):(0.2-0.3), the addition amount of N,N-dimethylacetamide is 10-15 times the mass of the diisocyanate, the polyether polyol, the bio-based polyester polyol, and the hydroxyl-terminated polydimethylsiloxane, and the reaction conditions are that the reaction is carried out at a temperature of 70-80℃ for 2-4h.

[0010] Preferably, the diisocyanate includes hexamethylene diisocyanate; The polyether polyol includes polyoxypropylene glycol; The bio-based polyester polyol is prepared by the following steps: (1) mixing a bio-based dihydric alcohol and a dibasic acid, and reacting at a temperature of 130-190℃ under a pressure of 0.03-0.1MPa until the acid value of the reaction mixture is ≤1mgKOH / g; (2) adding a catalyst, keeping the temperature at 190-210℃ until the acid value of the reaction mixture is less than 0.3 mgKOH / g, and then removing the water produced in the esterification reaction by vacuum distillation at a temperature of 120-140℃ and a pressure of 0.07-0.09 MPa to obtain a bio-based polyester polyol.

[0011] Preferably, in the step of preparing the composite finishing agent, in S2, the mass ratio of the polyurethane prepolymer solution to N-octadecyl diethanolamine is 100:(0.5-1), the molar ratio of brominated n-butane to N-octadecyl diethanolamine is 1:1, and the reaction conditions are 6-8 h at a temperature of 60-70℃, and the continuous reaction conditions are 2-3 h at a temperature of 80-100℃.

[0012] Preferably, in the step of preparing the composite finishing agent, in S3, the mass ratio of the polyurethane mixed solution to the composite weather-resistant additive is 100:(0.5-1), and the stirring conditions are 1-2 h at a stirring speed of 800-1200 r / min.

[0013] Preferably, the composite weather-resistant additive is prepared by the following steps: A. adding 1,18-octadecanediamine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, and triethylamine into N,N-dimethylformamide, reacting, precipitating after the reaction, filtering, and drying to obtain a modified hindered phenolic compound; B. adding the modified hindered phenolic compound into N,N-dimethylformamide, adding isocyanate nano zinc oxide, reacting, centrifuging and washing after the reaction, and drying to obtain the composite weather-resistant additive.

[0014] Preferably, in A, the molar ratio of 1,18-octadecanediamine to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride is 1:1, the amount of triethylamine added is 4%-8% of the mass sum of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, the amount of N,N-dimethylformamide added is 5-10 times the mass sum of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, and the reaction conditions are 20-30 h at a temperature of 50-70℃ in a nitrogen atmosphere.

[0015] Preferably, in B, the mass ratio of the modified hindered phenolic compound, isocyanate nano zinc oxide, and N,N-dimethylformamide is 54.5:(87.5-90.8):(500-800), and the reaction conditions are 3-5 h at room temperature.

[0016] Preferably, the isocyanate nano zinc oxide is prepared by the following steps: The nano zinc oxide is added into N,N-dimethylformamide, ultrasonic dispersion is carried out, then diisocyanate is added, ultrasonic dispersion is continuously carried out, then reaction is carried out, after the reaction is completed, centrifugal washing and drying are carried out, and isocyanate nano zinc oxide is obtained; The mass ratio of the nano zinc oxide, N,N-dimethylformamide and diisocyanate is 8:(80-120):(6-10), and the reaction condition is that the reaction is carried out at 80-90 DEG C for 20-30 hours.

[0017] Preferably, the diisocyanate comprises isophorone diisocyanate.

[0018] Preferably, the preparation raw material of the bamboo cotton fabric in the second step comprises bamboo fiber, cotton fiber and spandex fiber.

[0019] The application further discloses a waterproof and weather-resistant coating-based layered composite fabric prepared by the preparation method.

[0020] The application further discloses an application of the waterproof and weather-resistant coating-based layered composite fabric.

[0021] Preferably, the application comprises an application on outdoor sportswear.

[0022] Compared with the prior art, the application has the following beneficial effects: The composite fabric comprises an outer fabric and an inner fabric, the inner fabric is a bamboo cotton fabric, is soft and skin-friendly, and the bamboo fiber can improve the antibacterial performance of the inner fabric; the outer fabric is a nylon fabric, has good wear resistance, and a coating is formed on the nylon fabric through impregnation and solidification of the composite finishing agent, so that the waterproof performance and the weather resistance of the nylon fabric are effectively improved; and the preparation raw material of the nylon fabric is bio-based nylon, so that the use of the bio-based material can effectively reduce the use of non-renewable petroleum chemical materials. In the application, the diisocyanate, the polyether polyol, the bio-based polyester polyol and the hydroxyl-terminated polydimethylsiloxane are reacted in an organic solvent to prepare a polyurethane prepolymer solution, the organic silicon molecular chain introduced by the hydroxyl-terminated polydimethylsiloxane can effectively improve the hydrophobicity of the finishing agent and also improve the softness of the coating; the N-octadecyl diethanolamine is used as a chain extender to react with the polyurethane prepolymer, so that the molecular weight of the polyurethane is increased, the alkyl chain introduced by the N-octadecyl diethanolamine can also improve the hydrophobicity of the polyurethane, the improvement of the hydrophobicity of the polyurethane can effectively improve the waterproof performance of the nylon fabric after the coating is formed; in addition, the tertiary amine group introduced by the N-octadecyl diethanolamine reacts with n-bromobutane to generate a quaternary ammonium salt, so that the antibacterial performance of the polyurethane is improved; the composite weather resistance additive is introduced into the polyurethane, so that the weather resistance of the polyurethane is effectively improved. The composite weather-resistant additive in the application is composed of an organic weather-resistant component and an inorganic weather-resistant component, the organic weather-resistant component is a hindered phenol compound, the inorganic weather-resistant component is nano zinc oxide, the hindered phenol compound is obtained by the reaction of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride and the amino group at one end of the molecular chain of 1,18-octadecanediamine, the modified hindered phenol compound is obtained by the reaction of the amino group at the other end of the molecular chain of 1,18-octadecanediamine and isocyanate nano zinc oxide, not only the chemical bonding of the organic weather-resistant component and the inorganic weather-resistant component is realized, but also the compatibility between the weather-resistant component and the polyurethane matrix is improved through the entanglement between the alkyl chain and the polyurethane molecular chain, the weather-resistant performance is good, and the hydrophobicity of the polyurethane is further improved through the alkyl chain introduced by 1,18-octadecanediamine. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 It is a reaction schematic diagram for preparing the modified hindered phenol compound by the reaction of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in Example 4 of the application; Figure 2 It is a reaction schematic diagram for preparing the composite weather-resistant additive by the reaction of the modified hindered phenol compound and isocyanate nano zinc oxide in Example 4 of the application; Figure 3 It is a determination result diagram of the waterproof performance of the nylon fabric with a waterproof and weather-resistant coating prepared in Examples 4-6 and Comparative Examples 1-3 of the application; Figure 4 It is a determination result diagram of the antibacterial performance of the nylon fabric with a waterproof and weather-resistant coating prepared in Examples 4-6 and Comparative Examples 1-3 of the application; Figure 5 It is a determination result diagram of the weather-resistant performance of the composite finishing agent prepared in Examples 4-6 and Comparative Examples 1-3 of the application. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, but not all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0025] Example 1 The embodiment discloses a preparation method of a bio-based nylon fabric, comprising the following steps: The bio-based nylon is melted, the melt is spun through a spinneret, side blowing air cooling, drafting and winding to obtain bio-based nylon fibers; The melt temperature is 275℃, the pressure of the spinneret is 16 MPa, the air speed of the side blowing is 0.38 m / s, the temperature of the side blowing is 20℃, the oiling rate is 1.8%, the draw ratio is 1.2 times, and the winding speed is 5000 m / min. The bio-based nylon fiber is spun into a bio-based nylon yarn, the yarn count of the bio-based nylon yarn is 40S, the bio-based nylon yarn is spun into a fabric through a knitting process to obtain a bio-based nylon fabric, and the grammage of the bio-based nylon fabric is 200 g / m 2 .

[0026] Example 2 The embodiment discloses a preparation method of a bio-based polyester polyol, and comprises the following steps: (1) bio-based 1,4-butanediol and 1,6-hexanedioic acid are mixed, the molar ratio of bio-based 1,4-butanediol and 1,6-hexanedioic acid is 1.3:1, and the reaction is carried out at 180℃ under a pressure of 0.08 MPa; the acid value of the reaction mixture is determined by sampling every 30 min until the acid value of the reaction mixture is ≤1 mgKOH / g (the acid value of the reaction mixture is specifically 0.9 mgKOH / g); (2) bio-based 1,4-butanediol and 1,6-hexanedioic acid with a mass of 0.2% stannous octoate are added, and the reaction is carried out at 200℃; the acid value of the reaction mixture is determined by sampling every 30 min until the acid value of the reaction mixture is <0.3 mgKOH / g (the acid value of the reaction mixture is specifically 0.2 mgKOH / g); after the reaction is completed, the water generated in the esterification reaction is removed by vacuum distillation at 130℃ under a pressure of 0.08 MPa to obtain a bio-based polyester polyol; The number average molecular weight of the bio-based polyester polyol is measured by SEC-MALLS method (molecular exclusion chromatography and multi-angle laser light scattering method) to be 600 g / mol.

[0027] Example 3 The embodiment discloses a preparation method of isocyanate-modified nano zinc oxide, comprising the following steps: Nano zinc oxide is added into N,N-dimethylformamide, ultrasonic dispersion is carried out for 2 h under a frequency of 50 kHz, isophorone diisocyanate is added, the mass ratio of nano zinc oxide, N,N-dimethylformamide and isophorone diisocyanate is 8:100:8, ultrasonic dispersion is continued for 30 min under a frequency of 50 kHz, and reaction is carried out at 85℃ for 24 h; after the reaction is completed, the isocyanate-modified nano zinc oxide is washed with N,N-dimethylformamide for 3 times by centrifugation and dried in a vacuum drying oven at 80℃ until the weight is constant.

[0028] Example 4 The embodiment discloses a preparation method of a layered composite fabric based on a waterproof and weather-resistant coating, and comprises the following steps: Step one, the bio-based nylon fabric prepared in embodiment 1 is placed in a composite finishing agent, the mass ratio of the bio-based nylon fabric to the composite finishing agent is 1:15, and the dipping treatment is carried out at room temperature, two dipping and two rolling are carried out, the liquid carrying rate is 90%, after the dipping is completed, heating and curing are first carried out at 80 DEG C for 5 min, and then heating and curing are carried out at 140 DEG C for 5 min, after washing with ethanol, natural air drying is carried out, and the nylon fabric with the waterproof and weather-resistant coating is obtained; The composite finishing agent is prepared by the following steps: S1, hexamethylene diisocyanate, polyoxypropylene glycol, bio-based polyester polyol prepared in embodiment 2, and hydroxyl-terminated polydimethylsiloxane are added into N,N-dimethylacetamide, the molar ratio of hexamethylene diisocyanate, polyoxypropylene glycol, bio-based polyester polyol and hydroxyl-terminated polydimethylsiloxane is 1.5:0.4:0.4:0.2, the addition amount of N,N-dimethylacetamide is 10 times the mass sum of hexamethylene diisocyanate, polyoxypropylene glycol, bio-based polyester polyol and hydroxyl-terminated polydimethylsiloxane, and reaction is carried out at 70 DEG C for 4 h, after the reaction is completed, a polyurethane prepolymer solution is obtained; S2, N-octadecyl diethanolamine is added into the polyurethane prepolymer solution, the mass ratio of the polyurethane prepolymer solution to N-octadecyl diethanolamine is 100:0.5, reaction is carried out at 60 DEG C for 8 h, after the reaction is completed, bromo-n-butane is added dropwise, the molar ratio of bromo-n-butane to N-octadecyl diethanolamine is 1:1, after the dropwise addition is completed, reaction is continued at 80 DEG C for 3 h, after the reaction is completed, a polyurethane mixture is obtained; S3, a composite weather-resistant additive is added into the polyurethane mixture, the mass ratio of the polyurethane mixture to the composite weather-resistant additive is 100:0.5, stirring is carried out at a speed of 800 r / min for 2 h, and a composite finishing agent is obtained; The composite weather-resistant additive is prepared by the following steps: A, 1,18-octadecanediamine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine are added into N,N-dimethylformamide, the molar ratio of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1:1, the amount of triethylamine added is 4% of the mass sum of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, N,N-dimethylformamide is added in an amount of 5 times the mass sum of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, the reaction is carried out under a nitrogen atmosphere at a temperature of 50°C for 30h, after the reaction is completed, deionized water in an amount of 5 times the mass of N,N-dimethylformamide is added to precipitate, the precipitate is filtered and dried to constant weight in a vacuum drying oven at 25°C to obtain a modified hindered phenolic compound; B, the modified hindered phenolic compound is added into N,N-dimethylformamide, the isocyanate nano zinc oxide prepared in Example 3 is added, the mass ratio of the modified hindered phenolic compound, the isocyanate nano zinc oxide and N,N-dimethylformamide is 54.5:87.5:500, the reaction is carried out at room temperature for 3h, after the reaction is completed, the product is washed by centrifugation with ethanol for 3 times, and then dried to constant weight in a vacuum drying oven at 50°C to obtain a composite weather-resistant additive; Step two, the nylon fabric with a waterproof and weather-resistant coating is used as an outer layer fabric, the bamboo cotton fabric is used as an inner layer fabric, and the outer layer fabric and the inner layer fabric are sewn together by polyester threads to obtain a layered composite fabric based on a waterproof and weather-resistant coating.

[0029] Example 5 The embodiment discloses a preparation method of a layered composite fabric based on a waterproof and weather-resistant coating, comprising the following steps: Step one, the bio-based nylon fabric prepared in Example 1 is placed in a composite finishing agent, the mass ratio of the bio-based nylon fabric and the composite finishing agent is 1:25, and the bio-based nylon fabric is subjected to immersion treatment at room temperature, two immersions and two rollings, and the liquid retention rate is 90%, after the immersion is completed, the bio-based nylon fabric is first heated and solidified at a temperature of 90°C for 3 minutes, and then heated and solidified at a temperature of 150°C for 3 minutes, and then washed with ethanol and naturally air-dried to obtain a nylon fabric with a waterproof and weather-resistant coating; The composite finishing agent is prepared by the following steps: S1, hexamethylene diisocyanate, polypropylene glycol, the bio-based polyester polyol prepared in Example 2, and hydroxyl-terminated polydimethylsiloxane were added to N,N-dimethylacetamide. The molar ratio of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane was 2.5:0.6:0.6:0.3. The amount of N,N-dimethylacetamide added was 15 times the total mass of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane. The reaction was carried out at 80°C for 2 hours. After the reaction was completed, a polyurethane prepolymer solution was obtained. S2. Add N-octadecyl diethanolamine to the polyurethane prepolymer solution. The mass ratio of polyurethane prepolymer solution to N-octadecyl diethanolamine is 100:1. React at 70℃ for 6 hours. After the reaction is complete, add n-bromobutane dropwise. The molar ratio of n-bromobutane to N-octadecyl diethanolamine is 1:1. After the addition is complete, continue the reaction at 100℃ for 2 hours. After the reaction is complete, a polyurethane mixture is obtained. S3. Add composite weather-resistant additives to the polyurethane mixture. The mass ratio of polyurethane mixture to composite weather-resistant additives is 100:1. Stir at 1200 r / min for 1 h to obtain composite finishing agent. The composite weather-resistant additive is prepared by the following steps: A. 1,18-octadecanediamine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, and triethylamine were added to N,N-dimethylformamide. The molar ratio of 1,18-octadecanediamine to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was 1:1. The amount of triethylamine added was 8% of the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The amount of N,N-dimethylformamide added was 10 times the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The reaction was carried out under a nitrogen atmosphere at 70°C for 20 hours. After the reaction was completed, 5 times the mass of deionized water was added to precipitate the product. The precipitate was filtered and dried in a vacuum drying oven at 25°C until constant weight to obtain the modified hindered phenol compound. B. Add the modified hindered phenolic compound to N,N-dimethylformamide, and add the isocyanate-modified nano zinc oxide prepared in Example 3. The mass ratio of the modified hindered phenolic compound, the isocyanate-modified nano zinc oxide, and N,N-dimethylformamide is 54.5:90.8:800. React at room temperature for 5 hours. After the reaction is complete, wash three times with ethanol by centrifugation and dry in a vacuum drying oven at 50°C until constant weight to obtain the composite weather-resistant additive. Step 2: Use nylon fabric with a waterproof and weather-resistant coating as the outer layer and bamboo cotton fabric as the inner layer. Sew the outer and inner layers together with polyester thread in equal areas to obtain a layered composite fabric based on the waterproof and weather-resistant coating.

[0030] Example 6 This embodiment discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps: Step 1: Place the bio-based nylon fabric obtained in Example 1 into a composite finishing agent. The mass ratio of the bio-based nylon fabric to the composite finishing agent is 1:20. Impregnate the fabric at room temperature, performing two dips and two nips with a liquid retention rate of 90%. After impregnation, heat and cure the fabric at 85°C for 4 minutes, then heat and cure it at 145°C for 4 minutes. After washing with ethanol, air dry the fabric to obtain a nylon fabric with a waterproof and weather-resistant coating. The composite finishing agent is prepared by the following steps: S1, hexamethylene diisocyanate, polypropylene glycol, the bio-based polyester polyol prepared in Example 2, and hydroxyl-terminated polydimethylsiloxane were added to N,N-dimethylacetamide. The molar ratio of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane was 2:0.5:0.5:0.25. The amount of N,N-dimethylacetamide added was 12 times the total mass of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane. The reaction was carried out at 75°C for 3 hours. After the reaction was completed, a polyurethane prepolymer solution was obtained. S2. Add N-octadecyl diethanolamine to the polyurethane prepolymer solution. The mass ratio of polyurethane prepolymer solution to N-octadecyl diethanolamine is 100:0.8. React at 65℃ for 7 hours. After the reaction is complete, add n-bromobutane dropwise. The molar ratio of n-bromobutane to N-octadecyl diethanolamine is 1:1. After the addition is complete, continue the reaction at 90℃ for 2.5 hours. After the reaction is complete, a polyurethane mixture is obtained. S3. Add composite weather-resistant additives to the polyurethane mixture. The mass ratio of polyurethane mixture to composite weather-resistant additives is 100:0.8. Stir at 1000 r / min for 1.5 h to obtain composite finishing agent. The composite weather-resistant additive is prepared by the following steps: A. 1,18-octadecanediamine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, and triethylamine were added to N,N-dimethylformamide. The molar ratio of 1,18-octadecanediamine to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was 1:1. The amount of triethylamine added was 6% of the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, and the amount of N,N-dimethylformamide added was 8 times the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The reaction was carried out under a nitrogen atmosphere at 60°C for 24 hours. After the reaction was completed, 5 times the mass of deionized water was added to precipitate the product. The precipitate was filtered and dried in a vacuum drying oven at 25°C until constant weight to obtain the modified hindered phenol compound. B. Add the modified hindered phenolic compound to N,N-dimethylformamide, and add the isocyanate-modified nano zinc oxide prepared in Example 3. The mass ratio of the modified hindered phenolic compound, the isocyanate-modified nano zinc oxide, and N,N-dimethylformamide is 54.5:89.2:650. React at room temperature for 4 hours. After the reaction is complete, wash three times with ethanol by centrifugation and dry in a vacuum drying oven at 50°C until constant weight to obtain the composite weather-resistant additive. Step 2: Use nylon fabric with a waterproof and weather-resistant coating as the outer layer and bamboo cotton fabric as the inner layer. Sew the outer and inner layers together with polyester thread in equal areas to obtain a layered composite fabric based on the waterproof and weather-resistant coating.

[0031] Comparative Example 1 This comparative example discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps: Step 1: Place the bio-based nylon fabric obtained in Example 1 into a composite finishing agent. The mass ratio of the bio-based nylon fabric to the composite finishing agent is 1:15. Impregnate the fabric at room temperature, performing two dips and two nips with a liquid retention rate of 90%. After impregnation, heat and cure the fabric at 80°C for 5 minutes, then heat and cure it at 140°C for 5 minutes. After washing with ethanol, air dry the fabric to obtain a nylon fabric with a waterproof and weather-resistant coating. The composite finishing agent is prepared by the following steps: S1, hexamethylene diisocyanate, polypropylene glycol, the bio-based polyester polyol prepared in Example 2, and hydroxyl-terminated polydimethylsiloxane were added to N,N-dimethylacetamide. The molar ratio of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane was 1.5:0.4:0.4:0.2. The amount of N,N-dimethylacetamide added was 10 times the total mass of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane. The reaction was carried out at 70°C for 4 hours. After the reaction was completed, a polyurethane prepolymer solution was obtained. S2. Add N-octadecyl diethanolamine to the polyurethane prepolymer solution. The mass ratio of the polyurethane prepolymer solution to N-octadecyl diethanolamine is 100:0.5. React at 60°C for 8 hours. After the reaction is completed, a polyurethane mixture is obtained. S3. Add composite weather-resistant additives to the polyurethane mixture. The mass ratio of polyurethane mixture to composite weather-resistant additives is 100:0.5. Stir at 800 r / min for 2 h to obtain composite finishing agent. The composite weather-resistant additive is prepared by the following steps: A. 1,18-octadecanediamine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, and triethylamine were added to N,N-dimethylformamide. The molar ratio of 1,18-octadecanediamine to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was 1:1. The amount of triethylamine added was 4% of the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The amount of N,N-dimethylformamide added was 5 times the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The reaction was carried out in a nitrogen atmosphere at 50°C for 30 hours. After the reaction was completed, 5 times the mass of deionized water was added to precipitate the product. The precipitate was filtered and dried in a vacuum drying oven at 25°C until constant weight to obtain the modified hindered phenol compound. B. Add the modified hindered phenolic compound to N,N-dimethylformamide, and add the isocyanate-modified nano zinc oxide prepared in Example 3. The mass ratio of the modified hindered phenolic compound, isocyanate-modified nano zinc oxide, and N,N-dimethylformamide is 54.5:87.5:500. React at room temperature for 3 hours. After the reaction is complete, wash three times with ethanol by centrifugation and dry in a vacuum drying oven at 50°C until constant weight to obtain the composite weather-resistant additive. Step 2: Use nylon fabric with a waterproof and weather-resistant coating as the outer layer and bamboo cotton fabric as the inner layer. Sew the outer and inner layers together with polyester thread in equal areas to obtain a layered composite fabric based on the waterproof and weather-resistant coating.

[0032] Comparative Example 2 This comparative example discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps: Step 1: Place the bio-based nylon fabric obtained in Example 1 into a composite finishing agent. The mass ratio of the bio-based nylon fabric to the composite finishing agent is 1:15. Impregnate the fabric at room temperature, performing two dips and two nips with a liquid retention rate of 90%. After impregnation, heat and cure the fabric at 80°C for 5 minutes, then heat and cure it at 140°C for 5 minutes. After washing with ethanol, air dry the fabric to obtain a nylon fabric with a waterproof and weather-resistant coating. The composite finishing agent is prepared by the following steps: S1, hexamethylene diisocyanate, polypropylene glycol, the bio-based polyester polyol prepared in Example 2, and hydroxyl-terminated polydimethylsiloxane were added to N,N-dimethylacetamide. The molar ratio of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane was 1.5:0.4:0.4:0.2. The amount of N,N-dimethylacetamide added was 10 times the total mass of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane. The reaction was carried out at 70°C for 4 hours. After the reaction was completed, a polyurethane prepolymer solution was obtained. S2. Add 1,4-butanediol to the polyurethane prepolymer solution. The mass ratio of polyurethane prepolymer solution to 1,4-butanediol is 100:0.13. React at 60°C for 8 hours. After the reaction is completed, a polyurethane mixture is obtained. S3. Add composite weather-resistant additives to the polyurethane mixture. The mass ratio of polyurethane mixture to composite weather-resistant additives is 100:0.5. Stir at 800 r / min for 2 h to obtain composite finishing agent. The composite weather-resistant additive is prepared by the following steps: A. 1,18-octadecanediamine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, and triethylamine were added to N,N-dimethylformamide. The molar ratio of 1,18-octadecanediamine to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was 1:1. The amount of triethylamine added was 4% of the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The amount of N,N-dimethylformamide added was 5 times the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The reaction was carried out in a nitrogen atmosphere at 50°C for 30 hours. After the reaction was completed, 5 times the mass of deionized water was added to precipitate the product. The precipitate was filtered and dried in a vacuum drying oven at 25°C until constant weight to obtain the modified hindered phenol compound. B. Add the modified hindered phenolic compound to N,N-dimethylformamide, and add the isocyanate-modified nano zinc oxide prepared in Example 3. The mass ratio of the modified hindered phenolic compound, isocyanate-modified nano zinc oxide, and N,N-dimethylformamide is 54.5:87.5:500. React at room temperature for 3 hours. After the reaction is complete, wash three times with ethanol by centrifugation and dry in a vacuum drying oven at 50°C until constant weight to obtain the composite weather-resistant additive. Step 2: Use nylon fabric with a waterproof and weather-resistant coating as the outer layer and bamboo cotton fabric as the inner layer. Sew the outer and inner layers together with polyester thread in equal areas to obtain a layered composite fabric based on the waterproof and weather-resistant coating.

[0033] Comparative Example 3 This comparative example discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps: Step 1: Place the bio-based nylon fabric obtained in Example 1 into a composite finishing agent. The mass ratio of the bio-based nylon fabric to the composite finishing agent is 1:15. Impregnate the fabric at room temperature, performing two dips and two nips with a liquid retention rate of 90%. After impregnation, heat and cure the fabric at 80°C for 5 minutes, then heat and cure it at 140°C for 5 minutes. After washing with ethanol, air dry the fabric to obtain a nylon fabric with a waterproof and weather-resistant coating. The composite finishing agent is prepared by the following steps: S1, hexamethylene diisocyanate, polypropylene glycol, the bio-based polyester polyol prepared in Example 2, and hydroxyl-terminated polydimethylsiloxane were added to N,N-dimethylacetamide. The molar ratio of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane was 1.5:0.4:0.4:0.2. The amount of N,N-dimethylacetamide added was 10 times the total mass of hexamethylene diisocyanate, polypropylene glycol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane. The reaction was carried out at 70°C for 4 hours. After the reaction was completed, a polyurethane prepolymer solution was obtained. S2. Add N-octadecyl diethanolamine to the polyurethane prepolymer solution. The mass ratio of polyurethane prepolymer solution to N-octadecyl diethanolamine is 100:0.5. React at 60℃ for 8 hours. After the reaction is complete, add n-bromobutane dropwise. The molar ratio of n-bromobutane to N-octadecyl diethanolamine is 1:1. After the addition is complete, continue the reaction at 80℃ for 3 hours. After the reaction is complete, a polyurethane mixture is obtained. S3. Add composite weather-resistant additives to the polyurethane mixture. The mass ratio of polyurethane mixture to composite weather-resistant additives is 100:0.45. Stir at 800 r / min for 2 h to obtain composite finishing agent. The composite weather-resistant additive is prepared by the following steps: A. Add nano zinc oxide to a 95wt% ethanol aqueous solution and ultrasonically disperse it at a frequency of 50kHz for 30min. Then add γ-aminopropyltriethoxysilane (silane coupling agent KH550). The mass ratio of nano zinc oxide, 95wt% ethanol aqueous solution and γ-aminopropyltriethoxysilane is 10:250:10. React at 75℃ for 6h. After the reaction is completed, filter, rinse with ethanol 3 times, and dry in a vacuum drying oven at 45℃ to constant weight to obtain amino-modified nano zinc oxide. B. Amino-modified nano zinc oxide, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, and triethylamine were added to N,N-dimethylformamide. The mass ratio of amino-modified nano zinc oxide to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was 87.5:10. The amount of triethylamine added was 4% of the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The amount of N,N-dimethylformamide added was 5 times the total mass of amino-modified nano zinc oxide and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The reaction was carried out in a nitrogen atmosphere at 50°C for 30 hours. After the reaction was completed, the mixture was washed three times by centrifugation with ethanol and dried in a vacuum drying oven at 50°C until constant weight to obtain a composite weather-resistant additive. Step 2: Use nylon fabric with a waterproof and weather-resistant coating as the outer layer and bamboo cotton fabric as the inner layer. Sew the outer and inner layers together with polyester thread in equal areas to obtain a layered composite fabric based on the waterproof and weather-resistant coating.

[0034] In the above embodiments and comparative examples, the bio-based nylon was bio-based nylon PA56; the particle size of the nano zinc oxide was 200 nm; the polypropylene glycol was PPG-400 with a molecular weight of 400; the bamboo cotton fabric contained 67% bamboo fiber, 28% cotton fiber, and 5% spandex fiber, with a weight of 180 g / m². 2 The yarn count is 40s.

[0035] Test case (1) Waterproof performance: The static water contact angle of the nylon fabric samples with waterproof and weather-resistant coatings prepared in Examples 4-6 and Comparative Examples 1-3 was measured using an optical contact angle meter. The results are shown in Table 1. Table 1

[0036] As shown in Table 1, the nylon fabric with a waterproof and weather-resistant coating obtained by this invention has good waterproof performance. In this invention, during the preparation of the composite finishing agent, the organosilicon molecular chain introduced by hydroxyl-terminated polydimethylsiloxane effectively improves the hydrophobicity of the finishing agent. N-octadecyldiethanolamine, as a chain extender, also improves the hydrophobicity of the finishing agent. In the preparation of the composite weather-resistant additive, 1,18-octadecyldiamine, as a crosslinking agent between the organic and inorganic weather-resistant components, further improves the hydrophobicity of the polyurethane. Compared with Example 4, in Comparative Example 2, the chain extender was replaced by 1,4-butanediol, lacking the hydrophobic effect of the alkyl chain, resulting in a decrease in the hydrophobic performance of the finishing agent. In Comparative Example 2, 1,18-octadecyldiamine was not introduced during the preparation of the composite weather-resistant additive, and the hydrophobic performance of the finishing agent also decreased.

[0037] (2) Antibacterial properties: The antibacterial rate of the nylon fabric samples with waterproof and weather-resistant coatings prepared in Examples 4-6 and Comparative Examples 1-3 was determined according to the standard FZ / T73023-2006 "Antibacterial Knitted Fabrics" after 50 washes. The results are shown in Table 2. Table 2

[0038] As shown in Table 2, the nylon fabric with a waterproof and weather-resistant coating obtained by this invention exhibits excellent antibacterial properties. In the preparation of the composite finishing agent, the tertiary amine group introduced by the chain extender N-octadecyl diethanolamine reacts with bromobutane to generate a quaternary ammonium salt, which effectively improves the antibacterial properties of polyurethane. The inorganic weather-resistant component, nano-zinc oxide, also possesses good antibacterial properties. Furthermore, the nano-zinc oxide can enhance its compatibility with the polyurethane matrix through the entanglement between the alkyl chains introduced when bonding with the organic weather-resistant component and the polyurethane molecular chains, further improving its antibacterial performance. Compared with Example 4, in Comparative Examples 1 and 2, no quaternization reaction was carried out during the preparation of the composite finishing agent, resulting in a decrease in antibacterial performance. In Comparative Example 3, during the preparation of the composite weather-resistant additive, no alkyl chain was introduced during the bonding process between 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride and nano zinc oxide, so it could not entangle with the polyurethane molecular chain. The compatibility between the nano zinc oxide in the weather-resistant component and the polyurethane matrix decreased, and it was easy to fall off from the polyurethane base coating during washing, resulting in a decrease in antibacterial performance.

[0039] (3) Weather resistance: The composite finishing agents prepared in Examples 4-6 and Comparative Examples 1-3 were injected into stainless steel molds and heated to cure and form a film material sample with a thickness of 50 μm. The tensile strength retention rate of the film material sample after thermo-oxidative aging at 140℃ for 500 h and the tensile strength retention rate after ultraviolet irradiation at UVA 340 nm for 500 h were measured. The results are shown in Table 3. Table 3

[0040] As shown in Table 3, the composite finishing agent prepared in this invention exhibits excellent weather resistance. The composite weather-resistant additive in this invention is composed of hindered phenolic compound 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride and nano-zinc oxide, possessing both UV resistance and thermo-oxidative aging resistance. 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride and nano-zinc oxide are linked by 1,18-octadecanediamine. The entanglement between the alkyl chain and the polyurethane molecular chain improves the compatibility between the weather-resistant component and the polyurethane matrix, resulting in good weather resistance. Compared to Example 4, in Comparative Example 3, during the preparation of the composite weather-resistant additive, no alkyl chain was introduced during the bonding process of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride and nano-zinc oxide. Therefore, it could not entangle with the polyurethane molecular chain, leading to decreased compatibility between the weather-resistant component and the polyurethane matrix, and consequently, decreased weather resistance.

[0041] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, characterized in that, Includes the following steps: Step 1: Impregnate the bio-based nylon fabric in a composite finishing agent. After impregnation, cure, wash, and dry to obtain a nylon fabric with a waterproof and weather-resistant coating. Among them, composite finishing agent It is prepared by the following steps: S1, diisocyanate, polyether polyol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane are added to N,N-dimethylacetamide and reacted. After the reaction is completed, a polyurethane prepolymer solution is obtained. S2. Add N-octadecyldiethanolamine to the polyurethane prepolymer solution and react. After the reaction is complete, add n-bromobutane dropwise. After the addition is complete, continue the reaction. After the reaction is complete, a polyurethane mixture is obtained. S3. Add composite weather-resistant additives to the polyurethane mixture and stir to obtain composite finishing agent; Step 2: Use nylon fabric with a waterproof and weather-resistant coating as the outer layer and bamboo cotton fabric as the inner layer. Combine the outer and inner layers to obtain a layered composite fabric based on the waterproof and weather-resistant coating.

2. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 1, characterized in that, In step one, the mass ratio of bio-based nylon fabric to composite finishing agent is 1:(15-25). The impregnation treatment is carried out at room temperature, with two dips and two nips, and the liquid retention rate is 90%. The curing conditions are to first heat and cure at 80-90℃ for 3-5 minutes, and then heat and cure at 140-150℃ for 3-5 minutes.

3. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 1, characterized in that, In step one, when preparing the composite finishing agent, in S1, the molar ratio of diisocyanate, polyether polyol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane is (1.5-2.5):(0.4-0.6):(0.4-0.6):(0.2-0.3), and the amount of N,N-dimethylacetamide added is 10-15 times the sum of the masses of diisocyanate, polyether polyol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane. The reaction conditions are to react at 70-80℃ for 2-4 hours. The diisocyanate includes hexamethylene diisocyanate; The polyether polyol includes polyoxypropylene glycol; The bio-based polyester polyol is prepared by the following steps: (1) Mix bio-based diols and diacids, and keep them at 0.03-0.1 MPa pressure and 130-190℃ temperature until the acid value of the reaction mixture is ≤1 mgKOH / g; (2) Add catalyst and keep the reaction at 190-210℃ until the acid value of the reaction mixture is <0.3mgKOH / g. After the reaction is completed, remove the water generated by the esterification reaction by vacuum distillation at 120-140℃ and 0.07-0.09MPa to obtain bio-based polyester polyol.

4. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 1, characterized in that, In step one, when preparing the composite finishing agent, in S2, the mass ratio of polyurethane prepolymer solution to N-octadecyl diethanolamine is 100:(0.5-1), the molar ratio of bromobutane to N-octadecyl diethanolamine is 1:1, the reaction conditions are to react at 60-70℃ for 6-8h, and to continue the reaction at 80-100℃ for 2-3h.

5. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 1, characterized in that, In step one, when preparing the composite finishing agent, in S3, the mass ratio of polyurethane mixture to composite weather-resistant additive is 100:(0.5-1), and the stirring conditions are stirring at a speed of 800-1200 r / min for 1-2 hours.

6. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 5, characterized in that, The composite weather-resistant additive is prepared by the following steps: A. Add 1,18-octadecanediamine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride and triethylamine to N,N-dimethylformamide and react. After the reaction is complete, the precipitate is obtained, filtered, and dried to obtain the modified hindered phenol compound. B. Add the modified hindered phenolic compound to N,N-dimethylformamide, add isocyanate-modified nano zinc oxide, react, centrifuge, wash, and dry to obtain the composite weather-resistant additive.

7. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 6, characterized in that, In step A, the molar ratio of 1,18-octadecanediamine to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride is 1:1; the amount of triethylamine added is 4%-8% of the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride; the amount of N,N-dimethylformamide added is 5-10 times the total mass of 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride; and the reaction conditions are: reaction under a nitrogen atmosphere at 50-70°C for 20-30 hours.

8. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 6, characterized in that, In step B, the mass ratio of the modified hindered phenolic compound, isocyanate-modified nano zinc oxide, and N,N-dimethylformamide is 54.5:(87.5-90.8):(500-800), and the reaction conditions are 3-5 hours at room temperature.

9. A layered composite fabric based on a waterproof and weather-resistant coating, prepared by the method for preparing a layered composite fabric based on a waterproof and weather-resistant coating as described in any one of claims 1-8.

10. An application of the layered composite fabric based on a waterproof and weather-resistant coating as described in claim 9.

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