A layered composite fabric based on a waterproof and weather-resistant coating, a preparation method and applications

Abstract

The present application relates to the technical field of layered composite fabric, and particularly relates to a layered composite fabric based on waterproof and weather-resistant coating, a preparation method and application. The layered composite fabric comprises an outer fabric and an inner fabric, the inner fabric is a bamboo cotton fabric, and the outer fabric is a nylon fabric with a waterproof and weather-resistant coating, which is prepared by impregnating treatment of a bio-based nylon fabric in a composite finishing agent and solidification. The composite finishing agent is prepared by the following steps: including the following method: reacting diisocyanate, polyether polyol, bio-based polyester polyol and hydroxyl-terminated polydimethylsiloxane in N,N-dimethylacetamide to obtain a polyurethane prepolymer solution; adding N-octadecyl diethanolamine for chain extension reaction; adding bromo-n-butane for quaternization reaction; and finally adding a composite weather-resistant additive, stirring to obtain the composite finishing agent.

Description

Technical Field

[0001] This invention relates to the field of layered composite fabric technology, specifically to a layered composite fabric based on a waterproof and weather-resistant coating, its preparation method, and its application. Background Technology

[0002] With economic development, people have increasingly higher requirements for the functionality of clothing. Among them, outdoor sportswear inevitably faces climatic environments such as sun exposure, precipitation, and snowfall. In order to ensure the safety and comfort of athletes, its fabrics have high requirements for waterproof performance and weather resistance.

[0003] Chinese patent CN118418563B discloses a nylon bio-based composite double-layer fabric, its preparation method, and a waterproof and breathable fabric. In this method, the bio-based nylon 510 masterbatch in the preparation raw material of the nylon bio-based polyurethane liquefied resin matrix material undergoes melt liquefaction processing to form a film. The organic combination of the nylon bio-based material and related materials gives the fabric excellent weather resistance. The waterproofness is further enhanced by adding an acrylic-based fluorine-free waterproofing agent made from natural palm oil and its derivatives. However, the fabric's waterproof and weather-resistant properties are limited and need further improvement.

[0004] In addition, when in complex outdoor environments, it is necessary to improve the antibacterial properties of the fabric to further ensure the safety of athletes. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a layered composite fabric based on a waterproof and weather-resistant coating, thereby solving the problem that the waterproof performance, weather resistance, and antibacterial properties of existing fabrics need to be improved.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a layered composite fabric based on a waterproof and weather-resistant coating includes the following steps:

[0008] 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.

[0009] The composite finishing agent is prepared by the following steps:

[0010] 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.

[0011] 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.

[0012] S3. Add composite weather-resistant additives to the polyurethane mixture and stir to obtain composite finishing agent;

[0013] 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.

[0014] Preferably, 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 rolls, the liquid retention rate is 90%, and 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.

[0015] Preferably, the bio-based nylon fabric is prepared by the following steps:

[0016] Bio-based nylon is melted, the melt is spun through a spinneret, cooled by side blowing, drawn and wound to obtain bio-based nylon fibers.

[0017] The melting temperature is 270-280℃, the spinneret pressure is 15-18MPa, the side air velocity is 0.38m / s, the side air temperature is 15-20℃, the oiling rate is 1.6%-1.8%, the draw ratio is 1-1.2 times, and the winding speed is 4800-5000m / min.

[0018] Bio-based nylon fibers are spun into bio-based nylon yarn, which is then knitted into fabric to obtain bio-based nylon fabric. The bio-based nylon fabric has a weight of 200 g / m². 2 .

[0019] Preferably, 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), 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, and the reaction conditions are to react at 70-80℃ for 2-4 hours.

[0020] Preferably, the diisocyanate comprises hexamethylene diisocyanate;

[0021] The polyether polyol includes polyoxypropylene glycol;

[0022] The bio-based polyester polyol is prepared by the following steps:

[0023] (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;

[0024] (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.

[0025] Preferably, 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.

[0026] Preferably, in step one, when preparing the composite finishing agent, in step S3, the mass ratio of the polyurethane mixture to the 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.

[0027] Preferably, the composite weather-resistant additive is prepared by the following steps:

[0028] 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.

[0029] 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.

[0030] Preferably, in step A, 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%-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 in a nitrogen atmosphere at 50-70°C for 20-30 hours.

[0031] Preferably, in B, the mass ratio of the modified hindered phenolic compound, isocyanate-treated 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.

[0032] Preferably, the isocyanate-treated nano-zinc oxide is prepared by the following steps:

[0033] Nano zinc oxide was added to N,N-dimethylformamide, ultrasonically dispersed, then diisocyanate was added, ultrasonic dispersion was continued, and the reaction was carried out. After the reaction was completed, the nano zinc oxide was centrifuged, washed, and dried to obtain isocyanate-treated nano zinc oxide.

[0034] The mass ratio of nano zinc oxide, N,N-dimethylformamide, and diisocyanate is 8:(80-120):(6-10), and the reaction conditions are 20-30 h at 80-90℃.

[0035] Preferably, the diisocyanate includes isophorone diisocyanate.

[0036] Preferably, the raw materials for preparing the bamboo-cotton fabric in step two include bamboo fiber, cotton fiber, and spandex fiber.

[0037] The present invention also discloses a layered composite fabric based on a waterproof and weather-resistant coating, prepared by the preparation method of the layered composite fabric based on the waterproof and weather-resistant coating as described above.

[0038] An application of layered composite fabrics based on a waterproof and weather-resistant coating, as described above.

[0039] Preferably, the application includes application on outdoor sportswear.

[0040] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0041] The composite fabric in this invention comprises a two-layer structure: an outer layer and an inner layer. The inner layer is made of bamboo cotton, which is soft and skin-friendly. The bamboo fiber can improve the antibacterial properties of the inner layer. The outer layer is made of nylon, which has good abrasion resistance. Through impregnation and curing with a composite finishing agent, a coating is formed on the nylon fabric, which can effectively improve the waterproof and weather-resistant properties of the nylon fabric. Furthermore, the raw material for preparing the nylon fabric is bio-based nylon. The use of bio-based materials can effectively reduce the use of non-renewable petrochemical materials.

[0042] In this invention, during the preparation of the composite finishing agent, diisocyanate reacts with polyether polyol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane in an organic solvent to obtain a polyurethane prepolymer solution. The organosilicon molecular chains introduced by the hydroxyl-terminated polydimethylsiloxane effectively improve the hydrophobicity of the finishing agent and also enhance the softness of the coating. N-octadecyl diethanolamine is used as a chain extender to react with the polyurethane prepolymer, increasing the molecular weight of the polyurethane while the introduced alkyl chains also improve its hydrophobicity. This enhanced hydrophobicity, after curing and forming the coating, effectively improves the waterproof performance of the nylon fabric. Furthermore, the tertiary amine groups introduced by N-octadecyl diethanolamine react with n-bromobutane to generate quaternary ammonium salts, improving the antibacterial properties of the polyurethane. Finally, the introduction of composite weather-resistant additives into the polyurethane effectively improves its weather resistance.

[0043] The composite weather-resistant additive in this invention is composed of organic and inorganic weather-resistant components. The organic weather-resistant component is a hindered phenolic compound, and the inorganic weather-resistant component is nano-zinc oxide. The hindered phenolic compound 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride reacts with the amino group at one end of the 1,18-octadecanediamine molecular chain to obtain a modified hindered phenolic compound. The modified hindered phenolic compound reacts with the isocyanate-treated nano-zinc oxide through the amino group at the other end of the 1,18-octadecanediamine molecular chain. This not only achieves chemical bonding between the organic and inorganic weather-resistant components, but also improves the compatibility between the weather-resistant component and the polyurethane matrix through the entanglement between the alkyl chain and the polyurethane molecular chain, resulting in good weather resistance. Furthermore, the alkyl chain introduced by the 1,18-octadecanediamine can further improve the hydrophobicity of the polyurethane. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the reaction between 1,18-octadecanediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride to prepare a modified hindered phenolic compound in Example 4 of the present invention.

[0045] Figure 2 This is a schematic diagram of the reaction between the modified hindered phenolic compound and isocyanate-treated nano zinc oxide in Example 4 of the present invention to prepare a composite weather-resistant additive.

[0046] Figure 3 The graph shows the test results of the waterproof performance of the nylon fabrics with waterproof and weather-resistant coatings prepared in Examples 4-6 and Comparative Examples 1-3 of the present invention.

[0047] Figure 4 The graph shows the test results of the antibacterial properties of the nylon fabrics with waterproof and weather-resistant coatings prepared in Examples 4-6 and Comparative Examples 1-3 of the present invention.

[0048] Figure 5 The graph shows the results of the weather resistance test of the composite finishing agents prepared in Examples 4-6 and Comparative Examples 1-3 of the present invention. Detailed Implementation

[0049] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0050] Example 1

[0051] This embodiment discloses a method for preparing bio-based nylon fabric, including the following steps:

[0052] Bio-based nylon is melted, the melt is spun through a spinneret, cooled by side blowing, drawn and wound to obtain bio-based nylon fibers.

[0053] The melting temperature is 275℃, the spinneret pressure is 16MPa, the side air velocity is 0.38m / s, the side air temperature is 20℃, the oiling rate is 1.8%, the draw ratio is 1.2, and the winding speed is 5000m / min.

[0054] Bio-based nylon fibers are spun into bio-based nylon yarn with a yarn count of 40S. The bio-based nylon yarn is then knitted into fabric to obtain bio-based nylon fabric. The weight of the bio-based nylon fabric is 200 g / m². 2 .

[0055] Example 2

[0056] This embodiment discloses a method for preparing a bio-based polyester polyol, including the following steps:

[0057] (1) Mix bio-based 1,4-butanediol and 1,6-adipic acid in a molar ratio of 1.3:1. React at 0.08 MPa pressure and 180 °C. Take samples every 30 min to determine the acid value of the reaction mixture until the acid value of the reaction mixture is ≤1 mg KOH / g (the acid value of the reaction mixture is specifically 0.9 mg KOH / g).

[0058] (2) Add bio-based 1,4-butanediol and 1,6-adipic acid and 0.2% stannous octoate, and keep the reaction at 200℃. Take a sample every 30 min to determine the acid value of the reaction mixture until the acid value of the reaction mixture is <0.3mgKOH / g (the acid value of the reaction mixture is specifically 0.2mgKOH / g). After the reaction is completed, remove the water generated by the esterification reaction by vacuum distillation at 130℃ and 0.08MPa pressure to obtain bio-based polyester polyol;

[0059] The number-average molecular weight of the polymer was determined by the SEC-MALLS method (a combination of size exclusion chromatography and multi-angle laser light scattering), and the number-average molecular weight of the bio-based polyester polyol was 600 g / mol.

[0060] Example 3

[0061] This embodiment discloses a method for preparing isocyanate-modified nano zinc oxide, including the following steps:

[0062] Nano zinc oxide was added to N,N-dimethylformamide and ultrasonically dispersed at 50 kHz for 2 h. Then, isophorone diisocyanate was added. The mass ratio of nano zinc oxide, N,N-dimethylformamide, and isophorone diisocyanate was 8:100:8. After ultrasonic dispersion at 50 kHz for 30 min, the mixture was reacted at 85 ℃ for 24 h. After the reaction was completed, the mixture was centrifuged and washed three times with N,N-dimethylformamide and dried in a vacuum drying oven at 80 ℃ until constant weight was obtained to obtain isocyanate-treated nano zinc oxide.

[0063] Example 4

[0064] This embodiment discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps:

[0065] 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.

[0066] The composite finishing agent is prepared by the following steps:

[0067] 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.

[0068] 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.

[0069] 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.

[0070] The composite weather-resistant additive is prepared by the following steps:

[0071] 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.

[0072] 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.

[0073] 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.

[0074] Example 5

[0075] This embodiment discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps:

[0076] 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 1:25. 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 90°C for 3 minutes, then heat and cure it at 150°C for 3 minutes. After washing with ethanol, air dry the fabric to obtain a nylon fabric with a waterproof and weather-resistant coating.

[0077] The composite finishing agent is prepared by the following steps:

[0078] 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.

[0079] 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.

[0080] 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.

[0081] The composite weather-resistant additive is prepared by the following steps:

[0082] 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.

[0083] 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.

[0084] 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.

[0085] Example 6

[0086] This embodiment discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps:

[0087] 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.

[0088] The composite finishing agent is prepared by the following steps:

[0089] 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.

[0090] 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.

[0091] 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.

[0092] The composite weather-resistant additive is prepared by the following steps:

[0093] 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.

[0094] 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.

[0095] 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.

[0096] Comparative Example 1

[0097] This comparative example discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps:

[0098] 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.

[0099] The composite finishing agent is prepared by the following steps:

[0100] 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.

[0101] 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.

[0102] 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.

[0103] The composite weather-resistant additive is prepared by the following steps:

[0104] 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.

[0105] 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.

[0106] 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.

[0107] Comparative Example 2

[0108] This comparative example discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps:

[0109] 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.

[0110] The composite finishing agent is prepared by the following steps:

[0111] 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.

[0112] 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.

[0113] 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.

[0114] The composite weather-resistant additive is prepared by the following steps:

[0115] 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.

[0116] 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.

[0117] 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.

[0118] Comparative Example 3

[0119] This comparative example discloses a method for preparing a layered composite fabric based on a waterproof and weather-resistant coating, including the following steps:

[0120] 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.

[0121] The composite finishing agent is prepared by the following steps:

[0122] 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.

[0123] 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.

[0124] 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.

[0125] The composite weather-resistant additive is prepared by the following steps:

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] Test case

[0131] (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.

[0132] Table 1

[0133]

[0134] 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.

[0135] (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 after 50 washes, in accordance with the standard FZ / T73023-2006 "Antibacterial Knitted Fabrics". The results are shown in Table 2.

[0136] Table 2

[0137]

[0138] 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.

[0139] (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.

[0140] Table 3

[0141]

[0142] 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.

[0143] 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. 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 and reacted. After the reaction is completed, a polyurethane prepolymer solution is obtained. 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). The amount of N,N-dimethylacetamide added is 10-15 times the total mass of diisocyanate, polyether polyol, bio-based polyester polyol, and hydroxyl-terminated polydimethylsiloxane. The reaction conditions are 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. 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 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.

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 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.

5. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 4, 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.

6. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 5, 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.

7. The method for preparing a layered composite fabric based on a waterproof and weather-resistant coating according to claim 5, 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.

8. 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 1-7.

9. An application of the layered composite fabric based on a waterproof and weather-resistant coating as described in claim 8.

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