A puncture-resistant waterproof and moisture-permeable composite fabric containing polyethylene fibers

Abstract

The application relates to the field of layered composite fabrics, and discloses an anti-puncture waterproof and moisture-permeable composite fabric containing polyethylene fibers. A preparation method comprises the following steps: taking UHMWPE fiber fabric as a fabric layer, coating water-based polyurethane-based coating material on one side of the fabric layer to form a coating, and baking to obtain the anti-puncture waterproof and moisture-permeable composite fabric containing polyethylene fibers. The composite fabric has the waterproof and moisture-permeable performance and good anti-puncture performance.

Description

Technical Field

[0001] This invention relates to the field of layered composite fabrics, specifically to a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers. Background Technology

[0002] Puncture-resistant materials can be categorized into hard puncture-resistant materials, puncture-resistant materials, and flexible puncture-resistant materials. Flexible puncture-resistant materials are composite materials formed by combining high-performance fibers in different configurations to create fiber assemblies as reinforcements. The fiber assemblies, acting as reinforcements in flexible puncture-resistant materials, play a crucial role in absorbing puncture energy during the puncture process. Therefore, the properties of the fibers are critical to the puncture resistance of the puncture-resistant material.

[0003] Ultra-high molecular weight polyethylene (UHMWPE) is a linear homopolymer prepared by ethylene gas polymerization. Due to its extremely long polymer chains, semi-crystalline solid conformation, and highly ordered subsurface structure, UHMWPE possesses excellent impact resistance, along with high strength and high modulus. These properties make it widely used in flexible stab-resistant materials.

[0004] Existing technologies, such as Chinese patent application CN116623442A, disclose a wear-resistant and puncture-resistant glove and its processing technology. The wear-resistant and puncture-resistant glove is prepared by heat twisting, heat setting, surface impregnation with impregnation liquid, and coating with wear-resistant coating of ultra-high molecular weight polyethylene fiber. Although the puncture resistance is excellent, the waterproof and breathable properties of the fabric need to be improved. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers. This composite fabric has waterproof and breathable properties, as well as good puncture resistance.

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

[0007] A method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers includes the following steps:

[0008] Step (1): Prepare coating material;

[0009] S11. KH550, toluene, and nano-silicon carbide are mixed, ultrasonically dispersed, and reacted. After the reaction is complete, the mixture is washed and dried to obtain aminosilanized nano-silicon carbide.

[0010] S12. Mix aminosilanized nano-silicon carbide, dichloromethane, and triethylamine, add 2-bromoisobutyryl bromide solution dropwise, react, cool, filter, wash, and dry to obtain brominated modified nano-silicon carbide.

[0011] S13. Mix brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, and N,N-dimethylformamide, add cuprous bromide catalyst, react, and after the reaction is complete, purify and dry to obtain polyacrylate modified nano-silicon carbide.

[0012] S14. Polyacrylate-modified nano-silicon carbide and ethanol are mixed, ultrasonically dispersed, and then waterborne polyurethane, organosilicon defoamer and crosslinking agent are added. The mixture is stirred and cooled to obtain waterborne polyurethane-based coating material.

[0013] Step (2): Use UHMWPE (ultra-high molecular weight polyethylene) fiber fabric as the fabric layer, apply water-based polyurethane coating material to one side of the fabric layer to form a coating, bake, and obtain a puncture-resistant, waterproof and breathable composite fabric containing polyethylene fiber.

[0014] Preferably, in step (1) S11, the mass ratio of KH550, toluene, and nano-silicon carbide is 1.5-2:350-400:50; the reaction conditions are: stirring and reacting at 75-85℃ in a nitrogen atmosphere for 6-8 hours.

[0015] Preferably, in step (1) S12: the mass ratio of aminosilanized nano-silicon carbide, dichloromethane, triethylamine, and 2-bromoisobutyryl bromide is 2:40-50:4-4.3:9.3-9.5; the 2-bromoisobutyryl bromide solution is prepared by mixing 2-bromoisobutyryl bromide and dichloromethane in a volume ratio of 1:3.

[0016] Preferably, in step (1) S12, the reaction conditions are: reacting in a nitrogen atmosphere at 0°C for 3-4 hours, and then heating to 35-40°C to continue the reaction for 48-52 hours.

[0017] Preferably, in step (1) S13: the mass ratio of brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, catalyst cuprous bromide, and N,N-dimethylformamide is 2:0.14-0.15:3-4:2-3:0.11-0.12:40-50; the reaction conditions are: reaction at 85-90℃ for 48-52 hours in a nitrogen atmosphere.

[0018] Preferably, in step (1) S13: the purification operation includes: passing air, filtering, washing with acetone, water and ethanol in sequence, and removing impurities by Soxhlet extraction and filtration with dichloromethane.

[0019] Preferably, in step (1) S14: the mass ratio of polyacrylate modified nano silicon carbide, waterborne polyurethane, organosilicon defoamer and crosslinking agent is 3-4:100:1-2:2-3; the stirring and mixing conditions are: stirring and mixing at 40-50℃ for 30-40 min.

[0020] Preferably, in step (2): the coating material is applied at a rate of 50 g / m². 2 The baking conditions are: pre-baking at 70-80℃ for 3-5 minutes, and baking at 130-140℃ for 1 minute.

[0021] Preferably, the puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers is prepared by the preparation method of the puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers as described above.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] 1. This invention utilizes ultra-high molecular weight polyethylene fabric with excellent puncture resistance as the fabric layer, and water-based polyurethane as the matrix resin for constructing a waterproof and breathable coating. By adding hydrophobically modified nano-silicon carbide to the coating material, the waterproof performance of the coating is improved, while the high rigidity of the nano-silicon carbide further enhances the puncture resistance of the composite material.

[0024] 2. This invention uses aminosilane coupling agent KH550 to modify the surface of nano-silicon carbide, and then uses amino groups to react with 2-bromoisobutyryl bromide to obtain brominated nano-silicon carbide. Using it as an initiator, methyl methacrylate and 2-(perfluorobutyl)ethyl methacrylate are grafted onto the surface of nano-silicon carbide by atom transfer radical polymerization to form a hydrophobic organic polymer layer. This not only improves the dispersibility and compatibility of nano-silicon carbide in coating materials, but also improves the waterproof effect of coating materials due to its hydrophobic properties.

[0025] The addition of hydrophobically modified nano-silicon carbide coating material can effectively improve the puncture resistance of fabrics. This is because the polyurethane coating adheres to the fibers and yarns of the fabric layer, allowing more yarns to withstand the impact force during puncture, thus increasing the puncture load value of the fabric. Silicon carbide, on the other hand, increases the friction between fibers and yarns, transforming the fabric's failure mode into fiber breakage as the dominant process, thereby enabling it to withstand more puncture energy and thus improving the puncture resistance of the composite fabric. Attached Figure Description

[0026] Figure 1 These are hydrostatic bar charts of Examples 1-5 and Comparative Examples 1-2 in the performance test of this invention;

[0027] Figure 2 This is a bar chart showing the maximum puncture load in performance tests for Examples 1-5 and Comparative Examples 1-2 of this invention. Detailed Implementation

[0028] 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.

[0029] Example 1

[0030] This embodiment discloses a method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers, including the following steps:

[0031] Step (1): Prepare coating material;

[0032] S11. KH550, toluene, and nano-silicon carbide were mixed in a mass ratio of 1.5:350:50, ultrasonically dispersed, and stirred at 75°C for 8 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was washed with water and acetone in sequence, and dried at 105°C for 12 hours to obtain aminosilanized nano-silicon carbide.

[0033] S12. Mix aminosilanized nano-silicon carbide, dichloromethane, and triethylamine. Add 2-bromoisobutyryl bromide solution dropwise under a nitrogen atmosphere at 0°C. React at 0°C for 3 hours, then raise the temperature to 35°C and continue the reaction for 52 hours. After the reaction is complete, cool to room temperature, filter, wash with dichloromethane, water, and ethanol in sequence, and dry at 50°C for 24 hours to obtain brominated modified nano-silicon carbide.

[0034] The mass ratio of aminosilanized nano-silicon carbide, dichloromethane, triethylamine, and 2-bromoisobutyryl bromide is 2:40:4:9.3.

[0035] The 2-bromoisobutyryl bromide solution is prepared by mixing 2-bromoisobutyryl bromide and dichloromethane at a volume ratio of 1:3;

[0036] S13. Brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, and N,N-dimethylformamide were mixed. Cuprous bromide catalyst was added under a nitrogen atmosphere, and the mixture was heated to 85°C and reacted for 52 hours. After the reaction was completed, air was introduced, the mixture was filtered, and washed successively with acetone, water, and ethanol. The mixture was then removed by Soxhlet extraction and filtration with dichloromethane. The mixture was dried at 50°C for 24 hours to obtain polyacrylate-modified nano-silicon carbide.

[0037] The mass ratio of brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, catalyst cuprous bromide, and N,N-dimethylformamide is 2:0.14:4:2:0.11:40.

[0038] S14. Polyacrylate-modified nano-silicon carbide and ethanol are mixed at a mass ratio of 1:10, ultrasonically dispersed for 20 min, waterborne polyurethane, organosilicon defoamer and crosslinking agent are added, and the mixture is stirred and mixed at 50℃ for 30 min. The mixture is then cooled to room temperature to obtain a waterborne polyurethane-based coating material.

[0039] The mass ratio of polyacrylate-modified nano-silicon carbide, waterborne polyurethane, organosilicon defoamer, and crosslinking agent is 3:100:1:2.

[0040] Step (2): The surface density is 240 g / m³ 2 Using UHMWPE fiber fabric as the fabric layer, a water-based polyurethane coating material is applied to one side of the fabric layer to form a coating, with a coating amount of 50 g / m². 2 The fabric is pre-dried at 70℃ for 5 minutes and then baked at 130℃ for 1 minute to obtain a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers.

[0041] Example 2

[0042] This embodiment discloses a method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers, including the following steps:

[0043] Step (1): Prepare coating material;

[0044] S11. KH550, toluene, and nano-silicon carbide were mixed in a mass ratio of 1.8:380:50, ultrasonically dispersed, and stirred at 80°C for 7 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was washed with water and acetone in sequence, and dried at 105°C for 12 hours to obtain aminosilanized nano-silicon carbide.

[0045] S12. Mix aminosilanized nano-silicon carbide, dichloromethane, and triethylamine. Add 2-bromoisobutyryl bromide solution dropwise under a nitrogen atmosphere at 0°C. React at 0°C for 3.5 h, then raise the temperature to 38°C and continue the reaction for 50 h. After the reaction is complete, cool to room temperature, filter, wash with dichloromethane, water, and ethanol in sequence, and dry at 50°C for 24 h to obtain brominated modified nano-silicon carbide.

[0046] The mass ratio of aminosilanized nano-silicon carbide, dichloromethane, triethylamine, and 2-bromoisobutyryl bromide is 2:45:4.1:9.35.

[0047] The 2-bromoisobutyryl bromide solution is prepared by mixing 2-bromoisobutyryl bromide and dichloromethane at a volume ratio of 1:3;

[0048] S13. Brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, and N,N-dimethylformamide were mixed. Cuprous bromide catalyst was added under a nitrogen atmosphere, and the mixture was heated to 88°C and reacted for 50 h. After the reaction was completed, air was introduced, the mixture was filtered, and washed successively with acetone, water, and ethanol. The mixture was then removed by Soxhlet extraction and filtration with dichloromethane. The mixture was dried at 50°C for 24 h to obtain polyacrylate-modified nano-silicon carbide.

[0049] The mass ratio of brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, catalyst cuprous bromide, and N,N-dimethylformamide is 2:0.14:3.2:2.8:0.11:45.

[0050] S14. Polyacrylate-modified nano-silicon carbide and ethanol are mixed at a mass ratio of 1:10, ultrasonically dispersed for 20 min, waterborne polyurethane, organosilicon defoamer and crosslinking agent are added, and the mixture is stirred and mixed at 50℃ for 30 min. The mixture is then cooled to room temperature to obtain a waterborne polyurethane-based coating material.

[0051] The mass ratio of polyacrylate-modified nano-silicon carbide, waterborne polyurethane, organosilicon defoamer, and crosslinking agent is 3.3:100:1.5:2.5.

[0052] Step (2): The surface density is 240 g / m³ 2 Using UHMWPE fiber fabric as the fabric layer, a water-based polyurethane coating material is applied to one side of the fabric layer to form a coating, with a coating amount of 50 g / m². 2 Pre-dry at 75℃ for 4 minutes and bake at 135℃ for 1 minute to obtain a puncture-resistant, waterproof and breathable composite fabric containing polyethylene fibers.

[0053] Example 3

[0054] This embodiment discloses a method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers, including the following steps:

[0055] Step (1): Prepare coating material;

[0056] S11. KH550, toluene, and nano-silicon carbide were mixed in a mass ratio of 1.8:380:50, ultrasonically dispersed, and stirred at 80°C for 7 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was washed with water and acetone in sequence, and dried at 105°C for 12 hours to obtain aminosilanized nano-silicon carbide.

[0057] S12. Mix aminosilanized nano-silicon carbide, dichloromethane, and triethylamine. Add 2-bromoisobutyryl bromide solution dropwise under a nitrogen atmosphere at 0°C. React at 0°C for 3.5 h, then raise the temperature to 38°C and continue the reaction for 50 h. After the reaction is complete, cool to room temperature, filter, wash with dichloromethane, water, and ethanol in sequence, and dry at 50°C for 24 h to obtain brominated modified nano-silicon carbide.

[0058] The mass ratio of aminosilanized nano-silicon carbide, dichloromethane, triethylamine, and 2-bromoisobutyryl bromide is 2:45:4.15:9.4.

[0059] The 2-bromoisobutyryl bromide solution is prepared by mixing 2-bromoisobutyryl bromide and dichloromethane at a volume ratio of 1:3;

[0060] S13. Brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, and N,N-dimethylformamide were mixed. Cuprous bromide catalyst was added under a nitrogen atmosphere, and the mixture was heated to 88°C and reacted for 50 h. After the reaction was completed, air was introduced, the mixture was filtered, and washed successively with acetone, water, and ethanol. The mixture was then removed by Soxhlet extraction and filtration with dichloromethane. The mixture was dried at 50°C for 24 h to obtain polyacrylate-modified nano-silicon carbide.

[0061] The mass ratio of brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, catalyst cuprous bromide, and N,N-dimethylformamide is 2:0.145:3.5:2.5:0.115:45.

[0062] S14. Polyacrylate-modified nano-silicon carbide and ethanol are mixed at a mass ratio of 1:10, ultrasonically dispersed for 20 min, waterborne polyurethane, organosilicon defoamer and crosslinking agent are added, and the mixture is stirred and mixed at 50℃ for 30 min. The mixture is then cooled to room temperature to obtain a waterborne polyurethane-based coating material.

[0063] The mass ratio of polyacrylate-modified nano-silicon carbide, waterborne polyurethane, silicone defoamer, and crosslinking agent is 3.5:100:1.5:2.5.

[0064] Step (2): The surface density is 240 g / m³ 2 Using UHMWPE fiber fabric as the fabric layer, a water-based polyurethane coating material is applied to one side of the fabric layer to form a coating, with a coating amount of 50 g / m². 2 The fabric is pre-dried at 75℃ for 4 minutes and then baked at 135℃ for 1 minute to obtain a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers.

[0065] Example 4

[0066] This embodiment discloses a method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers, including the following steps:

[0067] Step (1): Prepare coating material;

[0068] S11. KH550, toluene, and nano-silicon carbide were mixed in a mass ratio of 1.8:380:50, ultrasonically dispersed, and stirred at 80°C for 7 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was washed with water and acetone in sequence, and dried at 105°C for 12 hours to obtain aminosilanized nano-silicon carbide.

[0069] S12. Mix aminosilanized nano-silicon carbide, dichloromethane, and triethylamine. Add 2-bromoisobutyryl bromide solution dropwise under a nitrogen atmosphere at 0°C. React at 0°C for 3.5 h, then raise the temperature to 38°C and continue the reaction for 50 h. After the reaction is complete, cool to room temperature, filter, wash with dichloromethane, water, and ethanol in sequence, and dry at 50°C for 24 h to obtain brominated modified nano-silicon carbide.

[0070] The mass ratio of aminosilanized nano-silicon carbide, dichloromethane, triethylamine, and 2-bromoisobutyryl bromide is 2:45:4.2:9.4.

[0071] The 2-bromoisobutyryl bromide solution is prepared by mixing 2-bromoisobutyryl bromide and dichloromethane at a volume ratio of 1:3;

[0072] S13. Brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, and N,N-dimethylformamide were mixed. Cuprous bromide catalyst was added under a nitrogen atmosphere, and the mixture was heated to 88°C and reacted for 50 h. After the reaction was completed, air was introduced, the mixture was filtered, and washed successively with acetone, water, and ethanol. The mixture was then removed by Soxhlet extraction and filtration with dichloromethane. The mixture was dried at 50°C for 24 h to obtain polyacrylate-modified nano-silicon carbide.

[0073] The mass ratio of brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, catalyst cuprous bromide, and N,N-dimethylformamide is 2:0.15:3.8:2.2:0.115:45.

[0074] S14. Polyacrylate-modified nano-silicon carbide and ethanol are mixed at a mass ratio of 1:10, ultrasonically dispersed for 20 min, waterborne polyurethane, organosilicon defoamer and crosslinking agent are added, and the mixture is stirred and mixed at 50℃ for 30 min. The mixture is then cooled to room temperature to obtain a waterborne polyurethane-based coating material.

[0075] The mass ratio of polyacrylate-modified nano-silicon carbide, waterborne polyurethane, silicone defoamer, and crosslinking agent is 3.8:100:1.5:2.5.

[0076] Step (2): The surface density is 240 g / m³ 2 Using UHMWPE fiber fabric as the fabric layer, a water-based polyurethane coating material is applied to one side of the fabric layer to form a coating, with a coating amount of 50 g / m². 2 The fabric is pre-dried at 75℃ for 4 minutes and then baked at 135℃ for 1 minute to obtain a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers.

[0077] Example 5

[0078] This embodiment discloses a method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers, including the following steps:

[0079] Step (1): Prepare coating material;

[0080] S11. KH550, toluene, and nano-silicon carbide were mixed in a mass ratio of 2:400:50, ultrasonically dispersed, and stirred at 85°C for 6 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was washed with water and acetone in sequence, and dried at 105°C for 12 hours to obtain aminosilanized nano-silicon carbide.

[0081] S12. Mix aminosilanized nano-silicon carbide, dichloromethane, and triethylamine. Add 2-bromoisobutyryl bromide solution dropwise under a nitrogen atmosphere at 0°C. React at 0°C for 4 hours, then raise the temperature to 40°C and continue the reaction for 48 hours. After the reaction is completed, cool to room temperature, filter, wash with dichloromethane, water, and ethanol in sequence, and dry at 50°C for 24 hours to obtain brominated modified nano-silicon carbide.

[0082] The mass ratio of aminosilanized nano-silicon carbide, dichloromethane, triethylamine, and 2-bromoisobutyryl bromide is 2:50:4.3:9.5.

[0083] The 2-bromoisobutyryl bromide solution is prepared by mixing 2-bromoisobutyryl bromide and dichloromethane at a volume ratio of 1:3;

[0084] S13. Brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, and N,N-dimethylformamide were mixed. Cuprous bromide catalyst was added under a nitrogen atmosphere, and the mixture was heated to 90°C and reacted for 48 hours. After the reaction was completed, air was introduced, the mixture was filtered, and washed successively with acetone, water, and ethanol. The mixture was then removed by Soxhlet extraction and filtration with dichloromethane. The mixture was dried at 50°C for 24 hours to obtain polyacrylate-modified nano-silicon carbide.

[0085] The mass ratio of brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, catalyst cuprous bromide, and N,N-dimethylformamide is 2:0.15:3:3:0.12:50.

[0086] S14. Polyacrylate-modified nano-silicon carbide and ethanol are mixed at a mass ratio of 1:10, ultrasonically dispersed for 20 min, waterborne polyurethane, organosilicon defoamer and crosslinking agent are added, and the mixture is stirred and mixed at 50℃ for 30 min. The mixture is then cooled to room temperature to obtain a waterborne polyurethane-based coating material.

[0087] The mass ratio of polyacrylate-modified nano-silicon carbide, waterborne polyurethane, organosilicon defoamer, and crosslinking agent is 4:100:2:3.

[0088] Step (2): The surface density is 240 g / m³ 2 Using UHMWPE fiber fabric as the fabric layer, a water-based polyurethane coating material is applied to one side of the fabric layer to form a coating, with a coating amount of 50 g / m². 2 The fabric is pre-dried at 80℃ for 3 minutes and then baked at 140℃ for 1 minute to obtain a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers.

[0089] Comparative Example 1

[0090] This comparative example discloses a method for preparing a composite fabric containing polyethylene fibers, comprising the following steps:

[0091] Step (1): Prepare coating material;

[0092] Nano-silicon carbide and ethanol were mixed at a mass ratio of 1:10 and ultrasonically dispersed for 20 min. Waterborne polyurethane, silicone defoamer, and crosslinking agent were added and stirred at 50°C for 30 min. The mixture was then cooled to room temperature to obtain a waterborne polyurethane-based coating material.

[0093] The mass ratio of nano-silicon carbide, waterborne polyurethane, organosilicon defoamer, and crosslinking agent is 3:100:1:2.

[0094] Step (2): The surface density is 240 g / m³ 2 Using UHMWPE fiber fabric as the fabric layer, a water-based polyurethane coating material is applied to one side of the fabric layer to form a coating, with a coating amount of 50 g / m². 2 The composite fabric containing polyethylene fibers is obtained by pre-drying at 70℃ for 5 minutes and then baking at 130℃ for 1 minute.

[0095] Comparative Example 2

[0096] This comparative example discloses a method for preparing a composite fabric containing polyethylene fibers, comprising the following steps:

[0097] Step (1): Prepare coating material;

[0098] S11. KH550, toluene, and nano-silicon carbide were mixed in a mass ratio of 1.5:350:50, ultrasonically dispersed, and stirred at 75°C for 8 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was washed with water and acetone in sequence, and dried at 105°C for 12 hours to obtain aminosilanized nano-silicon carbide.

[0099] S12. Mix aminosilanized nano-silicon carbide, dichloromethane, and triethylamine. Add 2-bromoisobutyryl bromide solution dropwise under a nitrogen atmosphere at 0°C. React at 0°C for 3 hours, then raise the temperature to 35°C and continue the reaction for 52 hours. After the reaction is complete, cool to room temperature, filter, wash with dichloromethane, water, and ethanol in sequence, and dry at 50°C for 24 hours to obtain brominated modified nano-silicon carbide.

[0100] The mass ratio of aminosilanized nano-silicon carbide, dichloromethane, triethylamine, and 2-bromoisobutyryl bromide is 2:40:4:9.3.

[0101] The 2-bromoisobutyryl bromide solution is prepared by mixing 2-bromoisobutyryl bromide and dichloromethane at a volume ratio of 1:3;

[0102] S13. Brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, and N,N-dimethylformamide were mixed, and cuprous bromide catalyst was added under a nitrogen atmosphere. The mixture was heated to 85°C and reacted for 52 hours. After the reaction was completed, air was introduced, and the mixture was filtered. It was washed successively with acetone, water, and ethanol. The mixture was then removed by Soxhlet extraction and filtration with dichloromethane. The mixture was dried at 50°C for 24 hours to obtain polyacrylate-modified nano-silicon carbide.

[0103] The mass ratio of brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, cuprous bromide catalyst, and N,N-dimethylformamide is 2:0.14:6:0.11:40.

[0104] S14. Polyacrylate-modified nano-silicon carbide and ethanol are mixed at a mass ratio of 1:10, ultrasonically dispersed for 20 min, waterborne polyurethane, organosilicon defoamer and crosslinking agent are added, and the mixture is stirred and mixed at 50℃ for 30 min. The mixture is then cooled to room temperature to obtain a waterborne polyurethane-based coating material.

[0105] The mass ratio of polyacrylate-modified nano-silicon carbide, waterborne polyurethane, organosilicon defoamer, and crosslinking agent is 3:100:1:2.

[0106] Step (2): The surface density is 240 g / m³ 2 Using UHMWPE fiber fabric as the fabric layer, a water-based polyurethane coating material is applied to one side of the fabric layer to form a coating, with a coating amount of 50 g / m². 2 The composite fabric containing polyethylene fibers is obtained by pre-drying at 70℃ for 5 minutes and then baking at 130℃ for 1 minute.

[0107] In the above embodiments and comparative examples: the particle size of nano-silicon carbide is 30-50nm; the crosslinking agent is AF6900; and the waterborne polyurethane is a polyether-type aliphatic waterborne polyurethane.

[0108] Test case

[0109] The composite fabrics prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests. The specific test results are shown in Table 1.

[0110] Table 1

[0111]

[0112] The tests for each indicator in Table 1 were conducted according to the following standards: For moisture permeability, refer to GB / T 12704.1 "Textiles - Test Methods for Moisture Permeability of Fabrics - Part 1: Moisture Absorption Method" and use a fabric moisture permeability meter for testing. The calculation method for moisture permeability (WVT) is: WVT = (M1 − M2) / A × 24; where M1 − M2 is the difference in weight of the sample before and after the test, i.e., the mass of liquid evaporated within 1 hour; A is the effective area during the test; and the unit of WVT is kg / m². 2 / d; Hydrostatic pressure is tested using a hydrostatic permeability tester on the coated side of the sample, referring to AATCC127-2017 "Water Resistance: Hydrostatic Test". Quasi-static puncture resistance is expressed by the maximum puncture load, and is tested using a universal tensile testing machine, referring to GB / T 12017-1989 "Puncture Resistance Technical Conditions and Test Methods for Puncture-resistant Shoes".

[0113] As can be seen from the test results in Table 1, the composite fabric prepared in this invention has good waterproof and breathable properties as well as good puncture resistance. This is because this invention uses ultra-high molecular weight polyethylene fabric with excellent puncture resistance as the fabric layer, and water-based polyurethane as the matrix resin for constructing the waterproof and breathable coating. By adding hydrophobically modified nano-silicon carbide to the coating material, the waterproof performance of the coating is improved, while the high rigidity of nano-silicon carbide further enhances the puncture resistance of the composite material.

[0114] In Comparative Example 1, nano-silicon carbide without surface modification was added to the coating material. The compatibility of nano-silicon carbide in the coating material decreased, it was easy to agglomerate, and it lacked the effect of hydrophobic groups to improve the hydrophobicity of the material. Therefore, the waterproof and breathable properties and puncture resistance of Comparative Example 1 decreased.

[0115] In Comparative Example 2, no 2-(perfluorobutyl)ethyl methacrylate was added during the preparation of polyacrylate-modified nano-silicon carbide. The lack of hydrophobic groups to improve the hydrophobicity of the material resulted in a decrease in the waterproof performance of Comparative Example 1.

[0116] 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 puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers, characterized in that, Includes the following steps: Step (1): Prepare coating material; Polyacrylate-modified nano-silicon carbide and ethanol are mixed, ultrasonically dispersed, and then water-based polyurethane, silicone defoamer, and crosslinking agent are added. The mixture is stirred and cooled to obtain the coating material. Polyacrylate-modified nano-silicon carbide is prepared by the following steps: S11. KH550, toluene, and nano-silicon carbide are mixed, ultrasonically dispersed, and reacted. After the reaction is complete, the mixture is washed and dried to obtain aminosilanized nano-silicon carbide. S12. Mix aminosilanized nano-silicon carbide, dichloromethane, and triethylamine, add 2-bromoisobutyryl bromide solution dropwise, react, cool, filter, wash, and dry to obtain brominated modified nano-silicon carbide. S13. Mix brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, and N,N-dimethylformamide, add cuprous bromide catalyst, react, and after the reaction is complete, purify and dry to obtain polyacrylate modified nano-silicon carbide. Step (2): Use UHMWPE fiber fabric as the fabric layer, apply coating material to one side of the fabric layer to form a coating, bake to obtain a puncture-resistant, waterproof and breathable composite fabric containing polyethylene fiber.

2. The method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers according to claim 1, characterized in that, In step (1), when preparing polyacrylate-modified nano-silicon carbide, the mass ratio of KH550, toluene, and nano-silicon carbide in S11 is 1.5-2:350-400:50; the reaction conditions are: stirring and reacting at 75-85℃ for 6-8 hours in a nitrogen atmosphere.

3. The method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers according to claim 1, characterized in that, In step (1), when preparing polyacrylate-modified nano-silicon carbide, the mass ratio of aminosilanized nano-silicon carbide, dichloromethane, triethylamine, and 2-bromoisobutyryl bromide in S12 is 2:40-50:4-4.3:9.3-9.5; the 2-bromoisobutyryl bromide solution is prepared by mixing 2-bromoisobutyryl bromide and dichloromethane in a volume ratio of 1:

3.

4. The method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers according to claim 1, characterized in that, In step (1), when preparing polyacrylate-modified nano-silicon carbide, the reaction conditions in S12 are: reacting for 3-4 hours in a nitrogen atmosphere at 0°C, and then continuing the reaction at 35-40°C for 48-52 hours.

5. The method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers according to claim 1, characterized in that, In step (1), when preparing polyacrylate-modified nano-silicon carbide, the mass ratio of brominated modified nano-silicon carbide, pentamethyldiethylenetriamine, methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, catalyst cuprous bromide, and N,N-dimethylformamide in S13 is 2:0.14-0.15:3-4:2-3:0.11-0.12:40-50.

6. The method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers according to claim 1, characterized in that, In step (1), when preparing polyacrylate-modified nano-silicon carbide, the reaction conditions in S13 are: reaction at 85-90℃ for 48-52 hours in a nitrogen atmosphere.

7. The method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers according to claim 1, characterized in that, In step (1), the mass ratio of polyacrylate-modified nano-silicon carbide, waterborne polyurethane, silicone defoamer, and crosslinking agent is 3-4:100:1-2:2-3; the mixing conditions are: mixing at 40-50℃ for 30-40 minutes.

8. The method for preparing a puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers according to claim 1, characterized in that, In step (2): the coating material is applied at a rate of 50 g / m². 2 The baking conditions are: pre-baking at 70-80℃ for 3-5 minutes, and baking at 130-140℃ for 1 minute.

9. A puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers, prepared by the preparation method of the puncture-resistant, waterproof, and breathable composite fabric containing polyethylene fibers as described in any one of claims 1-8.

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