A multilayer composite chemical protective clothing fabric and a process for making the same

Abstract

The present application relates to the technical field of fabric, in particular to a kind of multilayer composite chemical protective clothing fabric and its preparation process.A kind of preparation process of multilayer composite chemical protective clothing fabric, comprising: the preparation of hydrophobic modifier, the preparation of modified water-based polyurethane, the preparation of modified graphene filler, the preparation of protective barrier fabric, the preparation of chemical protective clothing fabric.The fabric of the present application adopts layered composite structure, the inner layer is made of spandex fiber, bamboo fiber, viscose fiber blend, can provide good flexibility, moisture permeability and wearing comfort;The outer layer is made of aramid fiber and nylon blend, impart high strength, wear resistance and tear resistance to the fabric, strengthen physical protection;Chloroprene rubber layer and protective barrier fabric are arranged in the middle, form double chemical barrier system, can efficiently block the penetration of various organic / inorganic chemical reagents.

Description

Technical Field

[0001] This invention relates to the field of fabric technology, specifically to a multi-layer composite chemical protective clothing fabric and its preparation process. Background Technology

[0002] As the core protective equipment against chemical hazards, the performance of chemical protective clothing fabric directly determines the protective effect and wearing safety. With the rapid development of the chemical industry and the increasing variety of hazardous chemicals, higher requirements are placed on the comprehensive performance of chemical protective clothing fabrics. They not only need to have excellent chemical barrier properties, but also need to take into account good mechanical strength, breathability and moisture permeability, structural stability and environmental protection, so as to meet the needs of long-term and complex operation.

[0003] Currently, most existing chemical protective clothing fabrics adopt a multi-layer composite structure design, combining single-layer materials with different functions to achieve complementary protective performance. For example, composite rubber fabrics are made by combining three types of rubber materials—fluororubber, butyl rubber, and neoprene rubber—with polyamide fabric and coating them with a barrier film. Although such fabrics can achieve excellent barrier protection performance, they generally suffer from being heavy and uncomfortable to wear, leading to fatigue for workers after prolonged wear. Furthermore, they can only block most common inorganic acid and alkali chemical liquids, and their protection against organic compounds is insufficient. Another example is composite barrier film fabrics, which combine polyethylene film with non-woven fabric or special thermoplastic barrier materials with high-strength nylon base fabric. While this can reduce the weight of the fabric, it suffers from the defect of limited barrier performance and poor chemical resistance, failing to meet the protection requirements effectively.

[0004] Therefore, this application aims to develop a multi-layer composite chemical protective clothing fabric and its preparation process that can achieve long-lasting, broad-spectrum chemical protection while also possessing excellent wearing comfort and mechanical durability, in order to solve the problems in the prior art. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a multi-layer composite chemical protective clothing fabric and its preparation process.

[0006] This invention provides a multi-layer composite chemical protective clothing fabric, comprising: an inner fabric, a neoprene layer, a protective barrier layer fabric, and an outer fabric. The inner fabric is made of a blend of spandex fiber, bamboo fiber and viscose fiber in a 3:1:1 ratio. The protective barrier layer fabric is made of high molecular weight polyethylene nonwoven fabric coated with functional coating adhesive; The functional coating adhesive is composed of 100-120 parts by weight of modified waterborne polyurethane, 5-8 parts by weight of modified graphene filler, 0.1-0.3 parts by weight of leveling agent, and 0.1-0.3 parts by weight of defoamer; The modified waterborne polyurethane is prepared from 16-18 parts by weight of isophorone diisocyanate, 40-50 parts by weight of polytetrahydrofuran ether diol, 7-8 parts by weight of hydrophobic modifier, 3-5 parts by weight of dihydroxy polymethyltrifluoropropylsiloxane, 0.05-0.08 parts by weight of catalyst and 2-3 parts by weight of 2,2-dimethylolpropionic acid as raw materials. The hydrophobic modifier is prepared from 10-12 parts by weight of sodium hydroxide, 35-40 parts by weight of 1H,1H,2H,2H-perfluoro-1-octanol, 30-32 parts by weight of epichlorohydrin, 1-2 parts by weight of 1,4-butanediol, 20-30 parts by weight of toluene, 2-3 parts by weight of boron trifluoride ether, and 35-40 parts by weight of propylene oxide as raw materials, through stepwise reaction, washing, concentration, dehydration and purification. The outer fabric is made of aramid fiber and nylon blended in a 1:1 ratio.

[0007] The present invention also provides a multi-layer composite chemical protective clothing fabric, comprising: S1: Preparation of hydrophobic modifier; The intermediate product was obtained by reacting 1H,1H,2H,2H-perfluoro-1-octanol with epichlorohydrin, and then reacted with 1,4-butanediol and propylene oxide under the catalysis of boron trifluoride ether. After purification, a hydrophobic modifier was obtained. S2: Preparation of modified waterborne polyurethane; Isophorone diisocyanate, polytetrahydrofuran ether diol, hydrophobic modifier and dihydroxy polymethyltrifluoropropylsiloxane were prepolymerized, and then 2,2-dimethylolpropionic acid was added for chain extension. After neutralization, modified waterborne polyurethane was obtained. S3: Preparation of modified graphene filler; Expandable graphite was expanded by microwave and exfoliated by liquid-phase ball milling to obtain ball-milled graphene. Then, using ammonium persulfate as an initiator, m-phenylenediamine was polymerized on the surface of the ball-milled graphene in an ammonia system to obtain modified graphene filler. S4: Preparation of protective barrier layer fabric; Modified waterborne polyurethane and modified graphene filler were mixed and additives were added to prepare a functional coating adhesive. The coating adhesive was applied to the surface of plasma-treated high molecular weight polyethylene nonwoven fabric and dried and cured to obtain a protective barrier layer fabric. S5: Preparation of chemical protective clothing fabric; The inner fabric, neoprene layer, protective barrier layer fabric, and outer fabric are hot-pressed together using hot melt adhesive to obtain a multi-layer composite chemical protective clothing fabric.

[0008] As a preferred aspect, S1: the preparation of the hydrophobic modifier specifically includes the following steps: S1.1: Mix 10-12 parts by weight of sodium hydroxide and 35-40 parts by weight of 1H,1H,2H,2H-perfluoro-1-octanol, then stir and mix at 35-40℃ for 20-30 min, then add 30-32 parts by weight of epichlorohydrin, stir and react for 6-8 h, after the reaction is complete, perform rotary evaporation, then wash with a deionized water-dichloromethane mixture under ice bath until neutral, and concentrate by rotary evaporation to obtain the intermediate product; S1.2: Under ice bath conditions, 1-2 parts by weight of 1,4-butanediol and 20-30 parts by weight of toluene are mixed, followed by the addition of 2-3 parts by weight of boron trifluoride diethyl ether and reaction for 20-30 min. Then, 30-40 parts by weight of intermediate product and 35-40 parts by weight of propylene oxide are added, and the reaction is continued for 4-5 h. After the reaction is completed, 4-5 parts by weight of deionized water are added, followed by rotary evaporation for concentration. The concentrated product is placed in an ice bath at 0 °C and purified by washing with a deionized water-dichloromethane mixture. After dehydration treatment with anhydrous magnesium sulfate, the hydrophobic modifier is obtained.

[0009] As a preferred aspect, the deionized water-dichloromethane mixture in step S1 is composed of deionized water and dichloromethane in a volume ratio of 1:1.

[0010] As a preferred aspect, S2: the preparation of modified waterborne polyurethane specifically includes the following steps: S2.1: Mix 16-18 parts by weight of isophorone diisocyanate, 40-50 parts by weight of polytetrahydrofuran ether diol, 7-8 parts by weight of hydrophobic modifier and 3-5 parts by weight of dihydroxy polymethyltrifluoropropylsiloxane, then preheat the mixture at 75-80℃ for 20-30 min, then raise the temperature to 75-85℃, add 0.05-0.08 parts by weight of catalyst dibutyltin dilaurate, and react for 2-3 h to obtain the prepolymer; S2.2: Then, at 75-80℃, add 2-3 parts by weight of 2,2-dimethylolpropionic acid to the prepolymer and react for 3-5 hours. After the reaction is completed, cool down to 45-48℃. During the cooling process, add 10-12 parts by weight of acetone to adjust the viscosity. After cooling, add 3-4 parts by weight of triethylamine and react for 10-12 minutes. After the reaction is completed, add 20-30 parts by weight of deionized water and stir and disperse at 1300-1400 rpm for 20-30 minutes. Then, remove acetone by vacuum distillation to obtain modified waterborne polyurethane.

[0011] As a preferred aspect, S3: the preparation of modified graphene filler specifically includes the following steps: S3.1: Add 2-3 parts by weight of expandable graphite powder to a quartz crucible, then place it in a microwave atmosphere sintering furnace and microwave heat treat it at 600-660℃ for 1-2 minutes under a nitrogen atmosphere. Add 2-3 parts by weight of the microwave heat treated graphite powder to 200-230 parts by weight of n-butanol, then ultrasonically disperse it for 20-30 minutes. Add the ultrasonically dispersed dispersion to a planetary ball mill and add zirconium oxide beads at a ball-to-material ratio of 8-10:1. Ball mill at 300-320 rpm for 40-48 hours, then centrifuge at 10000-12000 rpm for 20-30 minutes. The centrifuged suspension is then evaporated under vacuum at room temperature to obtain ball-milled graphene. S3.2: Add 3-5 parts by weight of ammonium persulfate to 30-50 parts by weight of ammonia water, stir and mix at 300-500 rpm for 20-30 min to obtain an initiator solution, add 10-12 parts by weight of ball-milled graphene and 20-22 parts by weight of m-phenylenediamine to 80-100 parts by weight of ammonia water, and then sonicate for 20-30 min to obtain a mixed solution; S3.3: Add the initiator solution to the mixed solution at 200-300 rpm, and then continue to stir the reaction at 25-30℃ for 3-5 h. After the reaction is completed, centrifuge at 8000-10000 rpm for 20-30 min, then wash the centrifuged precipitate with deionized water 3-5 times, and then vacuum dry to obtain the modified graphene filler.

[0012] As a preferred aspect, S4: the preparation of the protective barrier layer fabric specifically includes the following steps: S4.1: Add 5-8 parts by weight of modified graphene filler to 100-120 parts by weight of modified waterborne polyurethane, then add 0.1-0.3 parts by weight of leveling agent BYK-300 and 0.1-0.3 parts by weight of defoamer BYK-019. Stir and mix at 300-500 rpm for 30-40 minutes, then let stand for 1-2 hours to obtain functional coating adhesive. S4.2: Soak the high molecular weight polyethylene nonwoven fabric in anhydrous ethanol for 2-3 minutes, then wash it with deionized water 3-5 times, and then dry it in an oven at 30-40℃ for 10-12 hours. The dried nonwoven fabric is then subjected to plasma treatment with argon / oxygen to obtain pretreated nonwoven fabric. S4.3: Apply functional coating adhesive to the surface of the pretreated nonwoven fabric using a doctor blade coating machine. The wet coating thickness is 50-80 micrometers. Place the coated nonwoven fabric in an oven and dry it with hot air at 80-100℃ for 2-4 minutes. Then, raise the temperature to 120-130℃ for 3-5 minutes to obtain the protective barrier layer fabric.

[0013] As a preferred aspect, in step S4.2, the plasma treatment parameters are 80-100W for 30-40s, and the volume ratio of argon to oxygen is 9:1.

[0014] As a preferred aspect, S5: the preparation of chemical protective clothing fabric specifically includes the following steps: S5.1: The inner fabric is made by blending spandex fiber, bamboo fiber and viscose fiber in a ratio of 3:1:1, and the outer fabric is made by blending aramid fiber and nylon in a ratio of 1:1. S5.2: The inner layer fabric, PUR hot melt adhesive, neoprene rubber layer, PUR hot melt adhesive, protective barrier layer fabric, PUR hot melt adhesive and outer layer fabric are sequentially hot-pressed together to obtain chemical protective clothing fabric.

[0015] As a preferred aspect, in step S5.2, the hot-pressing temperature is 150-160℃, the pressure is 0.5-0.6MPa, and the hot-pressing time is 10-20s.

[0016] The present invention has the following advantages: 1. The inner layer fabric of this invention, made from a blend of spandex fiber, bamboo fiber, and viscose fiber, provides flexibility, moisture absorption, breathability, and comfort, reducing stuffiness during wear. The outer layer fabric, a blend of aramid fiber and nylon, imparts high strength, abrasion resistance, and tear resistance, enhancing physical protection. The middle neoprene layer has excellent chemical corrosion resistance, oil resistance, and barrier properties, effectively blocking the penetration of liquid or gaseous chemical reagents. The protective barrier layer fabric, as the core functional layer, forms a dual chemical barrier system with the neoprene layer, achieving efficient barrier against organic and inorganic chemical media, significantly improving the chemical protection level of the fabric. Through its multi-layer structure, a balance between comfort, abrasion resistance, and chemical protection is achieved, making it suitable for long-term use in complex chemical environments such as chemical and pharmaceutical industries.

[0017] 2. This invention incorporates a hydrophobic modifier and dihydroxy polymethyltrifluoropropylsiloxane in the polyurethane synthesis. The hydrophobic modifier contains fluoroalkyl groups derived from perfluorooctyl alcohol. The low surface energy of fluorine endows the coating with excellent hydrophobic and oleophobic properties, effectively preventing chemical liquids from wetting, spreading, and penetrating the coating surface, while simultaneously improving the coating's resistance to organic solvents and acid / alkali media. The dihydroxy polymethyltrifluoropropylsiloxane contains both siloxane and fluoroalkyl groups, further reducing the coating's surface energy and enhancing solvent resistance. The synergistic modification by both modifiers results in a hydrophobic modification... The perfluorinated long chains of the adhesive and the trifluoropropyl chains of dihydroxy polymethyltrifluoropropylsiloxane undergo intermolecular synergistic arrangement on the coating surface. The perfluorinated long chains provide a deep and durable oleophobic barrier, while the siloxane backbone and short fluorinated chains provide a denser surface coverage and a lower surface roughness critical point. This "long-short combination" and "fluorine-silicon synergy" molecular arrangement enables the functional coating adhesive to form a uniform, dense, low surface energy barrier film on the surface of polyethylene nonwoven fabric, significantly improving the protective fabric's ability to block chemicals such as acids, alkalis, and organic solvents.

[0018] 3. This invention incorporates modified graphene filler into the functional coating adhesive. The two-dimensional sheet structure of graphene creates a "maze effect" in the coating, physically blocking the diffusion paths of chemical molecules or ions and reducing the permeability of gases, liquids, or vapors. Simultaneously, graphene's high chemical stability and inertness resist various corrosive media, synergistically enhancing the overall barrier effect with polyurethane. Furthermore, the use of m-phenylenediamine to modify the graphene surface introduces amino polar groups. This addresses the issue of graphene's tendency to agglomerate, ensuring its uniform dispersion within the polyurethane matrix and preventing agglomeration that could lead to coating defects. The uniformly dispersed modified graphene filler forms a continuous and dense protective network, effectively improving chemical protection capabilities. On the other hand, the amino groups form hydrogen bonds with the hydroxyl and amino groups in the modified polyurethane, enhancing the interfacial bonding between the filler and the coating, making the filler less prone to detachment and significantly improving interfacial bonding strength. This allows stress to be effectively transferred from the relatively flexible polyurethane matrix to the high-strength graphene sheets, fully leveraging the reinforcing effect of graphene, improving the fabric's abrasion resistance, and preventing damage during the use of protective clothing.

[0019] 4. This invention involves argon / oxygen plasma treatment of high molecular weight polyethylene nonwoven fabric. The plasma treatment, through high-energy particle bombardment, introduces polar oxygen-containing groups such as hydroxyl and carboxyl groups onto the surface of the nonwoven fibers, significantly increasing the surface energy and wettability of the nonwoven fabric. This transforms it from a non-polar surface to a polar surface, allowing the subsequently applied functional coating adhesive to spread evenly and penetrate into the fiber interior. The coating adhesive can form hydrogen bonds or chemical bonds with the amino and hydroxyl groups in the functional coating adhesive, achieving chemical bonding and further strengthening the interfacial adhesion between the coating and the substrate. This prevents the coating from peeling or flaking during use. Furthermore, plasma etching can generate micro-nano-level roughness on the nonwoven fabric surface, increasing the specific surface area and further improving the coating's anchoring effect. Simultaneously, it maintains the original porous and breathable structure of the nonwoven fabric. The modified nonwoven fabric bonds more tightly with the functional coating adhesive, and the resulting protective barrier layer has no interfacial gaps, reducing the possibility of chemical media penetrating from the coating-substrate interface, ensuring the density of the protective barrier layer, and improving the overall chemical protection effect of the fabric. Attached Figure Description

[0020] Figure 1 This is a flowchart illustrating the manufacturing process of the multi-layer composite chemical protective clothing fabric used in an embodiment of the present invention.

[0021] Figure 2 The present invention provides the reactive structural formula of the hydrophobic modifier in an embodiment of the present invention. Detailed Implementation

[0022] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of this invention.

[0023] Example 1: A preparation process for a multi-layer composite chemical protective clothing fabric, referring to... Figures 1-2 ,include: S1: Preparation of hydrophobic modifier S1.1: Mix 10 parts by weight of sodium hydroxide and 35 parts by weight of 1H,1H,2H,2H-perfluoro-1-octanol, then stir and mix at 35°C for 20 min, then add 30 parts by weight of epichlorohydrin, stir and react for 6 h, after the reaction is complete, perform rotary evaporation, then wash with a deionized water-dichloromethane mixture under ice bath until neutral, concentrate by rotary evaporation to obtain intermediate product; S1.2: Under ice bath conditions, 1 part by weight of 1,4-butanediol and 20 parts by weight of toluene were mixed, followed by the addition of 2 parts by weight of boron trifluoride ether and reaction for 20 min. Then, 30 parts by weight of intermediate product and 35 parts by weight of propylene oxide were added, and the reaction was continued for 4 h. After the reaction was completed, 4 parts by weight of deionized water were added, followed by rotary evaporation for concentration. The concentrated product was placed in an ice bath at 0 °C and purified by washing with a deionized water-dichloromethane mixture. After dehydration treatment with anhydrous magnesium sulfate, the hydrophobic modifier was obtained. The deionized water-dichloromethane mixed system consists of deionized water and dichloromethane in a volume ratio of 1:1. S2: Preparation of modified waterborne polyurethane S2.1: Mix 16 parts by weight of isophorone diisocyanate, 40 parts by weight of polytetrahydrofuran ether diol, 7 parts by weight of hydrophobic modifier and 3 parts by weight of dihydroxy polymethyltrifluoropropylsiloxane, then preheat the mixture at 75°C for 20 min, then raise the temperature to 75°C, add 0.05 parts by weight of catalyst dibutyltin dilaurate, and react for 2 h to obtain the prepolymer; S2.2: Then, at 75°C, 2 parts by weight of 2,2-dimethylolpropionic acid were added to the prepolymer and reacted for 3 hours. After the reaction was completed, the temperature was lowered to 45°C. During the cooling process, 10 parts by weight of acetone were added to adjust the viscosity. After cooling, 3 parts by weight of triethylamine were added and reacted for 10 minutes. After the reaction was completed, 20 parts by weight of deionized water were added and stirred and dispersed at 1300 rpm for 20 minutes. Then, acetone was removed by vacuum distillation to obtain modified waterborne polyurethane. S3: Preparation of modified graphene fillers S3.1: Add 2 parts by weight of expandable graphite powder to a quartz crucible, then place it in a microwave atmosphere sintering furnace and microwave heat treat it at 600℃ for 1 min under a nitrogen atmosphere. Add 2 parts by weight of microwave heat treated graphite powder to 200 parts by weight of n-butanol, then ultrasonically disperse for 20 min. Add the ultrasonically dispersed dispersion to a planetary ball mill and add zirconia beads at a ball-to-material ratio of 8:1. Ball mill at 300 rpm for 40 h, then centrifuge at 10000 rpm for 20 min. The suspension after centrifugation is evaporated under vacuum at room temperature to obtain ball-milled graphene. S3.2: Add 3 parts by weight of ammonium persulfate to 30 parts by weight of ammonia water, stir and mix at 300 rpm for 20 min to obtain an initiator solution, add 10 parts by weight of ball-milled graphene and 20 parts by weight of m-phenylenediamine to 80 parts by weight of ammonia water, and then sonicate for 20 min to obtain a mixed solution. S3.3: The initiator solution was added to the mixed solution at 200 rpm, and then the reaction was continued to be stirred at 25°C for 3 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 20 min, and then the centrifuged precipitate was washed three times with deionized water and then vacuum dried to obtain the modified graphene filler. S4: Preparation of protective barrier layer fabric S4.1: Add 5 parts by weight of modified graphene filler to 100 parts by weight of modified waterborne polyurethane, then add 0.1 parts by weight of leveling agent BYK-300 and 0.1 parts by weight of defoamer BYK-019, stir and mix at 300 rpm for 30 min, and then let stand for 1 h to obtain functional coating adhesive. S4.2: Soak the high molecular weight polyethylene nonwoven fabric in anhydrous ethanol for 2 min, then wash it 3 times with deionized water, and then dry it in an oven at 30℃ for 10 h. The dried nonwoven fabric is then subjected to plasma treatment with argon / oxygen at 80 W for 30 s, with the volume ratio of argon to oxygen being 9:1, to obtain the pretreated nonwoven fabric. S4.3: The functional coating adhesive is applied to the surface of the pretreated nonwoven fabric by a doctor blade coating machine. The wet coating thickness is 50 micrometers. The coated nonwoven fabric is placed in an oven and then dried with hot air at 80°C for 2 minutes. After that, the temperature is raised to 120°C for 3 minutes to obtain the protective barrier layer fabric. S5: Preparation of Chemical Protective Clothing Fabrics S5.1: The inner fabric is made by blending spandex fiber, bamboo fiber and viscose fiber in a ratio of 3:1:1, and the outer fabric is made by blending aramid fiber and nylon in a ratio of 1:1. S5.2: The inner layer fabric, PUR hot melt adhesive, neoprene rubber layer, PUR hot melt adhesive, protective barrier layer fabric, PUR hot melt adhesive and outer layer fabric are sequentially hot-pressed to obtain chemical protective clothing fabric, wherein the hot-pressing temperature is 150℃, the pressure is 0.5MPa and the hot-pressing time is 10s.

[0024] Example 2, a preparation process for a multi-layer composite chemical protective clothing fabric, see [link to example]. Figures 1-2 ,include: S1: Preparation of hydrophobic modifier S1.1: 12 parts by weight of sodium hydroxide and 40 parts by weight of 1H,1H,2H,2H-perfluoro-1-octanol were mixed and stirred at 40°C for 30 min. Then, 32 parts by weight of epichlorohydrin were added and the mixture was stirred for 8 h. After the reaction was completed, the mixture was rotary evaporated. Then, a deionized water-dichloromethane mixture was added under ice bath and washed until neutral. The mixture was concentrated by rotary evaporation to obtain the intermediate product. S1.2: Under ice bath conditions, 2 parts by weight of 1,4-butanediol and 30 parts by weight of toluene were mixed, followed by the addition of 3 parts by weight of boron trifluoride ether and reaction for 30 min. Then, 40 parts by weight of the intermediate product and 35-40 parts by weight of propylene oxide were added, and the reaction was continued for 5 h. After the reaction was completed, 5 parts by weight of deionized water were added, followed by rotary evaporation for concentration. The concentrated product was placed in an ice bath at 0 °C and purified by washing with a deionized water-dichloromethane mixture. After dehydration treatment with anhydrous magnesium sulfate, the hydrophobic modifier was obtained. The deionized water-dichloromethane mixed system consists of deionized water and dichloromethane in a volume ratio of 1:1. S2: Preparation of modified waterborne polyurethane S2.1: Mix 18 parts by weight of isophorone diisocyanate, 50 parts by weight of polytetrahydrofuran ether diol, 8 parts by weight of hydrophobic modifier and 5 parts by weight of dihydroxy polymethyltrifluoropropylsiloxane, then preheat the mixture at 80°C for 30 min, then raise the temperature to 85°C, add 0.08 parts by weight of catalyst dibutyltin dilaurate, and react for 3 h to obtain the prepolymer; S2.2: Then, at 80℃, 3 parts by weight of 2,2-dimethylolpropionic acid were added to the prepolymer and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 48℃. During the cooling process, 12 parts by weight of acetone were added to adjust the viscosity. After cooling, 4 parts by weight of triethylamine were added and reacted for 12 minutes. After the reaction was completed, 30 parts by weight of deionized water were added and stirred and dispersed at 1400 rpm for 30 minutes. Then, acetone was removed by vacuum distillation to obtain modified waterborne polyurethane. S3: Preparation of modified graphene fillers S3.1: Add 3 parts by weight of expandable graphite powder to a quartz crucible, then place it in a microwave atmosphere sintering furnace and microwave heat treat it at 660°C for 2 min under a nitrogen atmosphere. Add 3 parts by weight of microwave heat treated graphite powder to 230 parts by weight of n-butanol, then ultrasonically disperse it for 30 min. Add the ultrasonically dispersed dispersion to a planetary ball mill and add zirconium oxide beads at a ball-to-material ratio of 10:1. Ball mill at 320 rpm for 48 h, then centrifuge at 12000 rpm for 30 min. The suspension after centrifugation is evaporated under vacuum at room temperature to obtain ball-milled graphene. S3.2: Add 5 parts by weight of ammonium persulfate to 50 parts by weight of ammonia water, stir and mix at 500 rpm for 30 min to obtain an initiator solution, add 12 parts by weight of ball-milled graphene and 22 parts by weight of m-phenylenediamine to 100 parts by weight of ammonia water, and then sonicate for 30 min to obtain a mixed solution. S3.3: The initiator solution was added to the mixed solution at 300 rpm, and then the reaction was continued at 30°C for 5 h. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 30 min. The centrifuged precipitate was then washed 5 times with deionized water and then vacuum dried to obtain the modified graphene filler. S4: Preparation of protective barrier layer fabric S4.1: Add 8 parts by weight of modified graphene filler to 120 parts by weight of modified waterborne polyurethane, then add 0.3 parts by weight of leveling agent BYK-300 and 0.3 parts by weight of defoamer BYK-019, stir and mix at 500 rpm for 40 min, and then let stand for 2 h to obtain functional coating adhesive. S4.2: Soak the high molecular weight polyethylene nonwoven fabric in anhydrous ethanol for 3 min, then wash it 5 times with deionized water, and then dry it in an oven at 40℃ for 12 h. The dried nonwoven fabric is then subjected to plasma treatment with argon / oxygen at 100W for 40 s, with the volume ratio of argon to oxygen being 9:1, to obtain the pretreated nonwoven fabric. S4.3: The functional coating adhesive is applied to the surface of the pretreated nonwoven fabric by a doctor blade coating machine. The wet coating thickness is 80 micrometers. The coated nonwoven fabric is placed in an oven and then dried with hot air at 100°C for 4 minutes. After that, the temperature is raised to 130°C for 5 minutes to obtain the protective barrier layer fabric. S5: Preparation of Chemical Protective Clothing Fabrics S5.1: The inner fabric is made by blending spandex fiber, bamboo fiber and viscose fiber in a ratio of 3:1:1, and the outer fabric is made by blending aramid fiber and nylon in a ratio of 1:1. S5.2: The inner layer fabric, PUR hot melt adhesive, neoprene rubber layer, PUR hot melt adhesive, protective barrier layer fabric, PUR hot melt adhesive and outer layer fabric are sequentially hot-pressed to obtain chemical protective clothing fabric, wherein the hot-pressing temperature is 160℃, the pressure is 0.6MPa and the hot-pressing time is 20s.

[0025] Example 3, a preparation process for a multi-layer composite chemical protective clothing fabric, see [link to example]. Figures 1-2 ,include: S1: Preparation of hydrophobic modifier S1.1: 11 parts by weight of sodium hydroxide and 37.5 parts by weight of 1H,1H,2H,2H-perfluoro-1-octanol were mixed and stirred at 37.5°C for 25 min. Then, 31 parts by weight of epichlorohydrin were added and the mixture was stirred for 7 h. After the reaction was completed, the mixture was rotary evaporated. Then, the mixture was washed with a deionized water-dichloromethane mixture under ice bath until neutral. The mixture was concentrated by rotary evaporation to obtain the intermediate product. S1.2: Under ice bath conditions, 1.5 parts by weight of 1,4-butanediol and 25 parts by weight of toluene were mixed, followed by the addition of 2.5 parts by weight of boron trifluoride ether and reaction for 25 min. Then, 35 parts by weight of intermediate product and 37.5 parts by weight of propylene oxide were added, and the reaction was continued for 4.5 h. After the reaction was completed, 4.5 parts by weight of deionized water were added, followed by rotary evaporation for concentration. The concentrated product was placed in an ice bath at 0 °C and purified by washing with a deionized water-dichloromethane mixture. After dehydration treatment with anhydrous magnesium sulfate, a hydrophobic modifier was obtained. The deionized water-dichloromethane mixed system consists of deionized water and dichloromethane in a volume ratio of 1:1. S2: Preparation of modified waterborne polyurethane S2.1: Mix 17 parts by weight of isophorone diisocyanate, 45 parts by weight of polytetrahydrofuran ether diol, 7.5 parts by weight of hydrophobic modifier and 4 parts by weight of dihydroxy polymethyltrifluoropropylsiloxane, then preheat the mixture at 77.5°C for 25 min, then raise the temperature to 80°C, add 0.065 parts by weight of catalyst dibutyltin dilaurate, and react for 2.5 h to obtain the prepolymer; S2.2: Then, at 77.5℃, 2.5 parts by weight of 2,2-dimethylolpropionic acid were added to the prepolymer and reacted for 4 hours. After the reaction was completed, the temperature was lowered to 46.5℃. During the cooling process, 11 parts by weight of acetone were added to adjust the viscosity. After cooling, 3.5 parts by weight of triethylamine were added and reacted for 11 minutes. After the reaction was completed, 25 parts by weight of deionized water were added and the mixture was stirred and dispersed at 1350 rpm for 25 minutes. Then, acetone was removed by vacuum distillation to obtain modified waterborne polyurethane. S3: Preparation of modified graphene fillers S3.1: 2.5 parts by weight of expandable graphite powder were added to a quartz crucible and then placed in a microwave atmosphere sintering furnace. The crucible was microwave heat-treated at 630°C for 1.5 min under a nitrogen atmosphere. 2.5 parts by weight of the microwave heat-treated graphite powder were added to 215 parts by weight of n-butanol and then ultrasonically dispersed for 25 min. The ultrasonically dispersed dispersion was added to a planetary ball mill and zirconia beads were added. The ball-to-material ratio was 9:1. The mixture was ball-milled at 310 rpm for 44 h and then centrifuged at 11000 rpm for 25 min. The suspension after centrifugation was evaporated under vacuum at room temperature to obtain ball-milled graphene. S3.2: Add 4 parts by weight of ammonium persulfate to 40 parts by weight of ammonia water, stir and mix at 400 rpm for 25 min to obtain an initiator solution, add 11 parts by weight of ball-milled graphene and 21 parts by weight of m-phenylenediamine to 90 parts by weight of ammonia water, and then sonicate for 25 min to obtain a mixed solution. S3.3: The initiator solution was added to the mixed solution at 250 rpm, and the reaction was continued at 27.5℃ for 4 h. After the reaction was completed, the mixture was centrifuged at 9000 rpm for 25 min. The centrifuged precipitate was then washed 4 times with deionized water and then vacuum dried to obtain the modified graphene filler. S4: Preparation of protective barrier layer fabric S4.1: Add 6.5 parts by weight of modified graphene filler to 110 parts by weight of modified waterborne polyurethane, then add 0.2 parts by weight of leveling agent BYK-300 and 0.2 parts by weight of defoamer BYK-019, stir and mix at 400 rpm for 35 min, and then let stand for 1.5 h to obtain functional coating adhesive. S4.2: Soak the high molecular weight polyethylene nonwoven fabric in anhydrous ethanol for 2.5 min, then wash it 4 times with deionized water, and then dry it in an oven at 35℃ for 11 h. The dried nonwoven fabric is then subjected to plasma treatment with argon / oxygen at 90 W for 35 s, with an argon to oxygen volume ratio of 9:1, to obtain the pretreated nonwoven fabric. S4.3: The functional coating adhesive is applied to the surface of the pretreated nonwoven fabric by a doctor blade coating machine. The wet coating thickness is 65 microns. The coated nonwoven fabric is placed in an oven and then dried with hot air at 90°C for 3 minutes. After that, the temperature is raised to 125°C for 4 minutes to obtain the protective barrier layer fabric. S5: Preparation of Chemical Protective Clothing Fabrics S5.1: The inner fabric is made by blending spandex fiber, bamboo fiber and viscose fiber in a ratio of 3:1:1, and the outer fabric is made by blending aramid fiber and nylon in a ratio of 1:1. S5.2: The inner layer fabric, PUR hot melt adhesive, neoprene rubber layer, PUR hot melt adhesive, protective barrier layer fabric, PUR hot melt adhesive and outer layer fabric are sequentially hot-pressed to obtain chemical protective clothing fabric, wherein the hot-pressing temperature is 155℃, the pressure is 0.55MPa and the hot-pressing time is 15s.

[0026] Comparative Example 1 differs from Example 1 in that the hydrophobic modifier in steps S1 and S2.1 is removed, while the remaining steps remain unchanged in the preparation of the chemical protective clothing fabric. This is referred to as Comparative Example 1.

[0027] Comparative Example 2 differs from Example 1 in that the dihydroxy polymethyltrifluoropropylsiloxane in step S2.1 is removed, while the remaining steps remain unchanged in the preparation of the chemical protective clothing fabric. This is referred to as Comparative Example 2.

[0028] Comparative Example 3 differs from Example 1 in that the hydrophobic modifier and dihydroxy polymethyltrifluoropropylsiloxane in steps S1 and S2.1 are removed, while the remaining steps remain unchanged in the preparation of the chemical protective clothing fabric. This is referred to as Comparative Example 3.

[0029] Comparative Example 4 differs from Example 1 in that step S3 is removed, and the modified graphene filler in step S4.1 is replaced with an equal amount of graphene filler, while the remaining steps remain unchanged in the preparation of chemical protective clothing fabric. This is referred to as Comparative Example 4.

[0030] Comparative Example 5 differs from Example 1 in that step S4.2 is removed, and the pre-treated nonwoven fabric in step S4.3 is replaced with high molecular weight polyethylene nonwoven fabric, while the remaining steps remain unchanged in the preparation of chemical protective clothing fabric. This is referred to as Comparative Example 5.

[0031] Chemical penetration resistance test: The chemical protective clothing fabrics prepared in Examples 1-3 and Comparative Examples 1-5 were tested for their chemical penetration resistance time against 48% hydrofluoric acid, 28% ammonia, n-hexane, phenol, methanol, 90% sulfuric acid, 37% hydrochloric acid, and 30% sodium hydroxide, respectively, in accordance with GB / T23462-2009. The tests were conducted three times, and the average value was taken. The test results are shown in Table 1.

[0032] Table 1. Results of chemical penetration resistance time determination for Examples 1-3 and Comparative Examples 1-5 48% hydrofluoric acid (min) 28% ammonia solution (min) n-Hexane (min) Phenol (min) Methanol (min) 90% sulfuric acid (min) 37% hydrochloric acid (min) 30% sodium hydroxide (min) Example 1 272 338 264 243 213 424 398 456 Example 2 286 347 277 258 224 435 407 463 Example 3 278 341 269 252 218 429 402 458 Comparative Example 1 167 205 152 141 128 322 315 350 Comparative Example 2 189 235 168 155 142 331 328 365 Comparative Example 3 144 168 125 118 98 248 239 273 Comparative Example 4 201 251 182 168 155 365 358 389 Comparative Example 5 239 287 224 208 179 382 375 415 As can be seen from the data in Table 1, the chemical protective clothing fabric prepared by this invention has good protective capabilities and good resistance to penetration by both organic and inorganic solvents.

[0033] The data from Comparative Examples 1-3 show that adding hydrophobic modifiers and dihydroxy polymethyltrifluoropropylsiloxane to polyurethane synthesis can significantly improve the protective performance of the fabric. Furthermore, the two have a synergistic effect. The functional coating adhesive prepared by polyurethane modified by the two can form a barrier film on the surface of polyethylene nonwoven fabric, thereby significantly improving the protective fabric's ability to block chemicals such as acids, alkalis, and organic solvents.

[0034] The data from Comparative Example 4 show that, compared to directly adding graphene filler, adding modified graphene filler can effectively improve chemical protection capabilities.

[0035] The data from Comparative Example 5 show that argon / oxygen plasma treatment of high molecular weight polyethylene nonwoven fabric can improve the overall chemical protection effect of the fabric.

[0036] Abrasion resistance test: The abrasion resistance of the chemical protective clothing fabrics prepared in Examples 1-3 and Comparative Example 4 was tested three times, and the average value was taken. The test results are shown in Table 2.

[0037] Abrasion resistance: The mass loss rate after 20,000 abrasion cycles was tested using a Martindale abrasion tester.

[0038] Table 2. Abrasion resistance test results of Examples 1-3 and Comparative Example 4 Quality loss rate (%) Example 1 0.12 Example 2 0.09 Example 3 0.11 Comparative Example 4 0.34 As can be seen from the data in Table 2, compared with directly adding graphene filler, the modified graphene filler added in this invention can significantly improve the abrasion resistance of the fabric and is less prone to damage during the use of protective clothing.

[0039] Air permeability and moisture permeability test: The air permeability and moisture permeability of the fabrics prepared in Examples 1-3 were tested three times, and the average value was taken. The test results are shown in Table 3. Air permeability: GB / T 5453-1997; Moisture permeability: ISO15496 (MVTR method).

[0040] Table 3. Results of air permeability tests in Examples 1-3 <![CDATA[Air permeability (L / m 2 ·s)]]> <![CDATA[Water vapor permeability (g / m 2 ·24 h)]]> Example 1 187 7284 Example 2 184 7276 Example 3 185 7289 As can be seen from the data in Table 3, the fabric prepared by this invention has good breathability and moisture permeability, which can reduce the stuffiness when wearing it and improve comfort.

[0041] It should be understood that those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims. Parts not described in detail in this specification are prior art known to those skilled in the art.

Claims

1. A multi-layer composite chemical protective clothing fabric, characterized in that, include: Inner fabric, neoprene layer, protective barrier layer fabric, and outer fabric; The inner fabric is made of a blend of spandex fiber, bamboo fiber and viscose fiber in a 3:1:1 ratio. The protective barrier layer fabric is made of high molecular weight polyethylene nonwoven fabric coated with functional coating adhesive; The functional coating adhesive is composed of 100-120 parts by weight of modified waterborne polyurethane, 5-8 parts by weight of modified graphene filler, 0.1-0.3 parts by weight of leveling agent, and 0.1-0.3 parts by weight of defoamer; The modified waterborne polyurethane is prepared from 16-18 parts by weight of isophorone diisocyanate, 40-50 parts by weight of polytetrahydrofuran ether diol, 7-8 parts by weight of hydrophobic modifier, 3-5 parts by weight of dihydroxy polymethyltrifluoropropylsiloxane, 0.05-0.08 parts by weight of catalyst and 2-3 parts by weight of 2,2-dimethylolpropionic acid as raw materials. The hydrophobic modifier is prepared from 10-12 parts by weight of sodium hydroxide, 35-40 parts by weight of 1H,1H,2H,2H-perfluoro-1-octanol, 30-32 parts by weight of epichlorohydrin, 1-2 parts by weight of 1,4-butanediol, 20-30 parts by weight of toluene, 2-3 parts by weight of boron trifluoride ether, and 35-40 parts by weight of propylene oxide as raw materials, through stepwise reaction, washing, concentration, dehydration and purification. The outer fabric is made of aramid fiber and nylon blended in a 1:1 ratio.

2. A preparation process for the multi-layer composite chemical protective clothing fabric as described in claim 1, characterized in that, include: S1: Preparation of hydrophobic modifier; The intermediate product was obtained by reacting 1H,1H,2H,2H-perfluoro-1-octanol with epichlorohydrin, and then reacted with 1,4-butanediol and propylene oxide under the catalysis of boron trifluoride ether. After purification, a hydrophobic modifier was obtained. S2: Preparation of modified waterborne polyurethane; Isophorone diisocyanate, polytetrahydrofuran ether diol, hydrophobic modifier and dihydroxy polymethyltrifluoropropylsiloxane were prepolymerized, and then 2,2-dimethylolpropionic acid was added for chain extension. After neutralization, modified waterborne polyurethane was obtained. S3: Preparation of modified graphene filler; Expandable graphite was expanded by microwave and exfoliated by liquid-phase ball milling to obtain ball-milled graphene. Then, using ammonium persulfate as an initiator, m-phenylenediamine was polymerized on the surface of the ball-milled graphene in an ammonia system to obtain modified graphene filler. S4: Preparation of protective barrier layer fabric; Modified waterborne polyurethane and modified graphene filler were mixed and additives were added to prepare a functional coating adhesive. The coating adhesive was applied to the surface of plasma-treated high molecular weight polyethylene nonwoven fabric and dried and cured to obtain a protective barrier layer fabric. S5: Preparation of chemical protective clothing fabric; The inner fabric, neoprene layer, protective barrier layer fabric, and outer fabric are hot-pressed together using hot melt adhesive to obtain a multi-layer composite chemical protective clothing fabric.

3. The preparation process of a multi-layer composite chemical protective clothing fabric according to claim 2, characterized in that, S1: The preparation of the hydrophobic modifier includes the following steps: S1.1: Mix 10-12 parts by weight of sodium hydroxide and 35-40 parts by weight of 1H,1H,2H,2H-perfluoro-1-octanol, then stir and mix at 35-40℃ for 20-30 min, then add 30-32 parts by weight of epichlorohydrin, stir and react for 6-8 h, after the reaction is complete, perform rotary evaporation, then wash with a deionized water-dichloromethane mixture under ice bath until neutral, and concentrate by rotary evaporation to obtain the intermediate product; S1.2: Under ice bath conditions, 1-2 parts by weight of 1,4-butanediol and 20-30 parts by weight of toluene are mixed, followed by the addition of 2-3 parts by weight of boron trifluoride diethyl ether and reaction for 20-30 min. Then, 30-40 parts by weight of intermediate product and 35-40 parts by weight of propylene oxide are added, and the reaction is continued for 4-5 h. After the reaction is completed, 4-5 parts by weight of deionized water are added, followed by rotary evaporation for concentration. The concentrated product is placed in an ice bath at 0 °C and purified by washing with a deionized water-dichloromethane mixture. After dehydration treatment with anhydrous magnesium sulfate, the hydrophobic modifier is obtained.

4. The preparation process of a multi-layer composite chemical protective clothing fabric according to claim 3, characterized in that, The deionized water-dichloromethane mixture in step S1 consists of deionized water and dichloromethane in a volume ratio of 1:

1.

5. The preparation process of a multi-layer composite chemical protective clothing fabric according to claim 2, characterized in that, S2: The preparation of modified waterborne polyurethane includes the following steps: S2.1: Mix 16-18 parts by weight of isophorone diisocyanate, 40-50 parts by weight of polytetrahydrofuran ether diol, 7-8 parts by weight of hydrophobic modifier and 3-5 parts by weight of dihydroxy polymethyltrifluoropropylsiloxane, then preheat the mixture at 75-80℃ for 20-30 min, then raise the temperature to 75-85℃, add 0.05-0.08 parts by weight of catalyst dibutyltin dilaurate, and react for 2-3 h to obtain the prepolymer; S2.2: Then, at 75-80℃, add 2-3 parts by weight of 2,2-dimethylolpropionic acid to the prepolymer and react for 3-5 hours. After the reaction is completed, cool down to 45-48℃. During the cooling process, add 10-12 parts by weight of acetone to adjust the viscosity. After cooling, add 3-4 parts by weight of triethylamine and react for 10-12 minutes. After the reaction is completed, add 20-30 parts by weight of deionized water and stir and disperse at 1300-1400 rpm for 20-30 minutes. Then, remove acetone by vacuum distillation to obtain modified waterborne polyurethane.

6. The preparation process of a multi-layer composite chemical protective clothing fabric according to claim 2, characterized in that, S3: the preparation of modified graphene filler specifically includes the following steps: S3.1: Add 2-3 parts by weight of expandable graphite powder to a quartz crucible, then place it in a microwave atmosphere sintering furnace and microwave heat treat it at 600-660℃ for 1-2 minutes under a nitrogen atmosphere. Add 2-3 parts by weight of the microwave heat treated graphite powder to 200-230 parts by weight of n-butanol, then ultrasonically disperse it for 20-30 minutes. Add the ultrasonically dispersed dispersion to a planetary ball mill and add zirconium oxide beads at a ball-to-material ratio of 8-10:

1. Ball mill at 300-320 rpm for 40-48 hours, then centrifuge at 10000-12000 rpm for 20-30 minutes. The centrifuged suspension is then evaporated under vacuum at room temperature to obtain ball-milled graphene. S3.2: Add 3-5 parts by weight of ammonium persulfate to 30-50 parts by weight of ammonia water, stir and mix at 300-500 rpm for 20-30 min to obtain an initiator solution, add 10-12 parts by weight of ball-milled graphene and 20-22 parts by weight of m-phenylenediamine to 80-100 parts by weight of ammonia water, and then sonicate for 20-30 min to obtain a mixed solution; S3.3: Add the initiator solution to the mixed solution at 200-300 rpm, and then continue to stir the reaction at 25-30℃ for 3-5 h. After the reaction is completed, centrifuge at 8000-10000 rpm for 20-30 min, then wash the centrifuged precipitate with deionized water 3-5 times, and then vacuum dry to obtain the modified graphene filler.

7. The preparation process of a multi-layer composite chemical protective clothing fabric according to claim 2, Its characteristic is that, S4: the preparation of the protective barrier layer fabric specifically includes the following steps: S4.1: Add 5-8 parts by weight of modified graphene filler to 100-120 parts by weight of modified waterborne polyurethane, then add 0.1-0.3 parts by weight of leveling agent BYK-300 and 0.1-0.3 parts by weight of defoamer BYK-019. Stir and mix at 300-500 rpm for 30-40 minutes, then let stand for 1-2 hours to obtain functional coating adhesive. S4.2: Soak the high molecular weight polyethylene nonwoven fabric in anhydrous ethanol for 2-3 minutes, then wash it with deionized water 3-5 times, and then dry it in an oven at 30-40℃ for 10-12 hours. The dried nonwoven fabric is then subjected to plasma treatment with argon / oxygen to obtain pretreated nonwoven fabric. S4.3: Apply functional coating adhesive to the surface of the pretreated nonwoven fabric using a doctor blade coating machine. The wet coating thickness is 50-80 micrometers. Place the coated nonwoven fabric in an oven and dry it with hot air at 80-100℃ for 2-4 minutes. Then, raise the temperature to 120-130℃ for 3-5 minutes to obtain the protective barrier layer fabric.

8. The preparation process of a multi-layer composite chemical protective clothing fabric according to claim 7, characterized in that, In step S4.2, the plasma treatment parameters are 80-100W for 30-40s, and the volume ratio of argon to oxygen is 9:

1.

9. The preparation process of a multi-layer composite chemical protective clothing fabric according to claim 2, characterized in that, S5: The preparation of chemical protective clothing fabric includes the following steps: S5.1: The inner fabric is made by blending spandex fiber, bamboo fiber and viscose fiber in a ratio of 3:1:1, and the outer fabric is made by blending aramid fiber and nylon in a ratio of 1:

1. S5.2: The inner layer fabric, PUR hot melt adhesive, neoprene rubber layer, PUR hot melt adhesive, protective barrier layer fabric, PUR hot melt adhesive and outer layer fabric are sequentially hot-pressed together to obtain chemical protective clothing fabric.

10. The preparation process of a multi-layer composite chemical protective clothing fabric according to claim 9, characterized in that, In step S5.2, the hot-pressing temperature is 150-160℃, the pressure is 0.5-0.6MPa, and the hot-pressing time is 10-20s.

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