A breathable rubber material for protection against harmful chemical agents, and a method for its production and use

Abstract

The application relates to a breathable rubber material for protecting harmful chemical reagents and a preparation method and application thereof, and belongs to the technical field of harmful chemical reagent protection materials. The breathable rubber material for protecting harmful chemical reagents provided by the application comprises a protection layer, an adsorption layer and a close-fitting layer which are sequentially connected and are bonded through hot melt glue between two adjacent layers; the adsorption layer comprises, in terms of weight fractions, 45-75 parts of rubber latex, 30-50 parts of adsorption particles, 0.5-2.5 parts of an anti-aging agent, 0.5-3 parts of sulfur, 0.5-5 parts of zinc oxide, 0.1-3 parts of a vulcanization accelerator, 0.1-1 part of an alkaline pH regulator and 0.01-0.1 part of a stabilizer. The adsorption layer of the breathable rubber material adopts rubber aerogel loaded adsorption particles, and is combined with the protection layer and the close-fitting layer, so that the prepared material is more excellent in breathability, good in adsorption performance and resistant to rubbing and machine washing, the breathability, chemical reagent protection performance and practicability of the rubber protection material are effectively improved, and the breathable rubber material can be widely applied to the field of protective clothing.

Description

Technical Field

[0001] This application relates to a breathable rubber material for protection against harmful chemical reagents, its preparation method and application, belonging to the technical field of materials for protecting against harmful chemical reagents. Background Technology

[0002] The primary purpose of chemical protective clothing is to protect the human body from external hazards such as chemicals, heat, mechanical agents, biological agents, and radiation, while maintaining a safe and comfortable microclimate around the skin. However, comfort and protective capability are two contradictory goals, and maximizing comfort while ensuring adequate protective capabilities is the main challenge facing chemical protective clothing.

[0003] Chemical protective clothing is mainly divided into two types: isolation protective clothing and breathable protective clothing. Isolation protective clothing is primarily made of non-breathable protective membrane material, offering excellent isolation performance but poor breathability and moisture permeability, making workers susceptible to heatstroke when used in hot conditions. Breathable protective clothing, on the other hand, blocks the intrusion of external toxic droplets and vapors while allowing internal water vapor to escape, combining protection and comfort, and thus has a wider range of applications.

[0004] However, the protective effect of breathable protective clothing in current technologies is not ideal, mainly because the adsorption efficiency of its internal adsorbent particles for harmful molecules is low. For example, Chinese patent CN202110585676 discloses a composite fabric for protective clothing and its preparation method, in which activated carbon is directly adhered to the adhesive-coated base fabric. Due to the excessively large contact area between the activated carbon and the adhesive, its breathability is greatly weakened. Chinese patent CN201821040739 discloses a composite structure including a fabric layer and a spherical activated carbon layer, wherein the surface of the fabric layer facing the spherical activated carbon has a recess extending from the surface to the interior of the fabric layer, and at least a portion of the outer surface of the spherical activated carbon is bonded to at least a portion of the inner surface of the recess, thereby avoiding the use of excessive adhesive. However, in this solution, the adhesion between the activated carbon and the base fabric is weak, and the activated carbon is prone to falling off after repeated use, especially after washing in a washing machine, thus affecting the protective effect.

[0005] Given the problems with existing breathable protective clothing, there is an urgent need to develop a breathable chemical protective material with high adsorption efficiency and washability. Summary of the Invention

[0006] To address the aforementioned issues, this application provides a breathable rubber material for protection against harmful chemical reagents, along with its preparation method and application. The breathable rubber material provided employs an adsorption layer with rubber aerogel loaded with adsorbent particles, combined with a protective layer and a close-fitting layer. The resulting material exhibits superior breathability, excellent adsorption performance, and resistance to rubbing and machine washing, effectively improving the breathability, chemical reagent protection performance, and practicality of the rubber protective material. It can be widely applied in the field of protective clothing.

[0007] This application provides a breathable rubber material for protection against harmful chemical reagents. The breathable rubber material includes a protective layer, an absorbent layer, and a skin-fitting layer connected in sequence, and adjacent layers are bonded together by hot melt adhesive. By weight, the adsorption layer comprises: 45-75 parts rubber latex, 30-50 parts adsorption particles, 0.5-2.5 parts antioxidant, 0.5-3 parts sulfur, 0.5-5 parts zinc oxide, 0.1-3 parts vulcanization accelerator, 0.1-1 parts alkaline pH adjuster, and 0.01-0.1 parts stabilizer.

[0008] Compared to the low chemical adsorption of traditional breathable protective clothing, this application can effectively improve the adsorption efficiency of adsorbent particles by uniformly dispersing adsorbent particles in aerogel. Moreover, this type of aerogel can also ensure that the protective clothing has good breathability, so that it has both breathability and high adsorption efficiency, effectively ensuring the comfort and personal safety of the wearer.

[0009] Optionally, the rubber latex is selected from one or more of natural rubber latex, nitrile rubber latex, styrene-butadiene rubber latex, chloroprene rubber latex, butyl rubber latex, and pentadiene rubber latex. Latex is a general term for colloidal emulsions formed by polymer microparticles dispersed in water, and the aqueous dispersion system of rubber microparticles is usually referred to as rubber latex. The preparation of rubber latex is a routine skill for those skilled in the art and requires no further explanation.

[0010] It should be noted that this application does not limit the specific type of rubber latex. In addition to the common rubber latexes listed above, those skilled in the art can select other rubber latexes or make compounding improvements or even modifications to the components of the rubber latex based on the inventive concept of this application.

[0011] Furthermore, this application is not limited to rubber latex. Other elastomers that can be used as protective materials can also achieve the same technical effect based on the inventive concept of this application. For example, one or more of the following: ethylene-styrene random copolymer, chlorosulfonated polyethylene, chlorinated polyethylene, butadiene homopolymer, isoprene homopolymer, butadiene-isoprene random or block copolymer, and random or block copolymer of ethylene and monomer A, wherein monomer A is selected from one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene.

[0012] Optionally, the adsorbent particles are selected from one or more of activated carbon, biochar, diatomaceous earth, organobentonite, zeolite, and silica aerogel powder.

[0013] Optionally, the average particle size of the adsorbed particles is not greater than 100 μm.

[0014] When the average particle size of the adsorbent particles is too large, the surface area of ​​the adsorbent particles decreases, and the gaps between the particles become larger. Although the air permeability will improve, the adsorption performance of the adsorbent particles will decrease, and they will be unable to adsorb harmful substances in a timely manner.

[0015] Optionally, the alkaline pH adjuster is selected from one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia, sodium bicarbonate, potassium carbonate, trisodium phosphate, sodium citrate, potassium citrate, and sodium lactate; and / or, The stabilizer is selected from one or more of casein, gelatin, sodium lauryl sulfate, potassium laurate, and phenacetin.

[0016] The pH value of the latex may change after the addition of reinforcing fillers. Adding a pH adjuster can maintain the latex pH within a reasonable range, preventing latex flocculation and thus affecting the dispersion effect of the reinforcing fillers. Adding a stabilizer can improve the uniform dispersion of the reinforcing fillers in aqueous mixtures, maintaining good flowability of the rubber latex system and ensuring that the performance of the resulting rubber aerogel is not affected. The synergistic effect of both effectively ensures the uniform dispersion of adsorbed particles within the aerogel cavities, guaranteeing a high adsorption capacity for chemical substances.

[0017] Optionally, the protective layer is selected from one or more of the following: polytetrafluoroethylene microporous membrane, nylon microporous membrane, polyvinylidene fluoride microporous membrane, aramid fiber microporous membrane, and polyurethane microporous fiber membrane; and / or, The inner layer is selected from one or more of the following: cotton fiber fabric, linen fiber fabric, wool fiber fabric, polyester fiber fabric, nylon fiber fabric, acetate fiber fabric, polypropylene fiber fabric, and spandex fiber fabric.

[0018] It should be noted that the present application does not limit the specific selection of the above-mentioned protective layer and the inner layer. In addition to the selections listed above, those skilled in the art can also choose other commonly used materials, and based on the inventive concept of the present application, the same technical effect can be achieved.

[0019] Optionally, the antioxidant is selected from one or more of antioxidants DNP, AW, TMQ, 6PPD, 4020, and BLE; and / or, The vulcanization accelerator is selected from one or more of the following: dithiocarbamates, aldehyde-amine vulcanization accelerators, thiuram vulcanization accelerators, thiazole vulcanization accelerators, and sulfenamide vulcanization accelerators.

[0020] It should be noted that the present application does not limit the specific selection of the antioxidants and vulcanization accelerators listed above. In addition to the selections listed above, those skilled in the art can also choose other commonly used materials, and based on the inventive concept of the present application, the same technical effect can be achieved.

[0021] This application provides a method for preparing the above-mentioned breathable rubber material for protection against harmful chemical reagents, the preparation method comprising the following steps: 1) Preparation of adsorbent layer latex: Add rubber latex, adsorbent particles, antioxidant, vulcanization accelerator, alkaline pH adjuster, stabilizer, sulfur, and zinc oxide into a mixer, add water and stir evenly, and adjust the pH value to 7.8~10 to obtain adsorbent layer latex. 2) Preparation of adsorption layer: After the adsorption layer latex is cast into shape, it is frozen, and then the frozen latex ice block is freeze-dried to obtain a porous rubber aerogel layer. Then the porous rubber aerogel layer is vulcanized to obtain the adsorption layer. 3) Preparation of breathable rubber material: The protective layer and the bonding layer are heated to melt adhesive on one side, and then the adsorption layer is added. After stacking in sequence, the layers are calendered to obtain the breathable rubber material used for protection against harmful chemical reagents.

[0022] This application uses rubber latex, which, compared to ordinary rubber materials, produces a rubber aerogel preparation system with a more uniform structure and better flowability. In addition, the added pH adjuster ensures that the entire latex system will not flocculate due to pH changes, resulting in uneven aerogel morphology or loss of good morphological characteristics, thus avoiding impact on air permeability. Freezing further ensures that the aerogel will not undergo morphological changes during the cooling process, ensuring uniform dispersion of adsorbed particles, ultimately facilitating the acquisition of aerogel products with high adsorption capacity and high air permeability.

[0023] Optionally, in step 1), before adding sulfur and zinc oxide to the rubber latex, they are first ground into a suspension with water; and / or, In step 1), before adding the vulcanization accelerator to the rubber latex, water is added to prepare an aqueous emulsion.

[0024] Formulating sulfur and zinc oxide into a suspension and vulcanization accelerator into an aqueous emulsion can ensure the uniformity and effective dispersion of these three substances in the latex system, ensuring that the latex can be vulcanized efficiently and improving the overall performance of the product.

[0025] Optionally, the thickness of the adsorption layer in step 2) is 4~8 mm; and / or, Vulcanization temperature 140~180℃, time 10~30min.

[0026] It should be noted that the thickness of the adsorption layer in this application can be flexibly adjusted according to specific protection and breathability requirements.

[0027] Optionally, a dispensing process can be used to heat and melt adhesive on one side of the protective layer and the bonding layer. This can reduce the amount of adhesive used to prevent clogging of the holes and increase the interlayer adhesion to prevent the layers from falling off.

[0028] This application provides the use of the above-mentioned breathable rubber material for protection against harmful chemical reagents in the preparation of protective products for protection against harmful chemical reagents.

[0029] Optionally, the product may be a protective suit, a face shield, or a protective blanket.

[0030] The beneficial effects of this application include, but are not limited to: 1. The breathable rubber material for protection against harmful chemical reagents according to this application, its preparation method and application, wherein the breathable rubber material adopts an adsorption layer structure in which rubber aerogel supports adsorbent particles, wherein the rubber aerogel acts as a skeleton to support the adsorbent particles, giving the adsorption layer a certain degree of flexibility and bending resistance, and the aerogel cavity increases the contact area between the adsorbent particles and harmful gas molecules, which can improve the adsorption efficiency. In addition, the aerogel can support the adsorbent particles, making the adhesion between the two stronger, thereby preventing the adsorbent particles from falling off, thus the performance of rubbing and machine washing is also good.

[0031] 2. The breathable rubber material for protection against harmful chemical reagents according to this application, its preparation method and application, wherein the protective layer, the absorbent layer and the close-fitting layer work together, wherein the protective layer has selective permeability, which can prevent harmful reagent droplets from passing through while allowing water molecules to pass through, thus providing initial protection; the close-fitting layer has sweat-wicking and moisture-absorbing properties, which can improve the wearing comfort of the human body; and together with the absorbent layer, it has the advantages of good breathability, absorbency and resistance to rubbing and machine washing.

[0032] 3. The breathable rubber material for protection against harmful chemical reagents according to this application, its preparation method and application, only include a protective layer, an absorbent layer and a close-fitting layer. Therefore, the preparation process is simple, and it can also have excellent chemical protection and breathability. At the same time, it can maintain excellent protective effect after multiple machine washes, making the solution of this application suitable for industrial application and having important economic value for industrial application. In particular, it is used to prepare breathable chemical protective clothing and breathable chemical protective masks, which has obvious technical advantages compared with the prior art. Attached Figure Description

[0033] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings: Figure 1 This is a schematic diagram of the structure of the breathable rubber material for protecting against harmful chemical reagents involved in the embodiments of this application. Detailed Implementation

[0034] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments. Unless otherwise specified, the raw materials and reagents in the embodiments of the present application are all purchased through commercial channels.

[0035] like Figure 1 As shown, this application provides a breathable rubber material for protection against harmful chemical reagents, wherein the outer layer is a protective layer, the inner layer is a close-fitting layer, and the middle layer is an adsorption layer containing rubber aerogel with adsorbed particles. The solution of this application will be described below through specific embodiments.

[0036] Example 1 A breathable rubber material for protection against harmful chemical reagents, comprising, in sequence: The protective layer is a polytetrafluoroethylene microporous membrane with a pore size of 200 nm and a thickness of 0.05 mm. The adsorption layer comprises the following components in parts by weight: 55 parts natural rubber latex, 40 parts activated carbon, 0.8 parts antioxidant 6PPD, 0.7 parts sulfur, 1 part zinc oxide, 1 part thiuram-based vulcanization accelerator TMTD, 0.2 parts ammonia, and 0.04 parts gelatin; wherein the average particle size of the activated carbon is 30µm. The inner layer is made of cotton fiber fabric.

[0037] The preparation method of this breathable rubber material includes the following steps: 1) Preparation of adsorbent layer latex: Rubber latex, adsorbent particles, antioxidant, vulcanization accelerator, alkaline pH adjuster, stabilizer, sulfur, and zinc oxide are added to a mixer according to the weight ratio, and water is used as a solvent to stir and disperse evenly. The pH value is adjusted to 8.5. Sulfur and zinc oxide are first added to water and ground into a suspension before being added to rubber latex, and vulcanization accelerator is first added to water to prepare an aqueous emulsion before being added to rubber latex. 2) Preparation of adsorption layer: The prepared latex was poured into a grooved copper mold with a thickness of 6 mm. The mold was placed in a refrigerator and frozen into ice. The frozen latex ice block was placed in a freeze dryer until all the water sublimated. The freeze dryer was set to a condensation temperature of -50℃, a vacuum degree of -0.05 MPa, and a drying time of 36 h to obtain a porous rubber aerogel layer. The adsorbed particles were uniformly loaded in the internal cavity of the aerogel. The material was then placed in an oven and vulcanized at 150℃ for 20 min. 3) Apply adhesive to one side of the protective layer and the bonding layer at a certain interval, then add the adsorption layer, stack them in sequence and calender them through a calendering roller. Set the calendering pressure to 0.5MPa, the temperature to 120℃, and the fabric advance speed to 1.5m / min to obtain a breathable rubber material that protects against harmful chemical reagents.

[0038] Example 2 A breathable rubber material for protection against harmful chemical reagents, comprising, in sequence: The protective layer is a nylon microporous membrane with a pore size of 200 nm and a thickness of 0.05 mm. The adsorption layer comprises the following materials in parts by weight: 45 parts nitrile rubber latex, 30 parts activated carbon, 0.5 parts antioxidant 4020, 0.5 parts sulfur, 0.5 parts zinc oxide, 0.1 parts sulfenamide vulcanization accelerator NOBS, 0.1 parts sodium hydroxide, and 0.01 parts casein; wherein the average particle size of the activated carbon is 30µm. The inner layer is made of hemp fiber fabric.

[0039] The preparation method of this breathable rubber material includes the following steps: 1) Preparation of adsorbent layer latex: Rubber latex, adsorbent particles, antioxidant, vulcanization accelerator, alkaline pH adjuster, stabilizer, sulfur, and zinc oxide are added to a mixer according to the weight ratio, and water is used as a solvent to stir and disperse evenly. The pH value is adjusted to 7.8. Sulfur and zinc oxide are first added to water and ground into a suspension before being added to rubber latex, and vulcanization accelerator is first added to water to prepare an aqueous emulsion before being added to rubber latex. 2) Preparation of adsorption layer: The prepared latex was poured into a grooved copper mold with a thickness of 4 mm. The mold was placed in a refrigerator and frozen into ice. The frozen latex ice block was placed in a freeze dryer until all the water sublimated. The freeze dryer was set to a condensation temperature of -40℃, a vacuum degree of -0.001 MPa, and a drying time of 24 h to obtain a porous rubber aerogel layer. The adsorbed particles were uniformly loaded in the internal cavity of the aerogel. The material was then placed in an oven and vulcanized at 140℃ for 10 min. 3) Preparation of breathable rubber material: Apply adhesive to one side of the protective layer and the bonding layer at a certain interval, then add the adsorption layer, stack them in sequence and calender them through a calendering roller. Set the calendering pressure to 0.3MPa, the temperature to 100℃, and the fabric advance speed to 1.2m / min to obtain a breathable rubber material that protects against harmful chemical reagents.

[0040] Example 3 A breathable rubber material for protection against harmful chemical reagents, comprising, in sequence: The protective layer is a polyvinylidene fluoride microporous membrane with a pore size of 200 nm and a thickness of 0.05 mm. The adsorption layer comprises the following materials in parts by weight: 75 parts styrene-butadiene rubber latex, 50 parts activated carbon, 2.5 parts antioxidant DNP, 3 parts sulfur, 5 parts zinc oxide, 3 parts thiazole vulcanization accelerator DM, 1 part potassium hydroxide, and 0.1 parts sodium dodecyl sulfate; wherein the average particle size of the activated carbon is 30µm. The inner layer is made of cotton fiber fabric.

[0041] The preparation method of this breathable rubber material includes the following steps: 1) Preparation of adsorbent layer latex: Rubber latex, adsorbent particles, antioxidant, vulcanization accelerator, alkaline pH adjuster, stabilizer, sulfur, and zinc oxide are added to a mixer according to the weight ratio, and water is used as a solvent to stir and disperse evenly. The pH value is adjusted to 10. Sulfur and zinc oxide are first added to water and ground into a suspension before being added to rubber latex, and vulcanization accelerator is first added to water to prepare an aqueous emulsion before being added to rubber latex. 2) Preparation of adsorption layer: The prepared latex was poured into a grooved copper mold with a thickness of 8 mm. The mold was placed in a refrigerator and frozen into ice. The frozen latex ice block was placed in a freeze dryer until all the water sublimated. The freeze dryer was set to a condensation temperature of -60℃, a vacuum degree of -0.01 MPa, and a drying time of 72 h to obtain a porous rubber aerogel layer. The adsorbed particles were uniformly loaded in the internal cavity of the aerogel. The material was then placed in an oven and vulcanized at 180℃ for 30 min. 3) Preparation of breathable rubber material: Apply adhesive to one side of the protective layer and the bonding layer at certain intervals, then add the absorbent layer, stack them in sequence, and calender them using calendering rollers. Set the calendering pressure to 0.8 MPa, the temperature to 130℃, and the fabric feed speed to 1.7 m / min. A breathable rubber material was obtained that provides protection against harmful chemical reagents.

[0042] Example 4 This embodiment is basically the same as Embodiment 1, except that the protective layer is a polyurethane microporous fiber membrane, the rubber latex is chloroprene rubber latex, and the adsorbent particles in the adsorption layer are diatomaceous earth with an average particle size of 50µm.

[0043] Example 5 This embodiment is basically the same as Embodiment 1, except that the protective layer is an aramid fiber microporous membrane, the rubber latex is butyl terephthalic rubber latex, and the adsorbed particles in the adsorption layer are silica aerogel powder with an average particle size of 100µm.

[0044] Example 6 This embodiment is basically the same as Embodiment 1, except that the adsorption layer includes the following materials in parts by weight: 55 parts of nitrile rubber latex, 20 parts of adsorption particles, 0.2 parts of antioxidant 4020, 0.2 parts of sulfur, 0.2 parts of zinc oxide, 0.05 parts of sulfenamide vulcanization accelerator NOBS, 0.05 parts of sodium hydroxide, and 0.01 parts of sodium dodecyl sulfate.

[0045] Example 7 This embodiment is basically the same as Embodiment 1, except that the adsorption layer includes the following materials in parts by weight: 55 parts of styrene-butadiene rubber latex, 60 parts of adsorption particles, 5 parts of antioxidant DNP, 4 parts of sulfur, 7 parts of zinc oxide, 5 parts of thiazole vulcanization accelerator DM, 3 parts of potassium hydroxide, and 3 parts of sodium dodecyl sulfate.

[0046] Example 8 This embodiment is basically the same as Embodiment 1, except that the thickness of the copper template is 2mm.

[0047] Example 9 This embodiment is basically the same as Embodiment 1, except that the thickness of the copper template is 10mm.

[0048] Example 10 This embodiment is basically the same as that of Embodiment 1, except that the average particle size of the activated carbon in the adsorption layer is 200µm.

[0049] Example 11 This embodiment is basically the same as Embodiment 1, except that sulfur and zinc oxide were not added to the rubber latex before being ground into a suspension, and vulcanization accelerator was not added to the rubber latex before being prepared into an aqueous emulsion.

[0050] Example 12 This embodiment is basically the same as Example 1, except that the pH value is adjusted to 6 in the preparation of the adsorption layer latex.

[0051] Example 13 This embodiment is basically the same as Example 1, except that the pH value is adjusted to 11 in the preparation of the adsorption layer latex.

[0052] Example 14 This embodiment is basically the same as Example 1, except that the adsorption layer is prepared by sulfurizing at 120°C for 5 minutes.

[0053] Example 15 This embodiment is basically the same as Example 1, except that the adsorption layer is prepared by sulfidation at 200°C for 40 minutes.

[0054] Comparative Example 1 This comparative example is basically the same as Example 1, except that it does not include the step of preparing a porous rubber aerogel layer, but directly uses calendering to form a film to obtain the rubber material. Specifically, based on step (1) of Example 1, 5g of adsorption layer latex is evenly coated onto a tetrafluoroethylene microporous membrane and cotton fiber fabric, dried at room temperature for 5h, and then fed into an extrusion calender to form a film. The calendering pressure is set to 0.25MPa, the temperature to 125℃, and the fabric advance speed to 2.2m / min. After cooling, the protective material is obtained by hot pressing and vulcanization. The vulcanization pressure is 1.5MPa, the vulcanization temperature is 150℃, and the vulcanization time is 15min.

[0055] Comparative Example 2 This comparative example is basically the same as Example 1, except that no adsorption particles are added to the adsorption layer.

[0056] Comparative Example 3 This comparative example is basically the same as Example 1, except that no stabilizer is added to the adsorption layer.

[0057] Comparative Example 4 This comparative example is the product disclosed in Chinese patent CN202110585676.

[0058] Comparative Example 5 This comparative example is the product disclosed in Chinese patent CN201821040739.

[0059] Comparative Example 6 This comparative example is the product disclosed in Chinese patent CN2023113590152.

[0060] Test Example 1 Water penetration: GB / T 24218.17 "Textiles - Nonwovens - Test methods - Part 17: Determination of water resistance (spray impact method)" is used to simulate the limited liquid splash protection performance of garments under EN13034+A1.

[0061] Particulate matter protection and filtration performance: The test method for fabric filtration efficiency in Chapter 5.7 of GB19082-2009 "Technical Requirements for Medical Disposable Protective Clothing" is adopted, that is, the test is conducted in an environment with relative humidity of 30%±10% and temperature of 25℃±5℃ using sodium chloride aerosol (median particle diameter of 0.075μm±0.02μm) and air flow rate of 15L / min±2L / min.

[0062] Fabric air permeability test: GB / T 24218.15-2018 "Textiles - Nonwovens - Test Methods - Part 15: Determination of air permeability".

[0063] Fabric moisture permeability test: The fabric was tested according to GB / T 12704.1-2009 "Textiles - Test Methods for Moisture Permeability of Fabrics - Part 1: Moisture Absorption Method", with a test environment of 38℃ and a relative humidity of 90%.

[0064] Mustard gas protection performance: In accordance with GJB 6629-2008 standard, the time it takes for mustard gas to penetrate the fabric is tested using standard testing instruments to evaluate the mustard gas protection performance of protective fabrics.

[0065] Toluene resistance: The time it takes for toluene to penetrate the fabric is tested using standard testing instruments according to GB / T 23462-2009 standard to evaluate the toluene resistance of protective fabrics.

[0066] Acid and alkali resistance: According to GB 24540-2009 "Protective Clothing - Acid and Alkali Chemical Protective Clothing", the time it takes for acid and alkali solutions to penetrate the fabric is used as a characterization of its acid and alkali resistance.

[0067] Machine wash resistance: Cut a sample and dry it in a 40℃ oven until the mass no longer changes or changes very little. Put the sample into a washing machine and wash for 15 minutes. Dry the washed sample again and measure its mass. The ratio of the mass of the detached material to the original total mass is the machine wash shedding rate.

[0068] The test results are shown in Table 1 below.

[0069] Table 1. Test results of chemical protection performance of rubber materials for protection against chemical reagents.

[0070] Table 1 (Continued from Table 1)

[0071] Table 1 (Continued from Table 2)

[0072] According to the test results in Table 1, the proposed solution can effectively improve the protective filtration performance, air permeability and moisture permeability of rubber protective materials, reduce water seepage, greatly improve the wearing comfort of protective clothing, and has a good ability to protect against organic reagents, effectively preventing wearers from being harmed by organic reagents.

[0073] A detailed analysis of the experimental results reveals that: According to the experimental results of Examples 1 and 6-7, the rubber protective material of this application needs to follow certain proportions and preparation parameters during preparation. If the proportions or preparation parameters are not appropriate, it will affect the air permeability, chemical reagent protection performance and wash fastness of the rubber protective material.

[0074] Based on the experimental results of Examples 1 and 8-9, it is evident that the thickness of the copper template used during the casting process determines the thickness of the adsorption layer. The thickness of the adsorption layer affects the air permeability and barrier properties of the protective material. When the template thickness decreases, the adsorption layer thickness decreases, increasing air permeability but reducing the barrier properties and chemical absorption capacity of the protective material. Conversely, when the template thickness increases, the adsorption layer thickness increases, decreasing air permeability but increasing the barrier properties and chemical absorption capacity of the material. It should be noted that those skilled in the art can design and select the thickness of the adsorption layer according to actual needs.

[0075] According to the experimental results of Examples 1 and 10, the particle size of the adsorbent particles in the adsorption layer will affect the adsorption and protective properties of the rubber material. This is because the smaller the average particle size of the adsorbent particles, the larger the surface area of ​​the material, which is more conducive to improving the protective properties of the rubber protective material against organic chemical reagents. However, if the average particle size of the adsorbent particles is too large, its protective performance will be poor.

[0076] According to the experimental results of Examples 1 and 12 and 13, the addition of pH adjuster plays an important role in the uniformity and fluidity of the entire aerogel preparation system. When the pH value of the system is too high or too low, the latex may settle or flocculate, thereby affecting the air permeability and barrier properties of the rubber protective material.

[0077] According to the experimental results of Example 1 and Comparative Example 1, the rubber protective material obtained by the traditional calendering method has higher density and therefore higher barrier properties. However, excessive density will have a significant impact on air permeability; at the same time, it will also reduce wash fastness, making the protective material less durable.

[0078] According to the experimental results of Example 1 and Comparative Example 2, compared with Example 1, the adsorption and protective performance of the rubber protective material decreased significantly when no adsorbent particles were added, indicating that the addition of adsorbent particles plays an important role in the performance of the rubber protective material of this application.

[0079] According to the experimental results of the examples and Comparative Example 3, the overall performance of the rubber protective material decreases when no stabilizer is added. This is because the addition of the stabilizer can ensure the uniformity of the system's fluidity, promote the stable synthesis of rubber aerogel, and the more uniform the aerogel morphology, the better the air permeability of the rubber protective material. It also ensures that the rubber protective material has good wash fastness.

[0080] Comparing this application's solution with Comparative Example 4, patent CN202110585676 uses a method of uniformly distributing spherical activated carbon on a rubber-coated base fabric. According to the data from the examples, this method significantly impacts air permeability, resulting in a final air permeability of 669 mm / s. In contrast, this application employs an adsorption layer structure with rubber aerogel supporting adsorbent particles. The rubber aerogel acts as a skeleton to support the adsorbent particles, giving the adsorption layer a certain degree of flexibility and bending resistance. Furthermore, the aerogel cavities increase the contact area between the adsorbent particles and harmful gas molecules, thereby improving adsorption efficiency, enhancing the adsorption capacity of the protective material, effectively blocking chemical substances, improving the protective performance of the material, and maintaining good air permeability.

[0081] Comparing the scheme of this application with Comparative Example 5, Patent CN201821040739 uses a composite structure of a fabric layer and a spherical activated carbon layer to obtain a rubber protective material with high comfort and high wash fastness. According to the results of the examples, its optimal wash fastness is 0.49%, which still has room for further optimization. In contrast, this application uses aerogel to load adsorbed particles, which makes the adhesion between the two stronger and thus prevents the adsorbed particles from falling off. This makes the rubber protective material not only have high breathability and protective performance, but also good resistance to rubbing and machine washing.

[0082] Compared with Comparative Example 6, Patent 2023113590152 uses a dual-effect finishing agent and non-woven fabric to prepare a dual-effect absorbent and fixing layer material. When combined with the skin-adhering layer material and the external barrier protective layer material, its air permeability is optimal at 118.52 mm / s, its mustard gas resistance time is optimal at >120 min, its toluene resistance time is optimal at 60 min, its acid resistance time is optimal at >60 min, and its alkali resistance time is optimal at >60 min. All of these have room for further optimization. The rubber material provided in this application, through the combination of the protective layer, the absorbent layer, and the skin-adhering layer, especially through the structural improvement of the absorbent layer, has both better air permeability and protective performance.

[0083] The above description is merely an embodiment of this application, and the scope of protection of this application is not limited to these specific embodiments, but is determined by the claims of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the technical concept and principles of this application should be included within the scope of protection of this application.

Claims

1. A breathable rubber material for protection against harmful chemical reagents, characterized in that, The breathable rubber material includes a protective layer, an absorbent layer, and a skin-fitting layer connected in sequence, and adjacent layers are bonded together by hot melt adhesive. By weight, the adsorption layer comprises: 45-75 parts rubber latex, 30-50 parts adsorption particles, 0.5-2.5 parts antioxidant, 0.5-3 parts sulfur, 0.5-5 parts zinc oxide, 0.1-3 parts vulcanization accelerator, 0.1-1 parts alkaline pH adjuster, and 0.01-0.1 parts stabilizer; the rubber latex is selected from one or more of natural rubber latex, nitrile rubber latex, styrene-butadiene rubber latex, chloroprene rubber latex, butyl rubber latex, and pentadiene rubber latex; the adsorption particles are selected from one or more of activated carbon, biochar, diatomaceous earth, organobentonite, zeolite, and silica aerogel powder, and the average particle size of the adsorption particles is not greater than 100 μm. The preparation method of the adsorption layer includes the following steps: 1) Preparing the adsorption layer latex: adding rubber latex, adsorption particles, antioxidant, vulcanization accelerator, alkaline pH adjuster, stabilizer, sulfur, and zinc oxide into a mixer, adding water and stirring evenly, and adjusting the pH value to 7.8~10 to obtain the adsorption layer latex; 2) Preparing the adsorption layer: casting the adsorption layer latex into a mold and then freezing it, then freeze-drying the frozen latex ice block to obtain a porous rubber aerogel layer, and then vulcanizing the porous rubber aerogel layer to obtain the adsorption layer; In step 1), before adding sulfur and zinc oxide to the rubber latex, they are first ground into a suspension with water; in step 1), before adding vulcanization accelerator to the rubber latex, they are first prepared into an aqueous emulsion with water.

2. The breathable rubber material for protection against harmful chemical reagents according to claim 1, characterized in that, The alkaline pH adjuster is selected from one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia, sodium bicarbonate, potassium carbonate, trisodium phosphate, sodium citrate, potassium citrate, and sodium lactate; and / or, The stabilizer is selected from one or more of casein, gelatin, sodium lauryl sulfate, potassium laurate, and phenacetin.

3. The breathable rubber material for protection against harmful chemical reagents according to claim 1, characterized in that, The protective layer is selected from one or more of the following: polytetrafluoroethylene microporous membrane, nylon microporous membrane, polyvinylidene fluoride microporous membrane, aramid fiber microporous membrane, and polyurethane microporous fiber membrane; and / or, The inner layer is selected from one or more of the following: cotton fiber fabric, linen fiber fabric, wool fiber fabric, polyester fiber fabric, nylon fiber fabric, acetate fiber fabric, polypropylene fiber fabric, and spandex fiber fabric.

4. A method for preparing a breathable rubber material for protection against harmful chemical reagents as described in any one of claims 1 to 3, characterized in that, The preparation method includes the following steps: 1) Preparation of adsorbent layer latex: Add rubber latex, adsorbent particles, antioxidant, vulcanization accelerator, alkaline pH adjuster, stabilizer, sulfur, and zinc oxide into a mixer, add water and stir evenly, and adjust the pH value to 7.8~10 to obtain adsorbent layer latex. 2) Preparation of adsorption layer: After the adsorption layer latex is cast into shape, it is frozen, and then the frozen latex ice block is freeze-dried to obtain a porous rubber aerogel layer. Then the porous rubber aerogel layer is vulcanized to obtain the adsorption layer. 3) Preparation of breathable rubber material: The protective layer and the inner layer are heated and melted on one side, and then the adsorption layer is added. After being stacked in sequence, the layers are calendered to obtain the breathable rubber material for protection against harmful chemical reagents. In step 1), before adding sulfur and zinc oxide to the rubber latex, they are first ground into a suspension with water; in step 1), before adding vulcanization accelerator to the rubber latex, they are first prepared into an aqueous emulsion with water.

5. The method for preparing a breathable rubber material for protection against harmful chemical reagents according to claim 4, characterized in that, In step 2), the thickness of the adsorption layer is 4-8 mm; and / or, Vulcanization temperature 140~180℃, time 10~30min.

6. The use of the breathable rubber material for protection against harmful chemical reagents as described in any one of claims 1 to 3 in the preparation of protective products for protection against harmful chemical reagents.

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