Rubber material for protecting harmful chemical reagents as well as preparation method and application of rubber material

Abstract

The invention relates to a rubber material for protecting harmful chemical reagents as well as a preparation method and application thereof, and belongs to the technical field of harmful chemical reagent protection materials. The microporous fiber membrane is used as a carrier, and different reinforcing layers and barrier layers are designed on the microporous fiber membrane according to the number and sequence of the reinforcing layers and the barrier layers. The reinforcing layer is prepared from 40 to 65 parts of nitrile rubber latex, 2 to 3 parts of a fiber nano reinforcing material, 0.5 to 1 part of an anti-aging agent, 0.5 to 1.5 parts of sulfur, 0.5 to 3 parts of zinc oxide, 0.5 to 1.5 parts of a vulcanization accelerator, 0.1 to 0.5 part of an alkaline pH regulator and 0.01 to 0.2 part of a stabilizer; the barrier layer is prepared from 40 to 65 parts of nitrile rubber latex, 2 to 3 parts of a flaky nano barrier material, 0.5 to 1 part of an anti-aging agent, 0.5 to 1.5 parts of sulfur, 0.5 to 3 parts of zinc oxide, 0.5 to 1.5 parts of a vulcanization accelerator, 0.1 to 0.5 part of an alkaline pH regulator and 0.01 to 0.2 part of a stabilizer. The rubber material which is lower in thickness and better in protection performance is prepared on the basis that the water-based mixed material is combined with a vacuum suction filtration method, harmful chemical substances can be effectively blocked, meanwhile, the rubber material has excellent deflection resistance and aging resistance, and the rubber material can be widely applied to the fields of protective clothing, protective masks and protective blankets.

Description

Technical Field

[0001] The present application relates to a rubber material for protecting against harmful chemical agents, a preparation method and application thereof, and belongs to the technical field of protective materials against harmful chemical agents. Background Art

[0002] During the production and transportation of toxic chemicals, toxic gas leaks or other accidents may occur, affecting production progress and even threatening human life. Therefore, it is necessary to develop chemical protective clothing to effectively protect people from chemical damage when facing toxic chemicals. The protective performance of chemical protective clothing depends on the protective materials used. The preparation of commonly used protective materials is mainly to compound polymer films with excellent solvent resistance such as chloroprene rubber, nitrile rubber, polyurethane, polytetrafluoroethylene, etc. to prepare multi-layer composite materials, and also with different functional fillers such as inorganic nanoparticles, fibers, etc.

[0003] For example, the protective clothing fabric disclosed in patent CN113622197B has very complicated preparation steps and complex processing technology, and the product thickness is relatively thick at about 0.5mm; for example, the protective clothing fabric disclosed in patent CN115679707B, its processing technology is still relatively complicated, requiring multiple mixing, and after mixing, it needs to be crushed to prepare glue; for example, the broad-spectrum long-acting chemical protective clothing disclosed in patent CN117734263B has a large number of structures and layers, a complex processing technology, and a reinforced barrier layer with a thickness of 0.08mm, including an interface transition layer, a reinforced barrier layer, a rubber airtight layer, a material oil-resistant layer, and a surface protective layer. The overall thickness must be greater; for example, patent CN113733684B fully combines the advantages of each component material to maximize the performance of the protective material, but it has the problem of complex and cumbersome production process. In addition, there is a problem of poor adhesion between the layers of materials, and the produced protective clothing is relatively thick, which is not conducive to long-term wear by personnel. In summary, the protective rubber materials in the prior art generally have the problem of complex preparation processes. In addition, there is no prior art that uses water-based mixed materials to prepare protective clothing rubber materials.

[0004] Therefore, it is urgent to develop a rubber material with simple production process, lower thickness, better protective performance and suitable for long-term wear. Summary of the invention

[0005] In order to solve the above problems, a rubber material for protecting against harmful chemical agents, a preparation method and application thereof are provided. The application scheme is based on an aqueous mixed material combined with a vacuum filtration method to prepare a protective rubber material with lower thickness and better protective performance. The material can effectively block harmful chemicals and has excellent flexural and aging resistance. The material can be widely used in the fields of protective clothing, protective masks, and protective blankets.

[0006] According to one aspect of the present application, a rubber material for protecting against harmful chemical agents is provided, the rubber material comprising a microporous fiber membrane, a reinforcing layer and a barrier layer, the rubber material uses the microporous fiber membrane as a carrier and has a reinforcing layer and a barrier layer stacked thereon, and the number and sequence of the reinforcing layer and the barrier layer can be freely adjusted; The reinforcing layer comprises, by weight: 40-65 parts of nitrile rubber latex, 2-3 parts of fiber nano-reinforcement material, 0.5-1 parts of antioxidant, 0.5-1.5 parts of sulfur, 0.5-3 parts of zinc oxide, 0.5-1.5 parts of vulcanization accelerator, 0.1-0.5 parts of alkaline pH regulator, and 0.01-0.2 parts of stabilizer; In parts by weight, the barrier layer includes: 40-65 parts of nitrile rubber latex, 2-3 parts of flaky nano barrier material, 0.5-1 part of antioxidant, 0.5-1.5 parts of sulfur, 0.5-3 parts of zinc oxide, 0.5-1.5 parts of vulcanization accelerator, 0.1-0.5 parts of alkaline pH adjuster, and 0.01-0.2 parts of stabilizer.

[0007] In the present application, the nanofibers in the reinforcing layer can improve the comprehensive mechanical properties of the rubber, including tensile strength, tear resistance, and flex resistance, and extend the service life of the rubber; the nanosheets in the barrier layer can improve the air tightness of the rubber and prevent the penetration of harmful chemical agents; the multi-layer combination of the reinforcing layer and the barrier layer, coupled with the acid, alkali and solvent resistance of the nitrile rubber itself, can provide long-term and efficient protection against harmful chemical agents. The preparation process adopts a vacuum filtration layer-by-layer assembly method, which can improve the bonding strength between layers and reduce the problem of interlayer shedding, and the material thickness can be controlled to be thinner, and a water-based mixed material is used. Both the reinforcing layer and the barrier layer use water as the solvent. On the one hand, the filtration preparation process is simpler, and on the other hand, the production process reduces the generation of VOCs and is more environmentally friendly.

[0008] Optionally, the acrylonitrile content of the nitrile rubber latex is 30-45%, the total solid content is 30-60%, and the viscosity is 9-90 mPa·s.

[0009] The nitrile rubber latex selected in the present application has suitable acrylonitrile content, solid content and viscosity. When the performance parameters of acrylonitrile latex are within the specified range, the solid and liquid contents in the nitrile rubber latex are appropriate, and the viscosity of the latex is not too high or too low, which is more suitable for vacuum filtration and is conducive to the uniform distribution of reinforcing materials in the latex; when the parameters of the nitrile rubber latex are lower than the specified range, the overall viscosity of the latex is low, and the subsequent latex is easily filtered out from the microporous fiber membrane, which is not conducive to vacuum filtration; when the parameters of the nitrile rubber latex are higher than the specified range, the overall viscosity of the latex is high, and the fluidity of the latex will also deteriorate, which is not conducive to the dispersion of reinforcing materials therein, and the larger viscosity will also lead to an increase in the thickness of the protective material.

[0010] Optionally, the fiber nano-reinforcement material is one or more of nylon staple fiber, aramid staple fiber, glass staple fiber, carbon nanotube, attapulgite, and halloysite nanotube.

[0011] Optionally, the fiber diameter of the fiber nano-reinforced material is not greater than 10 μm, and the aspect ratio is not less than 200. The use of fibers with small diameter and high aspect ratio can improve the efficiency of enhancing the mechanical properties of rubber, and can achieve relatively excellent results when added in small amounts. If a material with too large a diameter is used, not only will it not have any reinforcing effect, but it will also increase the physical defects inside the rubber, thereby reducing the performance. If a material with too small an aspect ratio is used, the effect of improving the mechanical properties of the rubber material is not obvious.

[0012] Optionally, the fiber nano-reinforcement material is one or more of carbon nanotubes, attapulgite, and halloysite nanotubes. The distribution uniformity of the above materials in the aqueous mixed material will be better and the enhancement effect will be more obvious.

[0013] Optionally, the sheet-like nano-barrier material is one or more of graphene, clay nano-sheets, boron nitride nano-sheets, and molybdenum disulfide nano-sheets.

[0014] Optionally, the nanosheet thickness of the sheet-like nano-barrier material is not greater than 500nm, and the sheet diameter is not less than 100nm. Using nanosheets with thin thickness and large sheet diameter can improve the efficiency of enhancing the barrier properties of rubber, and can achieve a relatively excellent effect when added in small amounts. If a material with too thick thickness is used, not only will it not have an enhancing effect, but it will also increase the physical defects inside the rubber, thereby reducing the performance. If a material with too small a sheet diameter is used, the barrier properties of the rubber material will not be significantly improved.

[0015] Optionally, the microporous fiber membrane is one or more of a cellulose membrane, a nylon membrane, a polypropylene membrane, a polyethersulfone membrane, a polytetrafluoroethylene membrane, and a polyvinylidene fluoride membrane.

[0016] Optionally, the pore size of the microporous fiber membrane is not greater than 10 μm, and the thickness is not greater than 0.5 mm. If the pore size of the microporous fiber membrane is too large, it is easy to cause the latex to be completely filtered out, and it is impossible to obtain a formed reinforcing layer or barrier layer; if the thickness of the microporous fiber membrane is too large, it will affect the thickness of the final rubber material product, resulting in excessive thickness and inconvenience in wearing.

[0017] Optionally, the alkaline pH regulator is one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, potassium carbonate, trisodium phosphate, sodium citrate, potassium citrate, and sodium lactate. After adding the reinforcing filler, the pH value of the latex may change. By adding the alkaline pH regulator, the pH of the latex can be adjusted to be maintained in a reasonable range to avoid latex flocculation, thereby affecting the dispersion effect of the reinforcing filler.

[0018] Optionally, the stabilizer is one or more of casein, gelatin, sodium lauryl sulfate, potassium laurate, and peregal O. By adding the stabilizer, the uniform dispersion effect of the enhanced filler in the aqueous mixed material can be promoted to avoid agglomeration and the degradation of the performance of the rubber material.

[0019] Optionally, the structure of the rubber material is microporous fiber membrane-barrier layer-reinforcement layer-barrier layer, or microporous fiber membrane-barrier layer-reinforcement layer, or microporous fiber membrane-barrier layer-reinforcement layer-barrier layer-reinforcement layer, or microporous fiber membrane-reinforcement layer-barrier layer-reinforcement layer, or microporous fiber membrane-reinforcement layer-barrier layer-reinforcement layer, or microporous fiber membrane-reinforcement layer-barrier layer-reinforcement layer-barrier layer.

[0020] Optionally, the antioxidant is one or more of antioxidant DNP, antioxidant AW, antioxidant TMQ, antioxidant 6PPD, antioxidant 4020 and antioxidant BLE.

[0021] Optionally, the vulcanization accelerator is one or more of dithiocarbamate vulcanization accelerators, aldehyde amine vulcanization accelerators, thiuram vulcanization accelerators, thiazole vulcanization accelerators and xanthate vulcanization accelerators.

[0022] According to another aspect of the present application, a method for preparing the above-mentioned rubber material for protecting against harmful chemical agents is provided, characterized in that the method comprises the following steps: 1) preparing reinforcing layer latex: adding nitrile rubber latex, fiber nano-reinforcement material, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a mixer according to the weight ratio, stirring and dispersing them evenly with water as solvent, and adjusting the pH value to 7.8-10; 2) preparing barrier layer latex: adding nitrile rubber latex, flaky nano barrier material, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a blender according to the weight ratio, stirring and dispersing the mixture evenly with water as solvent, and adjusting the pH value to 7.8-10; 3) Place the microporous fiber membrane flat in a filtration device, then pour the reinforcement layer latex or barrier layer latex evenly on the microporous fiber membrane, and drain the water in the latex by vacuum filtration; 4) The film material that has been drained and formed is taken out and subjected to hot pressing and vulcanization to obtain the rubber material.

[0023] Optionally, in step 4), the hot pressing vulcanization pressure is 1-5 MPa, the temperature is 140-200°C, and the time is 10-20 minutes. If the vulcanization pressure is too low, the rubber material is not tight enough, thereby affecting the air tightness of the protective material. If it is too high, it will affect the life of the equipment. If the temperature is too low, the production time will increase. If the temperature is too high, it will easily lead to reverse sulfurization, thereby damaging the mechanical properties of the product. If the temperature is too high, it will also cause rubber aging and cracking, which will also affect the mechanical properties. If the reaction time is too short, it will lead to insufficient vulcanization. If the reaction time is too long, it will also lead to reverse sulfurization.

[0024] Optionally, in the step 1) and the step 2), before adding sulfur and zinc oxide to the nitrile rubber latex, they are ground into a suspension with water; and / or, Before the vulcanization accelerator is added into the nitrile rubber latex, water is added to prepare a water emulsion.

[0025] By adding water to sulfur, zinc oxide and vulcanization accelerators in advance to prepare a suspension or water emulsion, after adding the corresponding suspension or water emulsion, the latex can be made more uniform, thereby improving the vulcanization efficiency and the performance of the product.

[0026] According to another aspect of the present application, there is provided a use of the above-mentioned rubber material for protecting against harmful chemical agents in preparing protective products for protecting against harmful chemical agents; Optionally, the product is protective clothing, a protective mask or a protective blanket.

[0027] The beneficial effects of this application include but are not limited to: 1. According to the rubber material for protecting against harmful chemical agents and its preparation method and application in the present application, the vacuum filtration heating and pressing vulcanization method is adopted in the present application scheme, and the rubber material prepared has the advantages of higher air tightness, lighter weight, and better flex resistance and aging resistance, which can effectively improve the protective performance and wearing comfort of the protective material, and is suitable for personnel to wear for a long time. Compared with the traditional production method of scraping or calendering film, it is simpler, faster and more efficient.

[0028] 2. According to the rubber material for protecting against harmful chemical agents and its preparation method and application in the present application, the reinforcement layer and the barrier layer are prepared by a method of forming a film based on a water-based mixed material in combination with vacuum filtration, and the nitrile rubber latex is obtained under the condition of using water as a diluent. Compared with the traditional latex preparation process using an organic solvent as a diluent, it is more environmentally friendly and will not produce toxic side effects on the human body.

[0029] 3. According to the rubber material for protecting against harmful chemical agents and its preparation method and application in this application, the vacuum filtration process is adopted in this application scheme, and the number of layers of protective rubber material can be selected and designed independently according to needs. The structural flexibility of the protective material is high, and both the barrier layer and the reinforcement layer use nitrile rubber latex as the main body of the protective material, so the adhesion between the reinforcement layer and the barrier layer is good in the subsequent hot pressing vulcanization. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings: Figure 1 Schematic diagram of a vacuum filtration device according to an embodiment of the present application; Figure 2 This is a schematic diagram of the product after filtration involved in the embodiments of the present application. DETAILED DESCRIPTION

[0031] The present application is described in detail below in conjunction with examples, but the present application is not limited to these examples. Unless otherwise specified, the raw materials and reagents in the examples of the present application are purchased through commercial channels.

[0032] The present application scheme is described below through specific embodiments.

[0033] Example 1 A rubber material for protecting against harmful chemical agents, comprising the following specific components: The reinforcing layer includes the following materials in parts by weight: 55 parts of nitrile rubber latex, 2.5 parts of carbon nanotubes, 0.7 parts of antioxidant DNP, 0.8 parts of sulfur, 0.9 parts of zinc oxide, 0.9 parts of dithiocarbamate vulcanization accelerator PX, 0.2 parts of ammonia water, and 0.05 parts of casein; The barrier layer includes the following materials in parts by weight: 55 parts of nitrile rubber latex, 2.5 parts of graphene, 0.7 parts of antioxidant DNP, 0.6 parts of sulfur, 0.7 parts of zinc oxide, 0.7 parts of dithiocarbamate vulcanization accelerator PX, 0.2 parts of ammonia water, and 0.05 parts of casein; The carbon nanotube has a diameter of 500 nm and an aspect ratio of 500; The graphene thickness is 100 nm and the flake diameter is 800 nm; The microporous fiber membrane is a nylon microporous membrane with a pore size of 2µm and a thickness of 0.08mm.

[0034] The preparation method comprises the following steps: (0) Preparation: Weigh the dithiocarbamate vulcanization accelerator PX, add water to prepare an emulsified solution with a mass fraction of 20wt%; weigh sulfur, grind it, add water to prepare a sulfur suspension with a mass fraction of 50wt%; weigh zinc oxide, grind it, add water to prepare a zinc oxide suspension with a mass fraction of 50wt%; (1) Preparation of reinforcing layer latex: Add nitrile rubber latex, carbon nanotubes, antioxidant, water-emulsified vulcanization accelerator, ammonia water, casein, suspended sulfur, and suspended zinc oxide into a blender according to the above weight ratio, stir and disperse them evenly with water as solvent, and adjust the pH to 9.0; (2) Preparation of barrier layer latex: Add nitrile rubber latex, graphene, antioxidant, water-emulsified vulcanization accelerator, ammonia water, casein, suspended sulfur, and suspended zinc oxide into a blender according to the above weight ratio, stir and disperse them evenly with water as solvent, and adjust the pH to 9.0; (3) Place the corresponding microporous fiber membrane flat in a 500 mL sand core filtration funnel in advance, then pour 3 g of the stirred barrier layer latex evenly on the fiber membrane, and drain the water in the latex by vacuum filtration; (4) After the first barrier layer is dried, pour 3 g of the stirred reinforcement layer latex evenly on the fiber membrane, and drain the water in the latex by vacuum filtration; (5) Referring to (4), pour the second barrier layer evenly on the drained reinforcement layer, and drain the water in the latex by vacuum filtration; (6) The three-layer film material that has been dried and formed is taken out together with the supporting filter membrane and subjected to hot pressing vulcanization to obtain a protective material. The vulcanization pressure is 1.5 MPa, the vulcanization temperature is 150°C, and the vulcanization time is 15 min.

[0035] like Figure 1 As shown, it is a vacuum filtration device. Figure 2 This is a picture of the product after vacuum filtration.

[0036] Example 2 A rubber material for protecting against harmful chemical agents, comprising the following specific components: The reinforcing layer includes the following materials in parts by weight: 40 parts of nitrile rubber latex, 2 parts of halloysite nanotubes, 0.5 parts of antioxidant AW, 0.5 parts of sulfur, 0.5 parts of zinc oxide, 0.5 parts of sodium hydroxide, 0.5 parts of thiuram vulcanization accelerator TMTD, 0.1 parts of ammonia water, and 0.01 parts of peregal O-20; The barrier layer includes the following materials in parts by weight: 40 parts of nitrile rubber latex, 2 parts of boron nitride nanosheets, 0.5 parts of antioxidant AW, 0.5 parts of sulfur, 0.5 parts of zinc oxide, 0.5 parts of sodium hydroxide, 0.5 parts of thiuram vulcanization accelerator TMTD, 0.1 parts of ammonia water, and 0.01 parts of Peregal O-20; The diameter of the halloysite nanotubes is 1 μm, and the aspect ratio is 300; The boron nitride nanosheets have a thickness of 300 nm and a diameter of 200 nm; The microporous fiber membrane is a polypropylene microporous membrane with a pore size of 1 μm and a thickness of 0.08 mm.

[0037] The preparation method comprises the following steps: (0) Preparation: Weigh thiuram vulcanization accelerator TMTD, add water to prepare an emulsified solution with a mass fraction of 20wt%; weigh sulfur, grind it, add water to prepare a sulfur suspension with a mass fraction of 50wt%; weigh zinc oxide, grind it, add water to prepare a zinc oxide suspension with a mass fraction of 50wt%; (1) Preparation of reinforcing layer latex: Add nitrile rubber latex, halloysite nanotubes, antioxidant, water-emulsified vulcanization accelerator, ammonia water, sodium hydroxide, peregal O-20, suspended sulfur, and suspended zinc oxide into a blender according to the above weight ratio, stir and disperse evenly with water as solvent, and adjust the pH to 7.8; (2) Preparation of barrier layer latex: Add nitrile rubber latex, boron nitride nanosheets, antioxidant, water-emulsified vulcanization accelerator, ammonia water, sodium hydroxide, Periga O-20, suspended sulfur, and suspended zinc oxide into a blender according to the above weight ratio, stir and disperse evenly with water as solvent, and adjust the pH to 7.9; (3) Place the corresponding microporous fiber membrane flat in a 500 mL sand core filtration funnel in advance, then pour 3 g of the stirred barrier layer latex evenly on the fiber membrane, and drain the water in the latex by vacuum filtration; (4) After the first barrier layer is dried, pour 3 g of the stirred reinforcement layer latex evenly on the fiber membrane, and drain the water in the latex by vacuum filtration; (5) Referring to (4), pour the second barrier layer evenly on the drained reinforcement layer, and drain the water in the latex by vacuum filtration; (6) The three-layer film material that has been dried and formed is taken out together with the supporting filter membrane and subjected to hot pressing vulcanization to obtain a protective material. The vulcanization pressure is 1 MPa, the vulcanization temperature is 140°C, and the vulcanization time is 20 min.

[0038] Example 3 A rubber material for protecting against harmful chemical agents, comprising the following specific components: The reinforcing layer includes the following materials in parts by weight: 65 parts of nitrile rubber latex, 3 parts of attapulgite, 1 part of antioxidant BLE, 1.5 parts of sulfur, 3 parts of zinc oxide, 1.5 parts of xanthate vulcanization accelerator ZBX, 0.5 parts of sodium bicarbonate, and 0.2 parts of sodium dodecyl sulfate; The barrier layer includes the following materials in parts by weight: 65 parts of nitrile rubber latex, 3 parts of molybdenum disulfide nanosheets, 1 part of antioxidant BLE, 1.5 parts of sulfur, 3 parts of zinc oxide, 1.5 parts of xanthate vulcanization accelerator ZBX, 0.5 parts of sodium bicarbonate, and 0.2 parts of sodium dodecyl sulfate; The diameter of attapulgite is 10 μm, and the aspect ratio is 200; The MoS2 nanosheets have a thickness of 500 nm and a diameter of 100 nm; The microporous fiber membrane is a polyethersulfone microporous membrane with a pore size of 10 μm and a thickness of 0.5 mm.

[0039] The preparation method comprises the following steps: (0) Preparation: Weigh the xanthate vulcanization accelerator ZBX, add water to prepare an emulsified solution with a mass fraction of 20wt%; weigh sulfur, grind it, add water to prepare a sulfur suspension with a mass fraction of 50wt%; weigh zinc oxide, grind it, add water to prepare a zinc oxide suspension with a mass fraction of 50wt%; (1) Preparation of reinforcing layer latex: Add nitrile rubber latex, attapulgite, antioxidant, water-emulsified vulcanization accelerator, sodium bicarbonate, sodium lauryl sulfate, suspended sulfur, and suspended zinc oxide into a blender according to the above weight ratio, stir and disperse them evenly with water as solvent, and adjust the pH to 10.0; (2) Preparation of barrier layer latex: Add nitrile rubber latex, molybdenum disulfide nanosheets, antioxidant, water-emulsified vulcanization accelerator, sodium bicarbonate, sodium dodecyl sulfate, suspended sulfur, and suspended zinc oxide into a blender according to the above weight ratio, stir and disperse them evenly with water as solvent, and adjust the pH to 10.0; (3) Place the corresponding microporous fiber membrane flat in a 500 mL sand core filtration funnel in advance, then pour 3 g of the stirred barrier layer latex evenly on the fiber membrane, and drain the water in the latex by vacuum filtration; (4) After the first barrier layer is dried, pour 3 g of the stirred reinforcement layer latex evenly on the fiber membrane, and drain the water in the latex by vacuum filtration; (5) Referring to (4), pour the second barrier layer evenly on the drained reinforcement layer, and drain the water in the latex by vacuum filtration; (6) The three-layer film material that has been dried and formed is taken out together with the supporting filter membrane and subjected to hot pressing vulcanization to obtain a protective material. The vulcanization pressure is 5 MPa, the vulcanization temperature is 200°C, and the vulcanization time is 10 min.

[0040] Example 4 This embodiment is basically the same as Embodiment 1, except that the microporous fiber membrane is a polyvinylidene fluoride membrane and does not contain a second barrier layer.

[0041] Example 5 This embodiment is basically the same as the embodiment 1, except that the microporous fiber membrane is a polytetrafluoroethylene membrane, and further includes a second reinforcement layer on the second barrier layer.

[0042] Example 6 This embodiment is basically the same as Embodiment 1, except that the fiber nano-reinforced material is nylon staple fiber with a diameter of 1 μm, an aspect ratio of 800, a hot pressing vulcanization pressure of 1 MPa, a vulcanization temperature of 120° C., and a time of 10 min.

[0043] Example 7 This embodiment is basically the same as Embodiment 1, except that the fiber nano-reinforced material is aramid staple fiber with a diameter of 0.1 μm, an aspect ratio of 300, a hot pressing vulcanization pressure of 5 MPa, a vulcanization temperature of 200° C., and a time of 20 min.

[0044] Example 8 This embodiment is basically the same as Embodiment 1, except that, in Embodiment 1, it is microporous fiber membrane-first barrier layer-reinforcement layer-second barrier layer, while in this embodiment, it is microporous fiber membrane-first reinforcement layer-barrier layer-second reinforcement layer, and the stabilizer in the barrier layer and the reinforcement layer is replaced with gelatin.

[0045] Example 9 This embodiment is basically the same as Embodiment 1, except that it includes a microporous fiber membrane-a first barrier layer-a first reinforcement layer-a second barrier layer-a second reinforcement layer-a third barrier layer, wherein the fiber nano-reinforcement material is glass staple fiber with a diameter of 0.1 μm and an aspect ratio of 500, wherein the sheet-like nano-barrier material is a clay nano-sheet with a thickness of 300 nm and a sheet diameter of 200 nm, and the stabilizer in the barrier layer and the reinforcement layer is replaced with potassium laurate.

[0046] Example 10 This embodiment is basically the same as embodiment 1, except that the vulcanization pressure is 0.5 MPa, the temperature is 100° C., and the time is 5 min.

[0047] Embodiment 11 This embodiment is basically the same as Embodiment 1, except that the vulcanization pressure is 6 MPa, the temperature is 240° C., and the time is 30 min.

[0048] Example 12 This embodiment is substantially the same as the embodiment 1, except that the thickness of the sheet-like nano-barrier material is 700 nm and the sheet diameter is 80 nm.

[0049] Example 13 This embodiment is substantially the same as the embodiment 1, except that the diameter of the fiber nano-reinforced material is 15 μm and the aspect ratio is 100.

[0050] Comparative Example 1 This comparative example is basically the same as Example 1, except that the rubber material is obtained by scraping and drying. Specifically, based on step (2) of Example 1, 3 g of isolation layer latex and 3 g of reinforcement layer latex are respectively scraped and evenly coated on the nylon microporous fiber membrane, dried at room temperature for 5 h, and then hot-pressed to obtain the protective material. The vulcanization pressure is 1.5 MPa, the vulcanization temperature is 150°C, and the vulcanization time is 15 min.

[0051] Comparative Example 2 This comparative example is basically the same as Example 1, except that the rubber material is obtained by calendering film forming. Specifically, based on step (2) of Example 1, 3 g of isolation layer latex and 3 g of reinforcement layer latex are respectively taken and evenly coated on the nylon microporous fiber membrane, dried at room temperature for 5 hours, and then sent to an extrusion calender for calendering film forming. The calendering pressure is set to 0.25 MPa, the temperature is set to 125°C, and the fabric forward speed is set to 2.2 m / min. After cooling, the protective material is obtained by hot pressing and vulcanization. The vulcanization pressure is 1.5 MPa, the vulcanization temperature is 150°C, and the vulcanization time is 15 min.

[0052] Comparative Example 3 This comparative example is substantially the same as Example 1, except that it only includes a microporous fiber membrane-barrier layer.

[0053] Comparative Example 4 This comparative example is substantially the same as Example 1, except that it only includes a microporous fiber membrane-reinforcement layer.

[0054] Comparative Example 5 This comparative example is basically the same as Example 1, except that nitrile rubber latex is not used but chloroprene rubber is used instead. The chloroprene rubber is mixed and vulcanized according to the nitrile rubber formula of Example 1. No alkaline pH adjuster and stabilizer are added to the formula. The mixing temperature is 170°C and the mixing time is 5 min. After the mixed rubber is obtained, 650 parts of ethyl acetate and 720 parts of gasoline diluent are added by weight to prepare reinforcing layer latex and barrier layer latex. On the basis of step (2) of Example 1, 3 g of the barrier layer latex and 3 g of the reinforcing layer latex are respectively taken and evenly scraped on the nylon microporous fiber membrane, dried at room temperature for 5 h, and sent to an extrusion calender for calendering to form a film. The calendering pressure is set to 0.3 MPa, the temperature is set to 150°C, and the fabric forward speed is set to 2.2 m / min. After cooling, the protective material is obtained by hot pressing and vulcanization. The vulcanization pressure is 1.5 MPa, the vulcanization temperature is 150°C, and the vulcanization time is 30 min.

[0055] Comparative Example 6 This comparative example is substantially the same as Example 1, except that no stabilizer is added to the reinforcing layer.

[0056] Comparative Example 7 This comparative example is substantially the same as Example 1, except that no stabilizer is added to the barrier layer.

[0057] Test Example 1 Permeability test method: According to GB 245392021 "Protective Clothing - Chemical Protective Clothing", the chemical substances used for permeability test include acetone (CAS No. 67-64-1, liquid), acetonitrile (CAS No. 75-05-8, liquid), carbon disulfide (CAS No. 75-15-0, liquid), dichloromethane (CAS No. 75-09-02, liquid), diethylamine (CAS No. 109-89-7, liquid), ethyl acetate (CAS No. 141-78-6, liquid), n-hexane (CAS No. 110-54-3, liquid), methanol (CAS No. 67-56-1, liquid), sodium hydroxide (mass fraction 30%, CAS No. 1310-73-2, liquid), sulfur Acid (mass fraction 96%, CAS number 7664-93-9, liquid), tetrahydrofuran (CAS number 109-99-9, liquid), toluene (CAS number 108-88-3, liquid), ammonia (volume fraction 99.9%, CAS number 7664-41-7, gas), chlorine (volume fraction 99.5%, CAS number 7782-50-5, gas) and hydrogen chloride (CAS number 7647-01-0, gas) and other 15 kinds, and the permeation performance is divided into 6 levels according to the permeation time, and the standard permeation time from level 1 to level 6 is>10min,>30min,>60min,>120min,>240min,>480min; The penetration time test method and steps refer to GB / T23462. The penetration performance is tested in the corresponding standard liquid chemical substance penetration test cell or the standard gaseous chemical substance penetration test cell and the final penetration time is recorded. Table 1 includes the test results of multiple substances, which are obtained by testing the listed multiple substances together after mixing.

[0058] Flame retardant performance test: refer to the vertical combustion method in GB / T 10707-2008 to test the flame retardant performance, and record the smoldering time, afterflaming time and damaged length.

[0059] Thickness: Tested by thickness tester.

[0060] Air tightness: The air tightness test is carried out using the pressure method. The pressure sensor is used to detect the pressure difference of the rubber protective material within a certain period of time, and the air tightness data is calculated.

[0061] Low-temperature flexural fatigue test: The rubber high and low temperature flexural fatigue tester GT-7011-DHD (GOTECH) was used to test the low-temperature flexural fatigue test of the obtained rubber protective material.

[0062] High temperature aging resistance test: The high temperature aging resistance test was performed on the rubber protective materials of the embodiment and the comparative example respectively, and the method is as follows: After heating the material at 72°C for 72 hours, observe whether the surface of the rubber protective material changes.

[0063] The test results are shown in Tables 1 and 2 below.

[0064] Table 1 Test results of chemical protection performance of rubber materials for protection against chemical reagents

[0065] Table 1 continued

[0066] Table 1 continued Table 2

[0067] Table 2 Test results of rubber material performance for protection against chemical agents

[0068] Table 2 continued from Table 1

[0069] Table 2 continuedTable 2

[0070] From the analysis of the test results in Table 1 and Table 2, it can be seen that the technical solution of the present invention can effectively reduce the thickness of the rubber protective material and improve its air tightness. The obtained protective material has better ability to protect against chemical reagents and better resistance to bending and aging.

[0071] Specifically, according to the experimental results of Examples 1 to 3, the rubber protective material obtained within the ratio range of the present invention has outstanding protective effect and flexural resistance and aging resistance, and is very suitable for the preparation of protective products for protecting against harmful chemical agents, such as protective clothing, protective masks or protective blankets.

[0072] According to the experimental results of Examples 1, 4-5 and Comparative Examples 3-4, it can be seen that the design of different numbers of protective materials will affect the protective performance and air tightness, flexural resistance and aging resistance. When the number of protective material layers is less, although the thickness can be greatly reduced, the protective performance of the protective material will be significantly reduced. The reason is that the fewer the number of protective material layers, the lower the air tightness, and harmful chemicals are easy to enter, which damages human health; when the number of protective material layers is more, the protective performance of the protective material will be significantly improved, but too many layers will increase the thickness of the protective material, affecting the flexural resistance of the protective material. At the same time, according to the experimental data, there is a difference in the performance of the protective layer and the reinforcement layer. The protective layer has better chemical barrier ability than the reinforcement layer, but the flexural resistance is average; the reinforcement layer mainly has better flexural resistance, and the strength and toughness of the material are better. The present application scheme has better protection against chemical reagents and flexural resistance and aging resistance through the cooperation of the reinforcement layer and the barrier layer.

[0073] According to the experimental results of Examples 1, 6-7, 10-11, the last step of hot pressing vulcanization requires controlling the appropriate vulcanization temperature, pressure and time. When the hot pressing vulcanization parameters are too high or too low, the performance of the protective material will be affected, making the material more susceptible to damage.

[0074] According to the experimental results of Examples 1 and 8, under the same number of layer designs, the different design sequences of the protective layers or the reinforcing layers will also lead to different performances of the protective materials. When the number of protective layers is greater than the number of reinforcing layers, the protective material has a stronger ability to block chemicals and a stronger air tightness. When the number of protective layers is less than the number of reinforcing layers, the protective material has better flexural resistance.

[0075] According to the experimental results of Examples 1, 12 to 13, the sheet-like nano-barrier material of the barrier layer and the fiber nano-reinforced processing material of the reinforcement layer need to have appropriate parameters. When the parameters are inappropriate, the barrier performance of the barrier layer and the flexural and aging resistance of the reinforcement layer will decrease.

[0076] According to the experimental results of Example 1 and Comparative Examples 1-2, the preparation method of the aqueous mixed material proposed in the present invention in combination with vacuum filtration is more conducive to obtaining a protective material with lower thickness, better protective performance and stronger air tightness. The reason is that the vacuum filtration processing method can compress the protective material as much as possible on the original basis and reduce the thickness of the protective material. At the same time, the protective material can be stacked to the maximum extent due to the effect of filtration, and the air tightness of the protective material is also improved.

[0077] According to the experimental results of Example 1 and Comparative Example 5, after replacing the nitrile rubber latex with chloroprene rubber, because the chloroprene rubber is in a solid state, ethyl acetate is required as a solvent and gasoline is used as a diluent to obtain the chloroprene rubber latex, but this method is easy to pollute the environment, and long-term contact will also have adverse effects on the human body; in addition, the interaction between chloroprene rubber and the reinforcing material is weak, so the barrier performance and flexural resistance of the protective material finally obtained are average.

[0078] According to the experimental results of Example 1 and Comparative Examples 6-7, the addition of the stabilizer has a huge impact on the entire preparation process. When the stabilizer is not added, the latex is prone to sedimentation or flocculation, which not only affects the filtration and increases the thickness of the protective material, but also reduces the barrier properties, flexural resistance and aging resistance of the protective material.

[0079] The above is only the embodiment of the present application, and the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application can have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.

Claims

1. A rubber material for protecting against harmful chemical agents, characterized in that: The rubber material comprises a microporous fiber membrane, a reinforcing layer and a barrier layer. The rubber material uses the microporous fiber membrane as a carrier and has the reinforcing layer and the barrier layer stacked thereon. The number and sequence of the reinforcing layer and the barrier layer can be freely adjusted. The reinforcing layer comprises, by weight: 40-65 parts of nitrile rubber latex, 2-3 parts of fiber nano-reinforcement material, 0.5-1 parts of antioxidant, 0.5-1.5 parts of sulfur, 0.5-3 parts of zinc oxide, 0.5-1.5 parts of vulcanization accelerator, 0.1-0.5 parts of alkaline pH regulator, and 0.01-0.2 parts of stabilizer; In parts by weight, the barrier layer includes: 40-65 parts of nitrile rubber latex, 2-3 parts of flaky nano barrier material, 0.5-1 part of antioxidant, 0.5-1.5 parts of sulfur, 0.5-3 parts of zinc oxide, 0.5-1.5 parts of vulcanization accelerator, 0.1-0.5 parts of alkaline pH adjuster, and 0.01-0.2 parts of stabilizer.

2. The rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The acrylonitrile content of the nitrile rubber latex is 30-45%, the total solid content is 30-60%, and the viscosity is 9-90 mPa·s.

3. The rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The fiber nano-reinforcement material is one or more of nylon staple fiber, aramid staple fiber, glass staple fiber, carbon nanotube, attapulgite, and halloysite nanotube; and / or, The fiber diameter of the fiber nano-reinforced material is not greater than 10 μm, and the aspect ratio is not less than 200.

4. The rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The sheet-like nano-barrier material is one or more of graphene, clay nano-sheets, boron nitride nano-sheets, and molybdenum disulfide nano-sheets; and / or, The thickness of the nanosheet of the flaky nano-barrier material is not greater than 500 nm, and the diameter of the nanosheet is not less than 100 nm.

5. The rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The microporous fiber membrane is one or more of a cellulose membrane, a nylon membrane, a polypropylene membrane, a polyethersulfone membrane, a polytetrafluoroethylene membrane, and a polyvinylidene fluoride membrane; and / or, The pore size of the microporous fiber membrane is no greater than 10 μm, and the thickness is no greater than 0.5 mm.

6. The rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The alkaline pH regulator is one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, potassium carbonate, trisodium phosphate, sodium citrate, potassium citrate, sodium lactate; and / or, The stabilizer is one or more of casein, gelatin, sodium lauryl sulfate, potassium laurate, and peregal O.

7. The rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The structure of the rubber material is microporous fiber membrane-barrier layer-reinforcement layer-barrier layer, or microporous fiber membrane-barrier layer-reinforcement layer, or microporous fiber membrane-barrier layer-reinforcement layer-barrier layer-reinforcement layer, or microporous fiber membrane-reinforcement layer-barrier layer-reinforcement layer, or microporous fiber membrane-reinforcement layer-barrier layer-reinforcement layer, or microporous fiber membrane-reinforcement layer-barrier layer-reinforcement layer-barrier layer.

8. The method for preparing a rubber material for protecting against harmful chemical agents according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: 1) preparing reinforcing layer latex: adding nitrile rubber latex, fiber nano-reinforcement material, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a mixer according to the weight ratio, stirring and dispersing them evenly with water as solvent, and adjusting the pH value to 7.8-10; 2) preparing barrier layer latex: adding nitrile rubber latex, flaky nano barrier material, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a blender according to the weight ratio, stirring and dispersing the mixture evenly with water as solvent, and adjusting the pH value to 7.8-10; 3) Place the microporous fiber membrane flat in a filtration device, then pour the reinforcement layer latex or barrier layer latex evenly on the microporous fiber membrane, and drain the water in the latex by vacuum filtration; 4) The film material that has been drained and formed is taken out and subjected to hot pressing and vulcanization to obtain the rubber material.

9. The method for preparing a rubber material for protecting against harmful chemical agents according to claim 8, characterized in that: In the step 4), the hot pressing vulcanization pressure is 1-5 MPa, the temperature is 140-200° C., and the time is 10-20 min; and / or, In the step 1) and the step 2), before adding sulfur and zinc oxide to the nitrile rubber latex, they are ground into a suspension with water; and / or, In the steps 1) and 2), before the vulcanization accelerator is added to the nitrile rubber latex, water is added to prepare a water emulsion.

10. Use of the rubber material for protecting against harmful chemical agents as claimed in any one of claims 1 to 7 in preparing protective products for protecting against harmful chemical agents.

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