A rubber material for protecting against harmful chemical agents, and a method for its preparation and use

Abstract

The application relates to a rubber material for protecting harmful chemical agents and a preparation method and application thereof, and belongs to the technical field of harmful chemical agent protection materials. A microporous fiber membrane is used as a carrier, and the microporous fiber membrane is provided with different reinforcing layers and barrier layers in terms of layer number and layer sequence design; the reinforcing layer comprises 40-65 parts of nitrile rubber latex, 2-3 parts of fiber nano reinforcing material, 0.5-1 part of an antioxidant, 0.5-1.5 parts of sulfur, 0.5-3 parts of zinc oxide, 0.5-1.5 parts of a vulcanization accelerator, 0.1-0.5 parts of an alkaline pH regulator and 0.01-0.2 parts of a stabilizer; and the barrier layer comprises 40-65 parts of nitrile rubber latex, 2-3 parts of sheet nano barrier material, 0.5-1 part of an antioxidant, 0.5-1.5 parts of sulfur, 0.5-3 parts of zinc oxide, 0.5-1.5 parts of a vulcanization accelerator, 0.1-0.5 parts of an alkaline pH regulator and 0.01-0.2 parts of a stabilizer. The rubber material with lower thickness and better protection performance is prepared based on water-based mixed materials and a vacuum filtration method, can effectively block harmful chemical substances, has excellent flex resistance and aging resistance, and can be widely applied in the fields of protective clothing, protective masks and protective blankets.

Description

TECHNICAL FIELD

[0001] The application relates to a 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. BACKGROUND

[0002] In the production and transportation process of toxic chemicals, toxic gas leakage or other accidents may occur, affecting the production progress and even threatening the safety of human life. Therefore, chemical protective clothing needs to be developed to effectively protect people from chemical hazards. The protective performance of the chemical protective clothing depends on the protective material used. The preparation of the commonly used protective material mainly involves compounding high-molecular films such as chloroprene rubber, nitrile rubber, polyurethane and polytetrafluoroethylene to prepare a multilayer composite material, and adding fillers with different functions such as inorganic nanoparticles and fibers.

[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 about 0.5 mm. The processing technology of the protective clothing fabric disclosed in patent CN115679707B is still relatively complex, and the rubber slurry needs to be prepared after multiple mixing and crushing. The broad-spectrum long-acting chemical protective clothing disclosed in patent CN117734263B has a complex processing technology and a large number of structures and layers, and the thickness of the enhanced barrier layer is 0.08 mm. The overall thickness of the interface transition layer, the enhanced barrier layer, the rubber airtight layer, the material oil-resistant layer and the surface protective layer is necessarily larger. The protective material in patent CN113733684B fully combines the advantages of each component material to maximize the performance of the protective material. However, the production process is complex and complicated. In addition, the adhesion between the layers is poor, and the produced protective clothing is heavy, which is not suitable for long-term wearing. In summary, the protective rubber material in the prior art generally has a complex preparation process, and there is no existing technology using water-based mixed materials to prepare protective clothing rubber materials.

[0004] Therefore, it is urgent to develop a rubber material with a simple production process, a lower thickness, a better protective performance and a long-term wearing suitability. SUMMARY

[0005] In order to solve the above problems, a rubber material for protecting harmful chemical reagents and a preparation method and application thereof are provided. The application is prepared based on a water-based mixed material combined with a vacuum filtration method to obtain a protective rubber material with a lower thickness and a better protective performance, which can effectively block harmful chemical substances and has excellent flexibility resistance and aging resistance. The rubber 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 harmful chemical agents is provided, the rubber material comprising a microporous fiber membrane, a reinforcing layer and a barrier layer, the rubber material taking the microporous fiber membrane as a carrier and having the reinforcing layer and the barrier layer stacked thereon, the number of layers and the sequence of layers of the reinforcing layer and the barrier layer being freely adjustable.

[0007] The reinforcing layer comprises, by weight fraction, 40-65 parts of nitrile rubber latex, 2-3 parts of fiber nano-reinforcing 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.

[0008] The barrier layer comprises, by weight fraction, 40-65 parts of nitrile rubber latex, 2-3 parts of sheet 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.

[0009] In the present application, the nano-fibers in the reinforcing layer can improve the comprehensive mechanical properties of the rubber, including tensile strength, tear resistance, and flex resistance, thereby prolonging the service life of the rubber; the nano-sheets in the barrier layer can improve the air tightness of the rubber and block the penetration of harmful chemical agents; the multi-layer combination of the reinforcing layer and the barrier layer, together with the acid and alkali resistance and solvent resistance of nitrile rubber itself, can provide long-term and efficient protection against harmful chemical agents. The preparation process uses a vacuum filtration layer-by-layer assembly method, which can improve the bonding force between layers, reduce the problem of layer separation, and control the thickness of the material to be thinner. Moreover, the water-based mixed material is used, and the reinforcing layer and the barrier layer both use water as the solvent, which is simpler in terms of preparation process and more environmentally friendly in terms of reducing the production of VOCs.

[0010] Optionally, the nitrile content of the nitrile rubber latex is 30-45%, the total solid content is 30-60%, and the viscosity is 9-90 mPa·s.

[0011] The selected nitrile rubber latex has suitable acrylonitrile content, solid content and viscosity. When the performance parameters of the acrylonitrile latex are within the limited range, the solid and liquid contents contained in the nitrile rubber latex are suitable, the viscosity of the latex is not too high or too low, the vacuum filtration is relatively suitable, and the uniform distribution of the reinforcing material in the latex is facilitated. When the parameters of the nitrile rubber latex are lower than the limited range, the overall viscosity of the latex is low, and the subsequent latex is easily filtered out of the microporous fiber membrane, which is not conducive to the vacuum filtration. When the parameters of the nitrile rubber latex are higher than the limited range, the overall viscosity of the latex is large, and the flowability of the latex will also deteriorate, which is not conducive to the dispersion of the reinforcing material therein, and the large viscosity will also increase the thickness of the protective material.

[0012] Optionally, the fiber nanoreinforcing material is one or more of nylon short fibers, aramid short fibers, glass short fibers, carbon nanotubes, attapulgite, and halloysite nanotubes.

[0013] Optionally, the fiber nanoreinforcing material has a fiber diameter of not greater than 10 μm and an aspect ratio of not less than 200. The use of small-diameter and high-aspect-ratio fibers can improve the reinforcing efficiency of the mechanical properties of the rubber, and excellent results can be achieved with a small amount of addition. If a material with too large a diameter is used, not only will the reinforcing effect not be achieved, but physical defects will also be increased in the rubber, thereby reducing the performance. If a material with too small an aspect ratio is used, the mechanical property improvement effect on the rubber material is not obvious.

[0014] Optionally, the fiber nanoreinforcing material is one or more of carbon nanotubes, attapulgite, and halloysite nanotubes. The above materials have better uniformity in the water-based mixed material, and the improvement effect is more obvious.

[0015] Optionally, the sheet-shaped nanobarrier material is one or more of graphene, clay nanosheets, boron nitride nanosheets, and molybdenum disulfide nanosheets.

[0016] Optionally, the sheet-shaped nanobarrier material has a nanosheet thickness of not greater than 500 nm and a sheet diameter of not less than 100 nm. The use of nanosheets with thin thickness and large sheet diameter can improve the reinforcing efficiency of the barrier properties of the rubber, and excellent results can be achieved with a small amount of addition. If a material with too thick thickness is used, not only will the reinforcing effect not be achieved, but physical defects will also be increased in the rubber, thereby reducing the performance. If a material with too small a sheet diameter is used, the barrier property improvement effect on the rubber material is not obvious.

[0017] Optionally, the microporous fiber membrane is one or more of a cellulose membrane, a nylon membrane, a polypropylene membrane, a polyether sulfone membrane, a polytetrafluoroethylene membrane, and a polyvinylidene fluoride membrane.

[0018] 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, the latex is easily filtered out, and a shaped reinforcing layer or barrier layer cannot be obtained. If the thickness of the microporous fiber membrane is too large, the thickness of the final rubber material product is affected, and the thickness is too large, which is inconvenient to wear.

[0019] Optionally, the basic pH regulator is one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia, sodium bicarbonate, potassium carbonate, trisodium phosphate, sodium citrate, potassium citrate, and sodium lactate. After the addition of the reinforcing filler, the pH value of the latex may change. By adding a basic pH regulator, the pH of the latex can be adjusted to a reasonable range, avoiding latex flocculation, thereby affecting the dispersion effect of the reinforcing filler.

[0020] Optionally, the stabilizer is one or more of casein, gelatin, sodium dodecyl sulfate, potassium laurate, and peregal O. By adding a stabilizer, the uniform dispersion effect of the reinforcing filler in the aqueous mixture can be promoted, and agglomeration that causes a decrease in the performance of the rubber material can be avoided.

[0021] Optionally, the structure of the rubber material is microporous fiber membrane-barrier layer-reinforcing layer-barrier layer, microporous fiber membrane-barrier layer-reinforcing layer, microporous fiber membrane-barrier layer-reinforcing layer-barrier layer-reinforcing layer, microporous fiber membrane-reinforcing layer-barrier layer-reinforcing layer, or microporous fiber membrane-reinforcing layer-barrier layer-reinforcing layer-barrier layer.

[0022] Optionally, the antioxidant is one or more of antioxidant DNP, antioxidant AW, antioxidant TMQ, antioxidant 6PPD, antioxidant 4020, and antioxidant BLE.

[0023] Optionally, the vulcanization accelerator is one or more of dithiocarbamate, aldehyde amine vulcanization accelerator, thiuram vulcanization accelerator, thiazole vulcanization accelerator, and xanthate vulcanization accelerator.

[0024] According to another aspect of the present application, a method for preparing the above-mentioned rubber material for protection against harmful chemical agents is provided, characterized in that the method comprises the following steps:

[0025] 1) Preparing a reinforcing layer latex: according to the weight ratio, the nitrile rubber latex, the fiber nano-reinforcing material, the antioxidant, the vulcanization accelerator, the basic pH regulator, the stabilizer, the sulfur, and the zinc oxide are added to a stirrer with water as the solvent to stir and disperse uniformly, and the pH value is adjusted to 7.8-10;

[0026] 2) Preparation of barrier layer latex: according to the weight ratio of the above-mentioned ingredients, nitrile rubber latex, sheet-shaped nano barrier material, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide are added into a stirring machine and stirred and dispersed uniformly with water as solvent, and the pH value is adjusted to 7.8-10;

[0027] 3) The microporous fiber membrane is placed flat in a suction filtration device, and then the reinforcing layer latex or the barrier layer latex is uniformly poured on the microporous fiber membrane, and the water in the latex is sucked dry by vacuum suction filtration;

[0028] 4) The formed film material is taken out and hot pressed to obtain the rubber material.

[0029] Optionally, 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. If the vulcanization pressure is too small, the rubber material is not compact enough, thereby affecting the air tightness of the protective material, and if the pressure is too large, the service life of the equipment will be affected; if the temperature is too low, the production time will be increased, and if the temperature is too high, the mechanical properties of the product will be damaged due to the reverse vulcanization, and the rubber will also be aged and cracked, which will also affect the mechanical properties; if the reaction time is too short, the vulcanization will be insufficient, and if the reaction time is too long, the reverse vulcanization will also occur.

[0030] Optionally, in the steps 1) and 2), the sulfur and zinc oxide are ground into a suspension before being added into the nitrile rubber latex; and / or,

[0031] The vulcanization accelerator is prepared into an aqueous emulsion before being added into the nitrile rubber latex.

[0032] By preparing the sulfur, zinc oxide and vulcanization accelerator into a suspension or an aqueous emulsion in advance, the latex can be more uniform after the corresponding suspension or aqueous emulsion is added, thereby improving the vulcanization efficiency and the performance of the product.

[0033] According to another aspect of the present application, the above-mentioned rubber material for protecting harmful chemical reagents is applied to the preparation of a protective product for protecting harmful chemical reagents.

[0034] Optionally, the product is a protective clothing, a protective mask or a protective blanket.

[0035] The beneficial effects of the present application include but are not limited to:

[0036] 1. The rubber material for protecting harmful chemical agents, and its preparation method and application according to the present application, the rubber material is prepared by the method of vacuum filtration and heat vulcanization, and has the advantages of higher air tightness, lighter weight and thinner thickness, better flex resistance and aging resistance, and can effectively improve the protection performance and wearing comfort of the protective material, and is suitable for long-term wearing, and is more simple, fast and efficient compared with the traditional production method of scraping or calendering film formation.

[0037] 2. The rubber material for protecting harmful chemical agents, and its preparation method and application according to the present application, the reinforced layer and the barrier layer are prepared by the method of water-based mixed material and vacuum filtration film formation, and the nitrile rubber latex is obtained under the condition of water as a diluent, which is more environmentally friendly compared with the traditional latex preparation process using organic solvents as diluents, and does not produce toxic side effects on the human body.

[0038] 3. The rubber material for protecting harmful chemical agents, and its preparation method and application according to the present application, the vacuum filtration process is used, the number of layers of the protective rubber material can be selected and designed according to the requirements, the structure of the protective material has high flexibility, and the barrier layer and the reinforced layer both use nitrile rubber latex as the main body of the protective material, so that the adhesion of the reinforced layer and the barrier layer is good in the subsequent heat vulcanization. BRIEF DESCRIPTION OF DRAWINGS

[0039] The drawings described herein are used to provide further understanding of the present application, and form a part of the present application, the schematic embodiments of the present application and the description thereof are used to explain the present application, and do not constitute an improper limitation on the present application. In the drawings:

[0040] Figure 1 It is a schematic diagram of the vacuum filtration device related to the embodiments of the present application;

[0041] Figure 2 It is a schematic diagram of the product after filtration. DETAILED DESCRIPTION

[0042] The present application will be described in detail below in combination with embodiments, but the present application is not limited to these embodiments, and the raw materials and reagents in the embodiments of the present application are all purchased through commercial channels unless otherwise specified.

[0043] The present application scheme will be described below through specific embodiments.

[0044] Example 1

[0045] A rubber material for protecting harmful chemical agents, comprising the following specific components:

[0046] The reinforcing layer comprises the following materials in weight parts: nitrile rubber latex 55 parts, carbon nanotubes 2.5 parts, antioxidant DNP 0.7 parts, sulfur 0.8 parts, zinc oxide 0.9 parts, dithiocarbamate vulcanizing accelerator PX 0.9 parts, ammonia 0.2 parts, casein 0.05 parts;

[0047] The barrier layer comprises the following materials in weight parts: nitrile rubber latex 55 parts, graphene 2.5 parts, antioxidant DNP 0.7 parts, sulfur 0.6 parts, zinc oxide 0.7 parts, dithiocarbamate vulcanizing accelerator PX 0.7 parts, ammonia 0.2 parts, casein 0.05 parts;

[0048] The carbon nanotubes have a diameter of 500 nm and an aspect ratio of 500;

[0049] The graphene has a thickness of 100 nm and a flake diameter of 800 nm;

[0050] The microporous fiber membrane is a nylon microporous membrane, with a membrane pore size of 2 µm and a thickness of 0.08 mm.

[0051] The preparation method comprises the following steps:

[0052] (0) Preparation: weigh the dithiocarbamate vulcanizing accelerator PX, add water to prepare an emulsified solution with a mass fraction of 20wt%; weigh the sulfur, grind and add water to prepare a sulfur suspension with a mass fraction of 50wt%; weigh the zinc oxide, grind and add water to prepare a zinc oxide suspension with a mass fraction of 50wt%;

[0053] (1) Reinforcing layer latex preparation: according to the above weight ratio, nitrile rubber latex, carbon nanotubes, antioxidants, water emulsified vulcanizing accelerator, ammonia, casein, sulfur suspension, and zinc oxide suspension are added to a stirrer with water as the solvent to stir and disperse uniformly, and the pH is adjusted to 9.0;

[0054] (2) Barrier layer latex preparation: according to the above weight ratio, nitrile rubber latex, graphene, antioxidants, water emulsified vulcanizing accelerator, ammonia, casein, sulfur suspension, and zinc oxide suspension are added to a stirrer with water as the solvent to stir and disperse uniformly, and the pH is adjusted to 9.0;

[0055] (3) Place the corresponding microporous fiber membrane flat in a 500mL sand core suction filter funnel in advance, then evenly pour 3g of the uniformly stirred barrier layer latex on the fiber membrane, and dry the water in the latex by vacuum suction filtration;

[0056] (4) After the first layer of barrier layer is dried, evenly pour 3g of the uniformly stirred reinforcing layer latex on the fiber membrane, and dry the water in the latex by vacuum suction filtration;

[0057] (5) Refer to (4) to evenly pour the second layer of barrier layer on the dried reinforced layer, and dry the water in the latex by vacuum filtration;

[0058] (6) Take out the three-layer film material dried and formed together with the bearing filter membrane and vulcanize by heat to obtain the protective material, the vulcanization pressure is 1.5 MPa, the vulcanization temperature is 150℃, and the vulcanization time is 15 min.

[0059] As shown in Figure 1 , a vacuum filtration device, Figure 2 , a picture of the product after vacuum filtration.

[0060] Example 2

[0061] A rubber material for protecting harmful chemical reagents, comprising the following specific components:

[0062] The reinforced layer comprises the following materials in parts by weight: nitrile rubber latex 40 parts, halloysite nanotubes 2 parts, antioxidant AW 0.5 parts, sulfur 0.5 parts, zinc oxide 0.5 parts, sodium hydroxide 0.5 parts, thiuram vulcanization accelerator TMTD 0.5 parts, ammonia 0.1 parts, and peregal O-20 0.01 parts;

[0063] The barrier layer comprises the following materials in parts by weight: nitrile rubber latex 40 parts, boron nitride nanosheet 2 parts, antioxidant AW 0.5 parts, sulfur 0.5 parts, zinc oxide 0.5 parts, sodium hydroxide 0.5 parts, thiuram vulcanization accelerator TMTD 0.5 parts, ammonia 0.1 parts, and peregal O-20 0.01 parts;

[0064] The halloysite nanotube has a diameter of 1 μm and an aspect ratio of 300;

[0065] The boron nitride nanosheet has a thickness of 300 nm and a sheet diameter of 200 nm;

[0066] The microporous fiber membrane is a polypropylene microporous membrane with a pore size of 1 μm and a thickness of 0.08 mm.

[0067] The preparation method comprises the following steps:

[0068] (0) Preparation: weigh the thiuram vulcanization accelerator TMTD, add water to prepare an emulsified solution with a mass fraction of 20wt%; weigh the sulfur, grind and add water to prepare a sulfur suspension with a mass fraction of 50wt%; weigh the zinc oxide, grind and add water to prepare a zinc oxide suspension with a mass fraction of 50wt%;

[0069] (1) Reinforced layer latex preparation: according to the above weight ratio, add nitrile rubber latex, halloysite nanotube, antioxidant, water emulsified vulcanization accelerator, ammonia, sodium hydroxide, peregal O-20, suspended sulfur, suspended zinc oxide into the stirrer, disperse uniformly with water as solvent, adjust pH to 7.8;

[0070] (2) Barrier layer latex preparation: according to the above weight ratio, add nitrile rubber latex, boron nitride nanosheet, antioxidant, water emulsified vulcanization accelerator, ammonia, sodium hydroxide, peregal O-20, suspended sulfur, suspended zinc oxide into the stirrer, disperse uniformly with water as solvent, adjust pH to 7.9;

[0071] (3) Place the corresponding microporous fiber membrane flat in a 500 mL sand core suction filter funnel in advance, then evenly pour 3 g of the uniformly stirred barrier layer latex on the fiber membrane, and dry the water in the latex by vacuum suction filtration;

[0072] (4) After the first layer of barrier layer is dried, evenly pour 3 g of the uniformly stirred reinforced layer latex on the fiber membrane, and dry the water in the latex by vacuum suction filtration;

[0073] (5) Refer to (4) to evenly pour the second layer of barrier layer on the dried reinforced layer, and dry the water in the latex by vacuum suction filtration;

[0074] (6) Take out the three-layer film material formed by suction together with the bearing filter membrane, and heat press vulcanize to obtain a protective material, with a vulcanization pressure of 1 MPa, a vulcanization temperature of 140°C, and a vulcanization time of 20 min.

[0075] Example 3

[0076] A rubber material for protecting harmful chemical reagents, comprising the following specific components:

[0077] The reinforced layer comprises the following materials by weight: nitrile rubber latex 65 parts, attapulgite 3 parts, antioxidant BLE 1 part, sulfur 1.5 parts, zinc oxide 3 parts, xanthate vulcanization accelerator ZBX 1.5 parts, sodium bicarbonate 0.5 parts, sodium dodecyl sulfate 0.2 parts;

[0078] The barrier layer comprises the following materials by weight: nitrile rubber latex 65 parts, molybdenum disulfide nanosheet 3 parts, antioxidant BLE 1 part, sulfur 1.5 parts, zinc oxide 3 parts, xanthate vulcanization accelerator ZBX 1.5 parts, sodium bicarbonate 0.5 parts, sodium dodecyl sulfate 0.2 parts;

[0079] The attapulgite has a diameter of 10 μm and an aspect ratio of 200;

[0080] The thickness of the molybdenum disulfide nanosheet is 500 nm, and the sheet diameter is 100 nm.

[0081] The microporous fiber membrane is a polyether sulfone microporous membrane, the membrane pore size is 10 μm, and the thickness is 0.5 mm.

[0082] The preparation method comprises the following steps:

[0083] (0) Preparation: weigh the xanthate type vulcanization accelerator ZBX, add water to prepare an emulsified solution with a mass fraction of 20wt%; weigh the sulfur, grind and add water to prepare a sulfur suspension with a mass fraction of 50wt%; weigh the zinc oxide, grind and add water to prepare a zinc oxide suspension with a mass fraction of 50wt%;

[0084] (1) Preparation of the reinforcing layer latex: according to the above weight ratio, the nitrile rubber latex, attapulgite, antioxidant, water emulsified vulcanization accelerator, sodium bicarbonate, sodium dodecyl sulfate, sulfur suspension and zinc oxide suspension are added into a stirrer to be uniformly dispersed in water as a solvent, and the pH is adjusted to 10.0;

[0085] (2) Preparation of the barrier layer latex: according to the above weight ratio, the nitrile rubber latex, molybdenum disulfide nanosheet, antioxidant, water emulsified vulcanization accelerator, sodium bicarbonate, sodium dodecyl sulfate, sulfur suspension and zinc oxide suspension are added into a stirrer to be uniformly dispersed in water as a solvent, and the pH is adjusted to 10.0;

[0086] (3) The corresponding microporous fiber membrane is placed flat in a 500mL sand core suction filter funnel in advance, then 3g of the uniformly stirred barrier layer latex is uniformly poured on the fiber membrane, and the water in the latex is sucked dry through vacuum suction filtration;

[0087] (4) After the first layer of barrier layer is sucked dry, 3g of the uniformly stirred reinforcing layer latex is uniformly poured on the fiber membrane, and the water in the latex is sucked dry through vacuum suction filtration;

[0088] (5) Referring to (4), the second layer of barrier layer is uniformly poured on the dried reinforcing layer, and the water in the latex is sucked dry through vacuum suction filtration;

[0089] (6) The three-layer film material formed by suction is taken out together with the bearing filter membrane and subjected to hot press vulcanization to obtain a protective material, the vulcanization pressure is 5MPa, the vulcanization temperature is 200℃, and the vulcanization time is 10min.

[0090] Example 4

[0091] This example is basically the same as example 1, except that the microporous fiber membrane is a polyvinylidene fluoride membrane, and the second layer of barrier layer is not contained.

[0092] Example 5

[0093] This example is substantially the same as Example 1, except that the microporous fiber membrane is a polytetrafluoroethylene membrane, and a second layer of the reinforcing layer is further included on top of the second layer of the barrier layer.

[0094] Example 6

[0095] This example is substantially the same as Example 1, except that the fiber nanoreinforcing material is nylon short fiber, the diameter is 1 μm, the aspect ratio is 800, the hot press vulcanization pressure is 1 MPa, the vulcanization temperature is 120 °C, and the time is 10 min.

[0096] Example 7

[0097] This example is substantially the same as Example 1, except that the fiber nanoreinforcing material is aramid short fiber, the diameter is 0.1 μm, the aspect ratio is 300, the hot press vulcanization pressure is 5 MPa, the vulcanization temperature is 200 °C, and the time is 20 min.

[0098] Example 8

[0099] This example is substantially the same as Example 1, except that the microporous fiber membrane-first layer of the barrier layer-reinforcing layer-second layer of the barrier layer in Example 1 is replaced by microporous fiber membrane-first layer of the reinforcing layer-barrier layer-second layer of the reinforcing layer, and the stabilizer in the barrier layer and the reinforcing layer is replaced by gelatin.

[0100] Example 9

[0101] This example is substantially the same as Example 1, except that it includes microporous fiber membrane-first layer of the barrier layer-first layer of the reinforcing layer-second layer of the barrier layer-second layer of the reinforcing layer-third layer of the barrier layer, wherein the fiber nanoreinforcing material is glass short fiber, the diameter is 0.1 μm, and the aspect ratio is 500, wherein the sheet-shaped nanobarrier material is clay nanosheet, the thickness is 300 nm, the sheet diameter is 200 nm, and the stabilizer in the barrier layer and the reinforcing layer is replaced by potassium laurate.

[0102] Example 10

[0103] This example is substantially the same as Example 1, except that the vulcanization pressure is 0.5 MPa, the temperature is 100 °C, and the time is 5 min.

[0104] Example 11

[0105] This example is substantially the same as Example 1, except that the vulcanization pressure is 6 MPa, the temperature is 240 °C, and the time is 30 min.

[0106] Example 12

[0107] This example is substantially the same as Example 1, except that the sheet-shaped nano-barrier material has a thickness of 700 nm and a sheet diameter of 80 nm.

[0108] Example 13

[0109] This example is substantially the same as Example 1, except that the fiber nano-reinforcing material has a diameter of 15 μm and an aspect ratio of 100.

[0110] Comparative Example 1

[0111] This comparative example is substantially the same as Example 1, except that the rubber material is obtained by using a doctor blade and drying, specifically, based on step (2) of Example 1, 3 g of the barrier layer latex and 3 g of the reinforcing layer latex are uniformly coated on the nylon microporous fiber membrane, and then dried at room temperature for 5 h, and then a protective material is obtained by hot pressing vulcanization, with a vulcanization pressure of 1.5 MPa, a vulcanization temperature of 150 °C, and a vulcanization time of 15 min.

[0112] Comparative Example 2

[0113] This comparative example is substantially the same as Example 1, except that the rubber material is obtained by using a calendering film forming method, specifically, based on step (2) of Example 1, 3 g of the barrier layer latex and 3 g of the reinforcing layer latex are uniformly coated on the nylon microporous fiber membrane, and then dried at room temperature for 5 h, and then a protective material is obtained by calendering film forming in an extrusion calender, with a calendering pressure of 0.25 MPa, a temperature of 125 °C, a speed of the fabric of 2.2 m / min, and then cooled and hot pressed vulcanized, with a vulcanization pressure of 1.5 MPa, a vulcanization temperature of 150 °C, and a vulcanization time of 15 min.

[0114] Comparative Example 3

[0115] This comparative example is substantially the same as Example 1, except that it only includes a microporous fiber membrane-barrier layer.

[0116] Comparative Example 4

[0117] This comparative example is substantially the same as Example 1, except that it only includes a microporous fiber membrane-reinforcing layer.

[0118] Comparative Example 5

[0119] The comparative example is basically the same as example 1, except that the nitrile rubber latex is not used, but is replaced by neoprene, and the neoprene is mixed and vulcanized according to the nitrile rubber formula of example 1, the formula does not add alkaline pH regulator and stabilizer, the mixing temperature is 170℃, the mixing time is 5min, after the mixing rubber is obtained, 650 parts of ethyl acetate and 720 parts of gasoline diluent are added, and the reinforced layer latex and the barrier layer latex are prepared, on the basis of step (2) of example 1, 3g of the barrier layer latex and 3g of the reinforced layer latex are evenly coated on the nylon microporous fiber membrane, and the coated membrane is dried at room temperature for 5h, then the coated membrane is sent into the extrusion calender to be calendered into a film, the calendering pressure is set to 0.3MPa, the temperature is 150℃, the speed of the fabric is 2.2m / min, and after cooling, the protective material is obtained by hot pressing vulcanization, the vulcanization pressure is 1.5MPa, the vulcanization temperature is 150℃, and the vulcanization time is 30min.

[0120] Comparative example 6

[0121] The comparative example is basically the same as example 1, except that the stabilizer is not added in the reinforced layer.

[0122] Comparative example 7

[0123] The comparative example is basically the same as example 1, except that the stabilizer is not added in the barrier layer.

[0124] Test example 1

[0125] Permeability test method: According to GB 24539-2021 "Protective clothing- Chemical protective clothing", the permeability test chemicals include 15 kinds of 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), sulfuric acid (mass fraction 96%, CAS No. 7664-93-9, liquid), tetrahydrofuran (CAS No. 109-99-9, liquid), toluene (CAS No. 108-88-3, liquid), ammonia (volume fraction 99.9%, CAS No. 7664-41-7, gaseous), chlorine (volume fraction 99.5%, CAS No. 7782-50-5, gaseous) and hydrogen chloride (CAS No. 7647-01-0, gaseous), and the permeability is divided into 6 levels according to the penetration time, and the standard penetration time of 1st to 6th level is >10 min, >30 min, >60 min, >120 min, >240 min, >480 min, respectively;

[0126] The permeation time test method and steps refer to GB / T23462, and the permeation performance test is carried out in the corresponding standard liquid chemical substance permeation test pool or standard gaseous chemical substance permeation test pool, and the final penetration time is recorded. The test results of a plurality of substances in Table 1 are obtained by mixing a plurality of substances listed together.

[0127] Flame retardant performance test: The flame retardant performance test is carried out by referring to the vertical burning method in GB / T 10707-2008, and the afterglow time, afterburning time and damage length are recorded.

[0128] Thickness: The thickness tester is used for testing.

[0129] Air tightness: The air tightness is tested by pressure method, the pressure difference of the rubber protective material within a certain time is detected by pressure sensor, and the air tightness data is calculated.

[0130] Low temperature bending resistance: The low temperature bending resistance of the obtained rubber protective material is tested by using rubber high and low temperature bending fatigue testing machine GT-7011-DHD (GOTECH).

[0131] High temperature aging resistance test: the rubber protective material of the examples and the comparative examples was tested for high temperature aging resistance, in the following way: after the material was treated at 72℃ for 72h, observation was made to see if the surface of the rubber protective material changed.

[0132] The test results are shown in Tables 1 and 2 below.

[0133] Table 1: Test results of the chemical protective performance of the rubber material for protecting chemical agents

[0134]

[0135] Table 1: Table 1 continued

[0136]

[0137] Table 1: Table 2 continued

[0138]

[0139] Table 2: Test results of the performance of the rubber material for protecting chemical agents

[0140]

[0141] Table 2: Table 1 continued

[0142]

[0143] Table 2: Table 2 continued

[0144]

[0145] From the analysis of the test results in Tables 1 and 2, it can be seen that the thickness of the rubber protective material can be effectively reduced by the technical scheme of the present application, and the air tightness thereof is improved, and the protective material obtained has better protective ability against chemical agents and better resistance to flexing and aging.

[0146] Specifically, according to the experimental results of Examples 1-3, it is shown that the rubber protective material obtained within the ratio range of the present application has outstanding protective effect and resistance to flexing and aging, and is extremely suitable for the preparation of protective products for protecting harmful chemical agents, such as protective clothing, protective masks or protective blankets, etc.

[0147] According to the experimental results of embodiments 1, 4-5 and comparative examples 3-4, the design of different layers of protective material will affect the protective performance and air tightness, flexibility and aging resistance. When the number of layers of protective material 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 layers of protective material, the lower the air tightness, and harmful chemicals are easy to enter, which will damage human health. When the number of layers of protective material is more, the protective performance of the protective material will be significantly improved, but too many layers of design will lead to an increase in the thickness of the protective material, affecting the flexibility of the protective material. At the same time, according to the experimental data, the performance of the protective layer and the reinforcing layer is different. The protective layer has better chemical barrier ability than the reinforcing layer, but the flexibility is generally poor. The reinforcing layer mainly has good flexibility, and the strength and toughness of the material are better. The application scheme combines the reinforcing layer and the barrier layer to have good chemical reagent protection ability and flexibility and aging resistance.

[0148] According to the experimental results of embodiments 1, 6-7, 10-11, the last step of hot pressing vulcanization needs to control the appropriate vulcanization temperature, pressure and time. When the hot pressing vulcanization parameters are too high or too low, it will affect the performance of the protective material, and the material is more prone to damage.

[0149] According to the experimental results of embodiments 1 and 8, under the same layer design, because the design of the layer sequence of the protective layer or the reinforcing layer is different, the performance of the protective material is also different. When the number of protective layers is greater than the number of reinforcing layers, the protective material has stronger chemical barrier ability and stronger air tightness. When the number of protective layers is less than the number of reinforcing layers, the protective material has better flexibility.

[0150] According to the experimental results of embodiments 1, 12-13, the sheet-shaped nano barrier material of the barrier layer and the fiber nano reinforcing treatment material of the reinforcing layer need to have appropriate parameters. When the parameters are not appropriate, the barrier performance of the barrier layer and the flexibility and aging resistance of the reinforcing layer will decrease.

[0151] According to the experimental results of embodiments 1 and comparative examples 1-2, the preparation method of water-based mixed material combined 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 basis of the original and reduce the thickness of the protective material. At the same time, the protective material can be stacked to the maximum due to the effect of filtration, and the air tightness of the protective material is also improved.

[0152] According to the experimental results of Example 1 and Comparative Example 5, when the butyl rubber latex is replaced by neoprene rubber, because the neoprene rubber is solid, it is necessary to use ethyl acetate as a solvent and gasoline as a diluent to obtain neoprene 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 neoprene rubber and reinforcing materials is weak, so the barrier performance, flex resistance and aging resistance of the final protective material are general.

[0153] According to the experimental results of Example 1 and Comparative Examples 6-7, the addition of stabilizers has a great influence on the entire preparation process. When no stabilizer is added, the latex is easy to settle or flocculate, which not only affects the suction filtration and increases the thickness of the protective material, but also reduces the barrier performance, flex resistance and aging resistance of the protective material.

[0154] The above is only an 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. The present application can have various changes and variations for those skilled in the art. Any modification, equivalent replacement, improvement, etc. within the technical idea and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a rubber material for protection against harmful chemical reagents, characterized in that, The rubber material includes 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 barrier layer superimposed on it. The number and order of the reinforcing layer and barrier layer can be freely adjusted. By weight, the reinforcing layer comprises: 40-65 parts of nitrile rubber latex, 2-3 parts of fiber nano-reinforcing 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; By weight, the barrier layer comprises: 40-65 parts of nitrile rubber latex, 2-3 parts of sheet-like 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; The fiber nanoreinforcing material is one or more of nylon short fibers, aramid short fibers, glass short fibers, carbon nanotubes, attapulgite, and halloysite nanotubes; the fiber diameter of the fiber nanoreinforcing material is not greater than 10 μm and the aspect ratio is not less than 200. The sheet-like nanobarrier material is one or more of graphene, clay nanosheets, boron nitride nanosheets, and molybdenum disulfide nanosheets; the thickness of the nanosheets of the sheet-like nanobarrier material is not greater than 500 nm, and the sheet diameter is not less than 100 nm. The method includes the following steps: 1) Preparation of reinforcing layer latex: According to the weight ratio, nitrile rubber latex, fiber nano-reinforcing material, antioxidant, vulcanization accelerator, alkaline pH adjuster, stabilizer, sulfur, and zinc oxide are added to a mixer and stirred and dispersed evenly with water as solvent, and the pH value is adjusted to 7.8~10. 2) Preparation of barrier layer latex: Add nitrile rubber latex, sheet-like nano barrier material, antioxidant, vulcanization accelerator, alkaline pH adjuster, stabilizer, sulfur, and zinc oxide to a mixer according to the weight ratio, and stir and disperse evenly with water as solvent, and adjust the pH value to 7.8~10. 3) Place the microporous fiber membrane flat in the vacuum filtration device, then pour the reinforcing layer latex or barrier layer latex evenly onto the microporous fiber membrane, and remove the water from the latex by vacuum filtration. 4) The dried and formed film material is taken out and hot-pressed and vulcanized to obtain the rubber material.

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

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

4. The method for preparing a rubber material for protection against harmful chemical reagents according to claim 1, characterized in that, The alkaline pH adjuster is one or more selected from 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 one or more of casein, gelatin, sodium dodecyl sulfate, potassium laurate, and phenazine.

5. The method for preparing a rubber material for protection against harmful chemical reagents according to claim 1, characterized in that, The structure of the rubber material is microporous fiber membrane-barrier layer-reinforcing layer-barrier layer, or microporous fiber membrane-barrier layer-reinforcing layer, or microporous fiber membrane-barrier layer-reinforcing layer-barrier layer-reinforcing layer, or microporous fiber membrane-reinforcing layer-barrier layer-reinforcing layer, or microporous fiber membrane-reinforcing layer-barrier layer-reinforcing layer, or microporous fiber membrane-reinforcing layer-barrier layer-reinforcing layer-barrier layer.

6. The method for preparing a rubber material for protection against harmful chemical reagents according to claim 1, characterized in that, In step 4), the hot-press vulcanization pressure is 1~5MPa, the temperature is 140~200℃, and the time is 10~20min; and / or, In steps 1) and 2), before adding sulfur and zinc oxide to the nitrile rubber latex, they are ground into a suspension with water; and / or, In steps 1) and 2), before adding the vulcanization accelerator to the nitrile rubber latex, water is added to prepare an aqueous emulsion.

7. A rubber material for protection against harmful chemical reagents, characterized in that, The rubber material is prepared by the preparation method described in any one of claims 1 to 6.

8. The use of the rubber material for protection against hazardous chemical reagents as described in claim 7 in the preparation of protective products for protection against hazardous chemical reagents.

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