WO2020244641A1 - Composite material containing activated carbon, preparation method therefor and use thereof - Google Patents

Abstract

Provided are a composite material containing an activated carbon, a preparation method therefor and the use thereof, belonging to the field of materials. The composite material contains a substrate, an activated carbon, and an adhesive composition between the substrate and the activated carbon, wherein the adhesive composition contains an adhesive and a thickener. According to the composite material, the effective gram weight of the activated carbon in the composite material is significantly improved, an excellent washing fastness and peeling strength can be acquired while excellent gas permeability and moisture permeability are achieved. In addition, the composite material also has an excellent adsorption property.

Description

Composite material containing activated carbon and preparation method and use thereof

This application claims the priority of an earlier application for a Chinese invention patent filed with the State Intellectual Property Office of China on June 6, 2019, with the application number 201910492736.8, and the title of the invention "composite material containing activated carbon and its preparation method and use". The entirety of this prior application is incorporated herein by reference.

Technical field

The invention belongs to the field of materials, and specifically relates to a composite material containing activated carbon and a preparation method and application thereof.

Background technique

In the fields of scientific research, chemical industry and safety protection, people usually need to be cautious about some reagents or atmospheres that may exist in the environment. These reagents or atmospheres may have high irritation or even neurotoxicity and other hazards. For this reason, protective materials and clothing are used to prevent humans from coming into contact with these substances or to avoid exposure to dangerous substances.

Some of the existing protective clothing used for the above purpose uses materials that are impermeable to air and water vapor to increase safety. However, because these materials are not breathable, it is difficult to dissipate the heat generated by human movement and exchange air, and they are usually relatively heavy, which is not conducive to the flexibility and comfort of the wearer, and also increases the wearer's burden. Improvements to such protective materials include the selection of protective materials that are impermeable to air but permeable to water vapor. Such materials generally include membranes that are impermeable to air but permeable to water vapor, and are used to block toxic substances. However, there is still a gap in the adsorption performance and protection performance of materials characterized by similar membrane systems. In addition, even such a film cannot ensure sufficient air permeability, especially when it is combined with fabric materials through an adhesive process such as hot melt adhesive. In addition, there have been attempts to provide a multilayer, woven, air-permeable filter material that includes an activated carbon adsorption layer in the form of carbon fibers. However, on the one hand, the activated carbon adsorption layer requires the hot melt adhesive layer to bond with the substrate, which not only increases the weight of the composite material, but also the hot melt adhesive is not uniformly distributed on the substrate after melting, and the air permeability is still unsatisfactory. . On the other hand, if the coverage of the hot melt adhesive layer is reduced in order to improve the weight and air permeability of the composite material, the washing fastness of the composite material and the performance after washing cannot meet the quality requirements.

Summary of the invention

In order to improve the deficiencies of the prior art, the present invention provides a composite material comprising a substrate, activated carbon and a binder composition between the substrate and the activated carbon, wherein the binder composition comprises a binder and Thickener.

According to the composite material of the present invention, the substrate includes a first substrate and a second substrate, the activated carbon is interposed between the first substrate and the second substrate, and the adhesive composition is respectively interposed Between the activated carbon and the first substrate, and between the activated carbon and the second substrate.

According to the composite material of the present invention, wherein the first substrate and the second substrate may be the same or different, and are independently selected from the group consisting of woven fabrics, circular knitted fabrics, looped knitted fabrics, non-woven plain cotton and linen fabrics, and adhesive Textile or cotton wool.

According to the composite material of the present invention, the first substrate and the second substrate may be selected from aramid materials such as aramid materials, aromatic polysulfone amides such as aramid materials, and non-woven fabrics. Such as non-woven or spunlace non-woven materials.

The non-woven or spunlace material may be selected from, for example, polyester, polypropylene, nylon, spandex, acrylic, viscose fiber, chitin fiber, superfine fiber, tencel, silk, bamboo fiber, wood pulp fiber , Seaweed fiber and other materials.

The non-woven fabric or spunlace material can be prepared from a single-component polyethylene, or can be composited by a two-component material of polyethylene and polyethylene terephthalate, or a double-component polyethylene and polypropylene The component materials are compounded.

As an example, the first substrate is selected from aramid materials such as aramid materials, aromatic polysulfone amides such as aramid materials; the second substrate is selected from non-woven fabrics such as non-woven materials Cloth or spunlace non-woven materials.

According to the composite material of the present invention, the grammage (mass per unit area) of the first substrate and the second substrate may be the same or different, and are independently selected from 5 to 200 g/m ² , for example, 10 to 150 g/m ² . As an example, the grammage of the first substrate is selected from 20 to 150 g/m ² , such as 50 to 120 g/m ² , such as 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105 or 110 g/m ² ; the gram weight of the second substrate is selected from 10-50 g/m ² , such as 15-35 g/m ² , such as 20, 25 or 30 g/m ² .

According to the composite material of the present invention, the breaking strength (N) of the first substrate and the second substrate may be the same or different, and are independently selected from 5-800, such as 6-50, such as 8-50, such as 8. -20, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50; or, for example 500-700, such as 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700;

The elongation at break (%) of the first substrate and the second substrate may be the same or different, and are independently selected from 10-250, such as 100-250, such as 100-200, such as 100, 105, 120 , 130, 140, 150, 155, 160, 170, 180, 190, 200, 250; or, such as 10-50, such as 15, 20, 25, 30, 35, 40, 45.

Preferably, the elongation at break (%) of the first substrate may be 25-35, such as 26, 27, 28, 29, 30, 31, 32, 33, 34, for example, 28-29% in the radial direction, Orientation is 32-33%; preferably, the elongation at break (%) of the second substrate may be, for example, 100-250, for example, 100, 105, 120, 130, 140, 150, 155, 160, 170, 180 , 190, 200, 250.

The breaking time of the first substrate and the second substrate may be the same or different, and are independently selected from 60 seconds or more. For example, the breaking time of the second substrate may be 60-120 seconds, such as 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120 seconds.

In the context of the present invention, the adhesive composition between the activated carbon and the first substrate can be referred to as the first adhesive composition, the adhesive composition between the activated carbon and the second substrate The substance may be referred to as a second adhesive composition.

In the context of the present invention, when the "adhesive composition" is described, it means that the "first adhesive composition and the second adhesive composition" are described at the same time. Also, when describing "substrate", it means that "first substrate and second substrate" are described at the same time.

According to the composite material of the present invention, the first adhesive composition and the second adhesive composition may be the same or different, respectively.

According to an embodiment of the present invention, in the adhesive composition, such as the first adhesive composition and the second adhesive composition, the content of the thickener may be 1-10 of that of the adhesive. The weight% is, for example, 1, 2, 5, 8, 10% by weight.

According to the composite material of the present invention, the adhesive may be selected from, for example, acrylic polymer and/or polyurethane adhesives, and the acrylic polymer adhesive may be acrylic acid self-polymerization or copolymerization with other monomers. The product, the other monomers can be selected from styrene, propylene, isopropylene, butene, isobutylene, pentene, isopentene, neopentene, hexene, isohexene, neohexene, styrene, methyl One or more of styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and methyl methacrylate.

As an example, you can choose an adhesive with the following structure:

Acrylic polymer adhesive:

Wherein, m is an integer between 3000-5000, n is an integer between 3000-5000, and p is an integer between 300-500.

Polyurethane adhesive:

Wherein, n1 is an integer between 100-200; n2 is an integer between 100-200.

According to the present invention, the adhesive may be in the form of an emulsion or a dispersion, such as an acrylic adhesive water-based emulsion or a polyurethane adhesive water-based dispersion.

According to the present invention, the viscosity of the adhesive may be 100-5000mpa·s, such as 150-3000mpa·s, such as 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300 , 1400, 1500, 1600, 1700, 1800, 1900, 2000mpa·s.

According to the present invention, the viscosity of the adhesive composition may be 15000-30000 mpa·s, such as 20000-25000 mpa·s, such as 20000 mpa·s, 25000 mpa·s. For example, the viscosity of the first adhesive composition and the second adhesive composition may be the same or different, and are independently selected from 15000-30000mpa·s, such as 20000-25000mpa·s, such as 20000, 21000, 22000, 23000 , 24000 or 25000mpa·s.

Preferably, the viscosity of the adhesive composition is the viscosity of the adhesive composition when it is attached to the substrate but not dried.

It should be understood that the thickener is not particularly limited in the composite material of the present invention, as long as it can increase the viscosity of the adhesive composition to the above-mentioned viscosity. For example, the thickener may be selected from acrylic copolymer thickeners (such as anionic polyurethane thickeners), polyurethane thickeners (such as nonionic polyurethane thickeners), polycarboxy anionic polymers Class thickener.

According to the composite material of the present invention, the weight of the first adhesive composition is ma1, the weight of the first substrate is ms1, and preferably, the ratio of ma1/(ma1+ms1) is 80% or less, for example, 70% or less , 65% or less, 60% or less, 50% or less, 40% or less or 30% or less; or preferably, the ratio of ma1/(ma1+ms1) is 5% or more, 8% or more, 10% or more or 12% or more . As an example, the ratio of ma1/(ma1+ms1) is 5-65%, such as 10-50%, and examples thereof can be 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18 %, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%.

According to the composite material of the present invention, the weight of the second adhesive composition is ma2, the weight of the second substrate is ms2, and the ratio of ma2/(ma2+ms2) is 90% or less, such as 85% or less, such as 80%. % Or less, preferably 75% or less, such as 50-72%, examples of which may be 55%, 60%, 65%, 70%.

According to a preferred embodiment of the present invention, the adhesive composition is distributed in dots on the substrate. More preferably, the first adhesive composition is distributed in dots on the first substrate, and the second adhesive composition is distributed in dots on the second substrate. More preferably, the activated carbon is in contact with the first binder composition and the second binder composition.

Preferably, the distribution density of the adhesive composition on the substrate is 4 million pieces/m ² or more, such as 5.5 million pieces/m ² or more, 5.6 million pieces/m ² or more, such as 4-7 million pieces/m ² , 5-7 million pieces/m ² .

According to an embodiment of the present invention, the diameter of the dots of the adhesive composition on the substrate is about 30-200 mesh, such as 40-150 mesh, such as 50-120 mesh, such as 60, 70, 80, 90 or 100 mesh .

According to an embodiment of the present invention, the distance between points of adjacent adhesive compositions on the substrate is 0.1-1.5 mm.

According to the composite material of the present invention, the activated carbon may be granular activated carbon, preferably spherical activated carbon or similar spherical activated carbon.

According to the present invention, the median particle diameter D _{50 of} the granular activated carbon may be 0.1-2.0 mm, for example 0.1-1.2 mm, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2mm.

According to the present invention, a specific surface area of the granular activated carbon is 700-1500m ² / g, such as 1000 ~ 1250m ² / g.

According to the present invention, the weight of activated carbon in the composite material can be 80-250g/m ² , such as 120-240g/m ² , preferably 160-220g/m ² , examples of which can be 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215g/m ² .

According to an embodiment of the present invention, the median pore diameter of the spherical activated carbon is 1 to 5 nm, such as 1.5 to 4.8 nm, such as 1.8 to 4.0 nm.

According to an embodiment of the present invention, the compressive strength of the spherical activated carbon is 5-300N, such as 10-150N, such as 20-100N, such as 30-70N. Wherein, the compressive strength refers to the maximum pressure value that each spherical activated carbon can withstand.

According to an embodiment of the present invention, the cracking rate of the spherical activated carbon may be less than 3.0%, such as 0.3-2.0%, such as 0.5-1.0%.

According to an embodiment of the present invention, the activated carbon is polymer-based activated carbon.

According to an embodiment of the present invention, the polymer can be prepared by mixing monomers and initiators for polymerization reaction. As an example, the polymer may be a homopolymer or a copolymer. Wherein, the homopolymer refers to a polymer prepared by the polymerization of one monomer, and the copolymer refers to a polymer prepared by the polymerization of two or more monomers.

According to an embodiment of the present invention, the monomer may be selected from compounds having 2 to 60 carbon atoms and at least 1 carbon-carbon double bond, for example, having 2 to 20 carbon atoms and at least 1 carbon-carbon Compounds with double bonds. For example, the monomer may be selected from the following materials: ethylene, propylene, isopropylene, butene, isobutylene, pentene, isopentene, neopentene, hexene, isohexene, neohexene, styrene, methyl Styrene, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butadiene, pentadiene, isoprene, pentadiene, isohexadiene, divinylbenzene, diethylene glycol diethylene Base ether.

Alternatively, the polymer matrix of the copolymer includes a structural unit derived from a first monomer and a structural unit derived from a second monomer, wherein the first monomer has 2-10 carbon atoms and contains at least one Carbon-carbon double bonds, the second monomer has 4-15 carbon atoms and contains at least two carbon-carbon double bonds.

Preferably, in the polymer matrix of the copolymer, the structural units derived from the first monomer account for 75% to 98% of the total structural units of the polymer network, preferably 80% to 90%; The structural units of the second monomer account for 25% to 2% of the total structural units of the polymer network, preferably 20% to 10%.

According to an embodiment of the present invention, the first monomer is selected from styrene, methyl styrene, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, and monoolefins having 2-6 carbon atoms One or more of the monoolefins with 2-6 carbon atoms, for example, ethylene, propylene, isopropylene, butene, isobutylene, pentene, isopentene, neopentene, hexene, isohexene , Neohexene, etc.

According to an embodiment of the present invention, the second monomer is selected from the group consisting of butadiene, pentadiene, isoprene, pentadiene, isohexadiene, divinylbenzene and diethylene glycol divinyl ether One or more.

According to an embodiment of the present invention, the polymerization reaction may be a suspension polymerization reaction; preferably, the polymerization reaction is also carried out in the presence of water, a dispersant, and a co-dispersant.

For example, the weight ratio of water: dispersant: auxiliary dispersant is 800-1000: 0.5-3.0: 0.05-0.2;

When the polymer is a homopolymer, the weight ratio of monomer:initiator may be 1:0.003-0.01.

If present, the weight ratio of the first monomer: the second monomer: the initiator may be 0.75-0.98: 0.02-0.25: 0.003-0.01.

Preferably, water, dispersant, and co-dispersant constitute the water phase, and the monomer of the homopolymer, the first monomer, the second monomer and/or the initiator of the copolymer constitute the oil phase; the oil phase and the water phase The weight ratio can be 1:4-6.

According to an embodiment of the present invention, the suspension polymerization reaction may include:

Put each component into the reaction kettle, pass compressed air or nitrogen into the reaction kettle, keep the pressure in the reaction kettle at a positive pressure of less than or equal to 0.5MPa gauge pressure, increase the temperature to 70°C-90°C, keep it warm for 2 hours- After 24 hours, the temperature is increased to 100°C-150°C, and the temperature is kept for 4 hours to 36 hours, and then washed with water, dried, and sieved to obtain spherical polymers.

In a preferred embodiment, the dispersant is an inorganic dispersant or an organic dispersant or a combination thereof, the inorganic dispersant is, for example, a silicate, a carbonate, or a phosphate, or a combination thereof, and the organic dispersant is, for example, Polyvinyl alcohol, gelatin, carboxymethyl cellulose or polyacrylate, or a combination thereof.

In a preferred embodiment, the co-dispersing agent is sodium lauryl sulfate, calcium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, calcium petroleum sulfonate, sodium petroleum sulfonate or barium stearate , Or a combination thereof.

In a preferred embodiment, the initiator is an organic peroxy compound, an inorganic peroxy compound or an azo compound, or a combination thereof.

In a preferred embodiment, the initiator is diacyl peroxide, dioxane peroxide, peroxy ester, azobisisobutyronitrile or persulfate, or a combination thereof.

Preferably, the polymerization reaction can also be carried out in the presence of a porogen. The porogen may be selected from paraffin, magnesium sulfate, sodium carbonate, gelatin or glycerin, or a combination thereof.

According to an embodiment of the present invention, the granular activated carbon, such as spherical activated carbon, may be commercially available or prepared by the following method:

1) Carbonize the spherical polymer;

2) Activate the product obtained in step 1).

According to the present invention, the definition of the polymer is as described above.

According to the present invention, the polymer may be a sulfonated polymer or an unsulfonated polymer. When a polymer that has not been sulfonated is used, the sulfonation may be performed before the carbonization step and/or the sulfonation may be performed in situ during the carbonization process.

As an example, the unsulfonated polymer can also be prepared according to known methods or commercially available.

The sulfonation can be performed using raw materials known in the art, for example, contacting an unsulfonated polymer with a sulfonating agent. The sulfonating agent can be selected from one or a mixture of sulfuric acid (such as concentrated sulfuric acid), fuming sulfuric acid, and SO ₃ .

According to the present invention, the total weight ratio of the unsulfonated spherical polymer to the sulfonating agent may be 3:1 to 1:3, such as 2:1 to 1:2, such as 1:1 to 1:1.5.

The temperature of the sulfonation step can be varied within a wide range.

For example, when the sulfonation is performed before the carbonization step, the temperature of the sulfonation step may be 60-200°C, such as 70-180°C, for example 80-150°C;

Preferably, the sulfonation step can perform the reaction while raising the temperature within the above-mentioned temperature range. The rate of temperature increase can be no more than 10°C/min, for example no more than 5°C/min, such as no more than 3°C/min.

The time of the sulfonation step can be 0.5-12 hours, preferably 1-10 hours, such as 2-10 hours.

Preferably, the sulfonation is carried out under an inert gas atmosphere, and the inert gas may be selected from one or more mixtures of nitrogen, helium, and argon.

According to the present invention, the carbonization in step 1) can be performed in an inert atmosphere or in a mixed atmosphere of an inert gas and oxygen.

Generally, the carbonization temperature may be 100-950°C, for example 150-900°C, such as 300-850°C.

When the sulfonation is performed before the carbonization step, the start temperature of the carbonization step may be equal to or higher than the end temperature of the sulfonation temperature.

Preferably, the carbonization step may be in the above-mentioned temperature range, and the reaction can be performed while raising the temperature. The rate of temperature increase can be no more than 10°C/min, for example no more than 5°C/min, such as no more than 3°C/min.

Preferably, the carbonization can be performed sequentially in 2 or more temperature regions, for example, in 2 to 10 temperature regions. And preferably, the temperatures of the temperature zones are different from each other. Alternatively, carbonization can be performed at a temperature that is gradually increased.

Preferably, the carbonization may have the same or different heating rate and the same or different holding time in different temperature regions.

Preferably, when the carbonization is carried out in two or more temperature regions in sequence, first carbonize in the first temperature region, and then sequentially enter the next temperature region, such as carbonization in the second temperature region; for example, the temperature of the first temperature region can be It is 100-500°C, for example 150-450°C; the temperature in the second temperature zone may be higher than the first temperature zone, for example 500-950°C, such as 650-950°C.

Preferably, the carbonization time is 30 minutes-10 hours, such as 1-8 hours, such as 2-6 hours.

Preferably, the inert gas is selected from at least one of nitrogen, helium, and argon;

Preferably, when the carbonization is performed in a mixed atmosphere of inert gas and oxygen, the volume percentage of oxygen in the mixed atmosphere is 1-5%.

It should be understood that if the temperature at which the spherical polymer is subjected to sulfonation, the spherical polymer can also be sulfonated in situ during the carbonization process.

According to the present invention, the activation of step 2) may include a first activation step and a second activation step.

Preferably, the first activation step is performed in an atmosphere containing water vapor; the second activation step is performed in an atmosphere containing CO ₂ .

Preferably, the temperature of the first activation treatment is 700-1300°C, such as 800-1200°C, such as 850-950°C; the time of the first activation step may be 1-24 hours, such as 5-15 hours , Such as 6-12 hours.

Preferably, the atmosphere of the first activation step contains water vapor, especially a water vapor/inert gas mixture, preferably a water vapor/nitrogen mixture, or consists of the above.

Preferably, the volume ratio (flow rate ratio) of the nitrogen and water vapor is above 3:1, for example 4:1-10:1, preferably 4:1-8:1.

According to the present invention, the atmosphere of the first activation step may not contain other gases, such as carbon oxides (such as CO ₂ ), oxygen, and ammonia.

Preferably, the temperature of the second activation step is 700-1300°C, preferably 800-1200°C, such as 850-950°C; the time of the second activation step is 1-10 hours, such as 3-8 hour.

Preferably, the atmosphere of the second activation step contains CO ₂ , such as CO ₂ or a mixture of CO ₂ and an inert gas, such as a mixture of CO ₂ and nitrogen.

Preferably, when the second activation atmosphere comprises a mixture of nitrogen and CO _2, nitrogen and CO ₂ volume ratio (flow rate ratio) can be 10: 1 to 1: 10, such as 10: 1 to 2: 1, e.g. 8:1～4:1, such as 3:1～2:1.

According to the present invention, the atmosphere of the second activation step may not contain other gases, such as water vapor.

According to the present invention, a gradient temperature increase can be used to increase the temperature. Alternatively, when the temperature is raised to a certain temperature, stay for 1 to 240 minutes, for example, 5 to 150 minutes, and then raise the temperature again.

Preferably, the heating process of the method of the present invention can be continuous or batchwise.

According to an embodiment of the present invention, the composite material preferably does not include a membrane that is impermeable to air and can permeate water vapor.

According to the present invention, there is also provided a garment including the composite material.

The present invention also provides a method for preparing the composite material, including the following steps:

1) Providing a first substrate comprising an adhesive composition, wherein the adhesive composition is distributed on the surface of the first substrate in dots;

2) The activated carbon is contacted with the point of the adhesive composition to obtain the first substrate for binding the activated carbon;

3) Adhere the activated carbon side of the first substrate to the second substrate through the adhesive composition.

The preparation method according to the present invention may further include the following steps:

1) Providing a first substrate comprising a first adhesive composition, wherein the first adhesive composition is distributed on the surface of the first substrate in dots;

2) The activated carbon is contacted with the point of the first adhesive composition to obtain the first substrate for binding the activated carbon;

3) Adhere the activated carbon side of the first substrate to the second substrate through the second adhesive composition.

According to an embodiment of the preparation method of the present invention, the adhesive in the adhesive composition undergoes a foaming step.

As an example, the foaming ratio value (the ratio of the volume after foaming to the volume before foaming) is about 1.1 to 1.4:1.

According to the embodiment of the preparation method of the present invention, drying is performed after step 2) and/or step 3). Preferably, the drying is heat drying. The heating and drying temperature is lower than the decomposition temperature of the first adhesive composition and the second adhesive composition, for example, 100-150°C.

According to an embodiment of the preparation method of the present invention, the surface of the side to be bonded of the second substrate in step 3) contains the second adhesive composition. Preferably, the second adhesive composition is coated on the surface of the second substrate.

The present invention also provides the use of the composite material for adsorbing gas and/or liquid. Preferably, the gas includes any gas derived from the spontaneous evolution of organic liquids and/or solids under normal temperature and pressure, such as those derived from the volatilization of volatile organic compounds with a melting point lower than room temperature and a boiling point between 50 and 260°C Gas, including but not limited to hydrocarbons, halogenated hydrocarbons, oxygenated hydrocarbons and nitrogen hydrocarbons, such as benzene series, organic chlorides, Freon series, organic ketones, amines, alcohols, ethers, esters, acids and petroleum hydrocarbon compounds, etc. , Such as propyl sulfide.

Benefits:

The inventor surprisingly found that the composite material prepared by the present invention significantly increases the effective weight of activated carbon in the composite material, and can achieve excellent washing fastness and peel strength while achieving excellent air permeability and moisture permeability. Tensile strength, flame retardant properties. It is especially important that on the basis of the above-mentioned properties, the composite material also has excellent adsorption performance or gas-gas protection time.

Description of the drawings

Figure 1 is a SEM electron micrograph of the product of Example 1;

Figure 2 is a SEM electron micrograph of the product of Comparative Example 1.

Detailed ways

Hereinafter, the preparation method of the present invention will be further described in detail in conjunction with specific examples. It should be understood that the following examples are only illustrative and explanation of the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the foregoing content of the present invention are covered by the scope of the present invention.

The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial sources.

Unless otherwise specified, the following aramid fiber base fabric is a commercially available MX-96 product, with a weight of about 100g/m ² , breaking strength: radial 733N, weft direction 752.6N; breaking elongation: radial 28.2% , Latitude 32.9%.

Unless otherwise specified, the model of the non-woven fabric below is a commercially available EP-SZ-30 product, with a weight of about 30g/m ² , breaking strength: about 32N, breaking elongation: about 165%, breaking time: about 94S .

The specific surface area is tested by MicrotracBEL Corp.'s Belsorp mini II nitrogen physical adsorption instrument. The compressive strength is tested by the pressure tester of Shanghai Yihuan Instrument Technology Co., Ltd.

Propyl sulfide "gas-gas protection time" is tested according to the method of GJB3253-98.

The tensile strength and elongation at break are tested according to the method of GB3923-83.

The flame retardant performance is tested according to the method of GB5455-2014.

Preparation Example 1: Preparation of spherical activated carbon

1.1 Preparation of spherical polymer matrix

Add 20 liters of water to a 50 liter polymerization kettle, heat to 40°C, add 12 g magnesium carbonate, 25 g sodium carboxymethyl cellulose and 0.18 g calcium dodecyl benzene sulfonate under stirring. 3.6kg of divinylbenzene, 1.2kg of diethylene glycol divinyl ether and 25g of sodium persulfate are mixed into the oil phase, then 2.2kg of sodium carbonate is added, the polymerization vessel is closed, and clean compressed air is introduced into the polymerization vessel. Keep the gas pressure in the kettle at 0.05MPa. Then, the stirring was turned on, the liquid beads in the kettle were adjusted to the appropriate particle size, the temperature was raised to 90°C, kept for 9 hours, and then raised to 120°C, kept for 20 hours, filtered, washed, dried and sieved to obtain a white spherical polymer 3.12 kg.

1.2 Sulfonation and carbonization

Put the polymer obtained in step 1.1 into a 50-liter reaction kettle, add 10kg of fuming sulfuric acid with a mass concentration of 105%, increase the temperature to 110°C, keep it warm for 16 hours, slowly add water after cooling down, and draw out 1/3 of the liquid when the kettle is full. Continue to add water dropwise until the sulfuric acid concentration in the kettle is less than 5%, and after drying, 4.28 kg of polymer microspheres are obtained. Subsequently, under a nitrogen atmosphere, the polymer microspheres were heated at a heating rate of 3°C/min as follows:

Heat to 120°C and stay for 110 minutes;

Heat to 180°C and stay for 250 minutes;

At a heating rate of 3°C/min, in a mixed atmosphere where the volume percentage of oxygen is 1%, perform the following heating treatment:

Heat to 250°C and stay for 360 minutes;

Heat to 450°C and stay for 240 minutes;

Then heat to 700°C and stay for 90 minutes. Cool down to obtain carbonized products.

1.3 Activation

In a rotary tube furnace, the carbonized product obtained in step 1.2 is heated to 800°C at a rate of 3°C/min under a mixed atmosphere of water vapor and nitrogen with a volume ratio of 1:7 (L/min), and after staying for 420 minutes , And then heated to 950°C at a rate of 4°C/min under a mixed atmosphere of carbon dioxide and nitrogen with a flow rate ratio of 1:7 (L/min) and stayed for 200 minutes. The temperature was lowered to obtain spherical activated carbon GSC3 with a yield of 42% based on the polymer. The median diameter of the product is 0.40mm, the median pore diameter is 2.95nm, the specific surface area is 1011m ² /g, the compressive strength is 78.24N, the bulk density is 514g/L, and the cracking rate is 3.32%.

Preparation Example 2: Preparation of Adhesive Composition A

The adhesive used in this embodiment is selected from commercially available acrylic polymer adhesives represented by the following formula:

Wherein, m is an integer between 3000-5000, n is an integer between 3000-5000, p is an integer between 300-500, viscosity is 100-500mpa·s, pH is 7-9, density is 1.04g/ cm ³ , solid content 52±1%.

The thickener used in this embodiment is selected from commercially available acrylic copolymer anionic thickeners, with a viscosity of 1.5% white pulp (urban tap water) above 90,000 mPa·s, and a solid content of ±1%.

Step 1: Pour the adhesive emulsion into the glue reservoir, turn on the mixer, about 7 minutes, and the foaming ratio (volume ratio) is about 1.3;

The second step: add thickener, the amount of thickener added is about 5% by weight of the binder, the stirring time is about 15min, the speed of the mixer is 80-120r/min, and the viscosity is 20000-25000mpa·s Composition A.

Preparation Example 3: Preparation of Adhesive Composition B

With reference to Preparation Example 2, the adhesive composition B with a viscosity of 20000-25000mpa·s was obtained, the difference being:

The adhesive is selected from commercially available polyurethane adhesive emulsions shown in the following formula:

Wherein, n1 is an integer between 100-200; n2 is an integer between 100-200; viscosity is 20-1500mpa·s, pH is 7-9, density is 1.04-1.09g/cm ³ , solid content is 60± 2%.

And the thickener is selected from polyurethane non-ionic thickeners, viscosity ≤ 3000CPS/25°C, and solid content 40%.

Example 1: Preparation of composite materials

A sulfonamide fiber base fabric with a gram weight of 100g/m ² is selected, and the adhesive composition A is coated on one side of the sulfonamide fiber base fabric in dots using a 120 mesh screen On the surface, a distribution density of 5579527 pieces/m ² was obtained, and the amount of glue (that is, the amount of adhesive composition A on the base cloth) was 30 g/m ² .

The spherical activated carbon obtained in Preparation Example 1 was contacted with the dot-coated adhesive composition A to obtain a first substrate bonded with activated carbon, and then sent to an oven for drying. After two stages of high temperature drying, the oven temperature was 100 ℃, drying time 5min.

Apply adhesive composition A in dots with a distribution density of 5579527 pcs/m ² on one side of the 30g/m ² non-woven fabric through dot sizing. The amount of glue is 30g/m ² , then Laminated and compounded with the first substrate bonded with activated carbon, the obtained composite layer is sent to an oven for drying, and after two stages of high-temperature drying, the oven temperature is 100 ℃, and the drying time is 5 minutes to obtain composite material 1. The SEM electron micrograph of the product As shown in Figure 1. In the composite material 1, the gram weight of the spherical activated carbon is about 210 g/m ² .

Example 2

With reference to the method of Example 1, a non-woven fabric with a grammage of 30 g/m ² was selected, and the adhesive composition A was spot-coated on one side surface of the non-woven fabric at a distribution density of 5579527 pieces/m ² . The amount of glue is 30g/m ² .

The spherical activated carbon obtained in Preparation Example 1 was contacted with the dot-coated adhesive composition A to obtain a first substrate bonded with activated carbon, and then sent to an oven for drying. After two stages of high temperature drying, the oven temperature was 100 ℃, drying time 5min.

Coat one side of the 100g/m ² aramid fiber base fabric with adhesive composition A by the same dot sizing method, the amount of sizing is 30g/m ² , and then with the activated carbon bonded first The substrate is laminated and compounded, and the obtained composite layer is sent to an oven for drying, and after two stages of high-temperature drying, the oven temperature is 100°C, and the drying time is 5 minutes, to obtain composite material 2. In the composite material 2, the gram weight of the spherical activated carbon is about 210 g/m ² .

Example 3

Repeat the method of Example 1, except that the spherical activated carbon product of Example 1 in Chinese patent application 201710781322.8 is selected to prepare composite material 3, with a gram weight of about 205g/m ² ;

The spherical activated carbon product of Example 2 in Chinese patent application 201710781322.8 was selected to prepare composite material 4, with a gram weight of about 200g/m ² ;

The spherical activated carbon product of Example 4 in Chinese patent application 201710781322.8 was selected to prepare composite material 5 with a gram weight of about 218 g/m ² .

Comparative example 1

Select the aramid fiber base fabric with a gram weight of 100g/m ² , and apply the adhesive composition A uniformly on one side surface of the aramid fiber base fabric by roller coating, and the glue amount is 80 g/m ² .

The spherical activated carbon obtained in Preparation Example 1 was contacted with the roller-coated adhesive composition A to obtain the first substrate bonded with activated carbon, which was then sent to an oven for drying, and after two stages of high temperature drying, the oven temperature was 100°C , Drying time is 5min.

Coat one side of the 30g/m ² non-woven fabric with adhesive composition A by roller gluing, with a gluing amount of 50 g/m ² , and then laminate with the first substrate bonded with activated carbon , The obtained composite layer was sent to an oven for drying, and after two stages of high temperature drying, the oven temperature was 100°C, and the drying time was 5 minutes, to obtain comparative composite material 1, and the SEM electron microscope photo of the product is shown in Figure 2. In Comparative Composite 1, the weight of spherical activated carbon is about 130 g/m ² .

Comparative example 2

With reference to the method of Example 1, select the aramid fiber base fabric with a grammage of 100g/m ² , and apply the adhesive composition A to the aramid fiber base at a distribution density of 5579527 pcs/m ² in dots. The amount of glue on one side of the cloth is 30g/m ² .

The spherical activated carbon obtained in Preparation Example 1 was contacted with the dot-coated adhesive composition A to obtain a first substrate bonded with activated carbon, and then sent to an oven for drying. After two stages of high temperature drying, the oven temperature was 100 ℃, drying time 5min.

Coat one side of the 30g/m ² non-woven fabric with adhesive composition A by roller gluing, with a gluing amount of 20 g/m ² , and then laminate with the first substrate bonded with activated carbon , The obtained composite layer is sent to an oven for drying, and after 2 stages of high-temperature drying, the oven temperature is 100° C., and the drying time is 5 minutes, to obtain comparative composite material 2.

In Comparative Composite 2, the weight of spherical activated carbon is about 180 g/m ² .

Test example 1: moisture permeability test

According to GB/T 12704.2-2009 Method A, the moisture permeability of the above composite materials was measured, and the results are shown in the following table:

Composite material	Moisture permeability (g/(m 2 *24h))
Composite material 1	3867
Composite material 2	3994
Comparative composite 1	930
Comparative composite 2	4232

Note: The unit of moisture permeability is g/(m ² *24h), which means the total mass of water vapor per square meter of composite fabric in 24 hours.

In addition, the composite materials 3, 4, and 5 of the present invention were used to perform the above tests respectively, and the results showed that the moisture permeability was between 3500 and 4000 g/(m ² *24h).

Test Example 2: Air permeability test

According to GB/T 5453-1997, the air permeability of the above-mentioned composite material was measured under an air pressure of 200Pa. The results are shown in the following table:

Composite material	Air permeability (L/(m 2 *s))
Composite material 1	1020
Composite material 2	958
Comparative composite 1	4.66
Comparative composite 2	1184

Note: The air permeability unit is L/(m ² *s), which means the air permeability of the composite material per square meter per second.

In addition, the composite materials 3, 4, and 5 of the present invention were also used to conduct the above-mentioned tests respectively, and the results showed that their air permeability was between 800-1200 L/(m ² *s).

Test case 3: Peel strength test

According to FZ/T 80007.1-2006, the peel strength of the above composite materials was measured, and the results are shown in the following table:

Composite material	Radial peel strength (N)	Weft peel strength (N)
Composite material 1	10.6	13.5
Composite material 2	10.5	13.5
Comparative composite 2	2.6	3.0

In addition, the composite materials 3, 4, and 5 of the present invention were also used for the above-mentioned tests, and the results showed that the peel strengths were all between 10 and 15N.

Test Example 4: Washing fastness test

Cut a 50cm×50cm composite material sample and put it into an oven at 40°C for drying until the quality no longer changes. Use the following type B washing machines specified in GB/T 8629:

Add 2 g of ECE standard detergent 98 (phosphorus-free washing powder without enzymes and fluorescent brighteners), 20 kg of water, and 7 abrasives (rubber with thickness of 1.5 mm) to the above-mentioned GB/T 8629 type B washing Cut block), water temperature 40℃, wash 3 times with the following washing procedure:

B-type standard washing machine washing program

The washed sample is dried at 105-110°C, and the mass of the dried sample is measured. The weight loss rate of the sample after washing is used to evaluate the adhesion fastness to machine washing. The weight loss is the weight of the detached spherical activated carbon. The results are shown in the following table.

To	Before washing (g)	After washing (g)	Loss rate (%)
Composite material 1	95.41	95.03	-0.4% (including drying and weighing error)
Composite material 2	75.51	75.22	-0.4% (including drying and weighing error)
Comparative composite 2	107.43	106.24	-1.1% (including drying and weighing error)

In addition, the composite materials 3, 4, and 5 of the present invention were also used for the above tests, and the results showed that the loss rates were all ≤-0.5%.

Test case 5: Gas-gas protection time

Select composite materials 1 and 2, and test the penetration time of propyl sulfide according to the test method of GJB-3253-98 Appendix A. The result shows that it remains impermeable at 190 minutes and the protection time exceeds 3 hours. The test confirmed that the composite material of the present invention has excellent organic gas adsorption and protection performance.

Test Example 6: Tensile strength and elongation at break

The composite material 1 is selected and tested according to the test method of GB3923-83. The results are as follows. The results show that the composite material of the present invention has excellent mechanical strength.

Test Example 7: Flame Retardant Performance

The composite material 1 is selected and tested according to the test method of GB5455-2014. The results are as follows. The results show that the composite material of the present invention also has excellent flame retardant properties.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above-mentioned embodiment. Any modification, equivalent replacement, improvement, etc., made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. A composite material includes a substrate, activated carbon, and a binder composition between the substrate and the activated carbon, wherein the binder composition includes a binder and a thickener.
2. The composite material according to claim 1, wherein the substrate comprises a first substrate and a second substrate, the activated carbon is interposed between the first substrate and the second substrate, and the binder is combined The substances are respectively between the activated carbon and the first substrate, and between the activated carbon and the second substrate.
3. The composite material according to claim 1 or 2, wherein the first substrate is selected from aromatic polyamides such as aramid materials, aromatic polysulfone amides such as aramid materials; the second base The material is selected from non-woven fabrics such as non-woven fabrics or spunlace non-woven fabrics.
4. The composite material according to any one of claims 1-3, wherein the content of the thickener in the adhesive composition is 1-10% by weight of the adhesive.
5. The composite material according to any one of claims 1 to 4, wherein the viscosity of the adhesive composition is 15000-30000 mpa·s, such as 20000-25000 mpa·s.
6. The composite material according to any one of claims 1 to 5, wherein the grammage of activated carbon in the composite material is 80-250 g/m ² , such as 120-240 g/m ² , preferably 160-220 g/m ² .
7. The composite material according to any one of claims 1 to 6, wherein the adhesive composition is distributed in dots on the substrate;

   Preferably, the first adhesive composition is distributed in dots on the first substrate, and the second adhesive composition is distributed in dots on the second substrate;

   More preferably, the activated carbon is in contact with the first binder composition and the second binder composition. .
8. A garment comprising the composite material according to any one of claims 1-7.
9. The preparation method of the composite material according to any one of claims 2-7, comprising the following steps:

   1) Providing a first substrate comprising an adhesive composition, wherein the adhesive composition is distributed on the surface of the first substrate in dots;

   2) The activated carbon is contacted with the point of the adhesive composition to obtain the first substrate for binding the activated carbon;

   3) Adhere the activated carbon side of the first substrate to the second substrate through the adhesive composition.
10. The use of the composite material of any one of claims 1-7 for adsorbing gas and/or liquid.

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