CN109954329B - Plant fiber self-supporting graphene haze-proof filter layer material and preparation method and application thereof - Google Patents
Plant fiber self-supporting graphene haze-proof filter layer material and preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0001—Making filtering elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
Abstract
The invention relates to a plant fiber self-supporting graphene haze-proof filter layer material and a preparation method and application thereof, and the haze-proof filter layer material comprises a high-molecular filter layer material and a three-dimensional porous structure layer which is formed on the surface of the high-molecular filter layer material and is self-assembled by at least one of graphene and graphene oxide and plant fibers, wherein the plant fibers are at least one of pinus kesiya, flax, needle leaves, bamboo fibers, bagasse fibers, flax and cellulose fibers; preferably, the graphene comprises at least one of three-dimensional graphene and few-layer graphene.
Description
Technical Field
The invention relates to a graphene haze-proof filter layer material self-supported by plant fibers, and a preparation method and application thereof, and belongs to the field of haze prevention.
Background
With the development of modern industry, environmental pollution becomes increasingly serious, and atmospheric pollution as a part of environmental pollution poses serious threats to human health. One product of atmospheric pollution is haze. The principle of haze generation is complex, and the chemical composition and structure thereof are also complex. The main harmful component of haze is PM2.5, which is solid particles with the size of 2.5 microns or less in the atmosphere, can directly enter bronchus and alveolus of a human body to cause bronchitis and asthma, and enter blood circulation to cause congestive heart failure and heart disease, and meanwhile, PM2.5 dust contains various toxic and harmful substances, can cause poisoning of the human body and cause the incidence rate of lung cancer, can influence the development of fetuses and the like, and causes great harm to the human society. The mask, especially the haze-preventing mask capable of blocking PM2.5 particles, is an effective means for protecting human health. However, most of masks in the market at present can not effectively block PM2.5, and can generate peculiar smell after being worn for a period of time, so that the overall comfort is influenced.
Graphene is a hexagonal honeycomb two-dimensional material composed of carbon atoms, and the theoretical specific surface area of the material is 2630m2And/g), the graphene with the functional group can be assembled into a three-dimensional porous graphene structure, and has good adsorption performance and the capability of blocking tiny particles. However, the existing method for constructing the three-dimensional graphene mostly adopts a template-assisted CVD method or a hydrothermal reduction method, so that the preparation cost is high, the process is complex, and the prepared material has poor mechanical strength and is not beneficial to large-scale practical use.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a haze-proof mask filter layer material which has high PM2.5 filtering efficiency, does not influence breathing resistance, can automatically remove peculiar smell, is low in price and simple in process, and a preparation method and application thereof.
On one hand, the invention provides a plant fiber self-supporting graphene haze-proof filter layer material, which comprises a high polymer filter layer material and a three-dimensional porous structure layer formed on the surface of the high polymer filter layer material and formed by self-assembling at least one of graphene and graphene oxide and plant fibers, wherein the plant fibers are at least one of pinus kesiya, flax, needle leaves, bamboo fibers, bagasse fibers, flax and cellulose fibers; preferably, the graphene comprises at least one of three-dimensional graphene, few-layer graphene (e.g., microwave-reduced graphene oxide, physically exfoliated low-defect graphene).
The plant fibers (such as pinus sylvestris, flax, needle leaves, bamboo fibers, bagasse fibers, flax, cellulose fibers and the like) selected by the invention have various oxygen-containing functional groups (such as hydroxyl, carboxyl, carbonyl, epoxy groups, ether groups, ester groups, amide groups and the like), the fibers can be assembled into a three-dimensional porous structure to a certain extent (similar to a papermaking process) on a polymer filter layer through the combined action of hydrogen bonds, van der waals force and the like of the fiber surface groups, meanwhile, the existence of the oxygen-containing groups (carboxyl, hydroxyl, carbonyl, epoxy groups and the like) on the surface of graphene oxide can also be assembled on the surface of the fibers through interaction with the fibers, and the sheet-shaped structure of the graphene oxide or the graphene oxide is favorable for isolating PM 2.5. The three-dimensional graphene structure contains a porous structure, and can construct more abundant pore channels together with a fiber framework, so that PM2.5 micro particles are blocked. In a word, the introduction of the plant fiber can support graphene, three-dimensional graphene or/and graphene oxide to prevent the graphene and the three-dimensional graphene or/and graphene oxide from agglomerating, and meanwhile, the plant fiber can also be introduced into a multi-stage pore structure, so that the plant fiber has extremely high porosity, extremely good adsorption and filtration effects, and extremely high practical application value in the field of haze protection. In addition, the plant fibers and the graphene with a specific structure can be mutually connected through the action of hydrogen bonds, van der waals force and the like, so that the structure of the plant fibers is stabilized, and the graphene or/and graphene oxide can be prevented from falling off. In addition, the three-dimensional graphene with the specific structure also comprises a three-dimensional porous structure prepared by a hydrothermal method and a CVD method, and the three-dimensional porous structure and the fiber can jointly construct a richer pore channel structure.
Preferably, the ratio of the mass of the plant fiber to the mass of the graphene or/and the graphene oxide is 3:1 to 1:5, preferably 1:1 to 1: 4. Too high a fibre content causes a denser fibre stack and smaller pores, which in turn leads to an increased breathing resistance. Too few fibers can not play a role in supporting and fixing the graphene sheet.
Preferably, the thickness of the three-dimensional porous structure layer is 50 to 300 μm.
Preferably, the polymer filter layer material is at least one of polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride, polyvinyl chloride and polyvinylidene fluoride, and is preferably polypropylene non-woven fabric or polypropylene melt-blown fabric. The reason for selecting the high polymer material is that the material has better stability, and the subsequent treatment does not influence the structure of the material. The thickness of the polymer filter layer material is 80-150 μm.
Preferably, a binder layer is further included between the polymer filter layer material and the three-dimensional porous structure layer, the binder layer is obtained by drying a polymer binder, and raw material components of the polymer binder include a polymer base component, a thickening agent, a regulator, a cross-linking agent, an initiator and a solvent; the high molecular polymer base component comprises at least one of polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinyl acetate, the thickening agent comprises at least one of konjac glucomannan, carboxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose and carboxylated chitosan, the regulator comprises at least one of acrylic acid, acrylamide and methacrylamide, the initiator is at least one of potassium persulfate, ammonium persulfate and azodiisobutyramidine hydrochloride V-50, and the crosslinking agent is N-N methylene bisacrylamide; in the raw material components of the binder, by weight, the content of a high molecular polymer base component is 10-50 wt%, the dosage of a thickening agent is 1-20 wt% of the high molecular polymer base component, the dosage of a regulator is 1-10 wt% of the high molecular polymer base component, the dosage of a crosslinking agent is 0-20 wt% of the high molecular polymer base component, the dosage of an initiator is 0-1 wt% of the high molecular polymer base component, and the balance is a solvent. The solvent comprises at least one of deionized water, absolute ethyl alcohol, acetone and petroleum ether, and is preferably deionized water. The polymer binder contains various oxygen-containing functional groups (including specific functional groups such as carboxyl, hydroxyl, epoxy, amide and the like), and can be assembled with graphene or/and graphene oxide with functional groups (such as carboxyl, hydroxyl, epoxy and the like) on the surface through hydrogen bonds or van der waals force to construct a local porous structure, so that the graphene oxide, the graphene and the three-dimensional graphene can be better bonded with the polymer filter layer material. Meanwhile, the polymer binder can form a gel structure after being dried, and also has certain functions of deodorizing and preventing graphene sheets with specific structures from falling off.
On the other hand, the invention also provides a preparation method of the plant fiber self-supporting graphene haze-proof filter layer material, which comprises the following steps:
dispersing plant fibers in a solution containing graphene, three-dimensional graphene or/and graphene oxide to obtain a mixed solution:
and spraying the obtained mixed solution on the surface of a polymer filter layer material, and drying to obtain the plant fiber self-supporting graphene anti-haze filter layer material.
Preferably, the concentration of the solution containing graphene or/and graphene oxide is 0.5-15 mg/ml, and the amount of the plant fiber is 0.1-50 wt%, preferably 0.1-20 wt%, and more preferably 0.1-10 wt% of the total mass of the solution containing graphene or/and graphene oxide.
Preferably, the parameters of the spraying include: the spraying speed is 50-200 ml/min. During continuous production, the spray gun is opened all the time until production of a batch of products is finished.
Preferably, the drying temperature is 60-120 ℃ and the drying time is 1-30 minutes.
In another aspect, the invention also provides a mask comprising the plant fiber self-supporting graphene anti-haze filter layer material.
The invention has the beneficial effects that:
construct local three-dimensional hierarchical pore structure with vegetable fibre and specific structure graphite alkene self-assembly, can realize that the high efficiency blocks PM2.5, reach and prevent the haze purpose, and through adjusting the vegetable fibre's of adding kind, concentration and adjusting specific structure graphite alkene concentration, drying temperature etc. come the size in adjustment hole, the density in hole and then control PM2.5 filtration efficiency and gauze mask respiratory resistance, realize high-efficient haze prevention and remove the preparation of flavor gauze mask. The process is simple and easy to implement, has low requirement on equipment, the PM2.5 filtration efficiency can reach more than 99 percent, the filtration resistance is as low as 80-130Pa, and large-scale popularization and production can be realized.
Drawings
Fig. 1a shows a physical diagram of the plant fiber self-supporting graphene haze-proof filter layer material of 1mg/ml graphene and 1mg/ml fiber prepared in example 1, and it can be seen from the physical diagram that graphene is uniformly dispersed on the surface of the filter layer material, and the color is light due to low concentration;
fig. 1b shows a physical diagram of the plant fiber self-supporting graphene haze-proof filter layer material of 2mg/ml graphene and 1mg/ml fiber prepared in example 2, and it can be seen from the physical diagram that graphene is uniformly dispersed on a substrate material, the concentration of graphene is increased, and the color is deepened;
FIG. 1c is a diagram showing a substance of the 4mg/ml graphene and 1mg/ml fiber plant fiber self-supporting graphene haze-proof filter layer material prepared in example 3, and it can be seen that the concentration of graphene is further increased and the color is deepened;
fig. 2 is a diagram of a plant fiber self-supporting graphene anti-haze mask prepared in example 2;
fig. 3 is an SEM image of the three-dimensional porous structure layer in the graphene haze prevention mask self-supported by plant fibers of example 2;
fig. 4 is a test chart for tearing the adhesive tape of the three-dimensional porous structure layer in the graphene haze-proof mask self-supported by plant fibers in embodiment 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
According to the invention, a local three-dimensional porous structure is constructed by the self-assembly effect between the plant fiber and the graphene or/and the graphene oxide for the first time, so that the plant fiber supported graphene efficient haze-proof filter layer material is prepared, and the efficient filtration of PM2.5 is further realized.
The plant fiber self-supporting graphene haze-proof filter layer material comprises a polymer filter layer material and a three-dimensional porous structure layer formed on the surface of the polymer filter layer material and formed by self-assembling at least one of graphene and graphene oxide and plant fibers, wherein the plant fibers are at least one of pinus khasys, flax, needle leaves, bamboo fibers, bagasse fibers, flax and cellulose fibers. The ratio of the mass of the plant fiber to the mass of the graphene or/and the graphene oxide can be 3: 1-1: 5, and preferably 1: 1-1: 4. The thickness of the three-dimensional porous structure layer can be 50-300 mu m. The plant fiber used in the invention contains various oxygen-containing functional groups, so that the graphene sheet can be well supported to form a hierarchical pore structure, and meanwhile, the plant fiber can be connected with graphene (graphene or/and graphene oxide) with a specific structure through hydrogen bond action and the like to stabilize the structure, so that the graphene is prevented from falling off. In the present invention, the graphene may be few-layer graphene (e.g., microwave-reduced graphene oxide, physically exfoliated low-defect graphene, etc.), three-dimensional graphene (three-dimensional porous graphene), or the like. The graphene or/and graphene oxide may include at least one of three-dimensional porous graphene having a pore size distributed in a range of 10 to 20 micrometers, few-layer graphene having a size of 4 to 5 micrometers, reduced graphene oxide having a single-piece size of 30 to 50 micrometers, and the like.
The preparation method is simple and easy to implement, low in production cost, good in filtering effect and capable of realizing large-scale production. The preparation method of the plant fiber self-supporting graphene haze-proof filter layer material provided by the invention is exemplarily described as follows.
And (3) preparing a solution containing graphene or/and graphene oxide (graphene or/and graphene oxide dispersion liquid). And ultrasonically dispersing graphene or/and graphene oxide in a certain solvent to obtain a graphene or/and graphene oxide solution. The selected solvent can be one or a mixture of more than two of deionized water, absolute ethyl alcohol, acetone and petroleum ether. The concentration of the solution containing graphene or/and graphene oxide is 0.5-15 mg/ml. Wherein the power of ultrasonic treatment can be 100-300W, and the time is 0.5-4 h. The graphene or graphene oxide can be physically stripped low-defect graphene, graphene oxide prepared by an improved Hummers method, three-dimensional porous graphene and/or microwave-reduced graphene oxide. The raw material for preparing the graphene or the graphene oxide selects graphite powder with the mesh number of 200-1000 meshes.
Dispersing plant fibers in a solution (water or/and alcohol) containing graphene or/and graphene oxide, and then carrying out ultrasonic treatment and stirring for a period of time to obtain a mixed solution. The fiber is one or more of pinus khasys, flax, needle leaf, bamboo fiber, bagasse fiber, flax, and cellulose fiber. Keeping the mass ratio of the use amount of the plant fibers to the graphene or/and the graphene oxide to be 3: 1-1: 5, preferably: 1:1 to 1: 4. Wherein the mixing means is stirring and ultrasonic mixing. The power of the ultrasonic mixing sonication can be 100-300W, and is preferably 0.5-6 h. The stirring time is 0.5-8 h.
The method comprises the steps of spraying a mixed solution containing plant fibers on the surface of a polymer filter layer material, then placing the polymer filter layer material at a certain temperature for drying for a period of time, and self-assembling partial functional groups in graphene or/and graphene oxide and oxygen-containing functional groups of the plant fibers to construct a three-dimensional hierarchical pore structure, thereby preparing the graphene haze-preventing filter layer material with the fibers self-supported. Wherein the drying temperature is 60-120 ℃, and the drying time is 1-30 minutes. The parameters of the spraying include: the spraying speed is 50-200 ml/min. The polymer filtering layer material comprises one or more than two of non-woven fabrics, melt-blown fabrics or filter screens such as polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene fluoride and the like.
Or spraying a layer of adhesive before spraying the mixed solution on the surface of the molecular filter layer material. The adhesive is used for the mask, preferably is a high-molecular adhesive, and the raw material components of the high-molecular adhesive comprise a high-molecular polymer base component, a thickening agent, a regulator, a cross-linking agent, an initiator and a solvent. Wherein, the high molecular polymer base component comprises at least one of polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinyl acetate. The thickener comprises at least one of konjac glucomannan, carboxymethyl cellulose, hydroxypropyl methyl cellulose, carboxylated chitosan and hydroxyethyl cellulose. Wherein in the raw material components of the binder, the content of the high molecular polymer base component is 10-50 wt%, preferably 20-40 wt%. The dosage of the regulator is 1-10% of the base component of the high molecular polymer. The amount of the thickener is 1-20 wt% of the base component of the high molecular polymer, preferably 2-10 wt%. The molecular weight of the high molecular polymer basic component can be 1000-6000. The solvent comprises at least one of deionized water, absolute ethyl alcohol, acetone and petroleum ether, and is preferably deionized water. The cross-linking agent comprises N-N methylene-bisacrylamide, and the initiator is at least one of potassium persulfate, ammonium persulfate and V-50. The amount of the cross-linking agent is 0-20 wt% of the base component of the high molecular polymer, preferably 2-10 wt%. The amount of the initiator is 0-1% of the base component of the high molecular polymer, preferably 0.05-0.5 wt%. The balance being solvent.
The following exemplarily illustrates a method for preparing the adhesive for the haze prevention mask according to the present invention.
Dissolving a solution containing 10-50 wt% of a high molecular polymer base component in the solvent, and adding the regulator, the cross-linking agent and the initiator; stirring for 20 minutes to 8 hours at the temperature of 25-90 ℃ to obtain the anti-haze mask binder. Specifically, one or two solutions of polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinyl acetate with a certain concentration (for example, 10% -50%) are slowly dissolved in a certain solvent at a certain temperature (25 ℃ -90 ℃) to form a high molecular solution (the concentration of the high molecular solution can be 5% -40%) according to a certain proportion. Wherein the molecular weight of polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinyl acetate is 1000-6000. Adding one or more of konjac glucomannan, carboxylated cellulose, hydroxypropyl methylcellulose and hydroxyethyl cellulose, or dissolving the above regulator in a solvent, slowly adding into the above polymer solution, stirring for a period of time (0.5-8 hr (preferably 0.5-6 hr), and heating to 25-90 deg.C) to obtain a uniform mixed solution, which is the binder for the anti-haze mask. The dosage of the konjac glucomannan, the carboxylated cellulose, the hydroxypropyl methyl cellulose and the hydroxyethyl cellulose is 1 to 20 percent of the dosage of the regulator. The selected solvent is one or a mixture of more than two of deionized water, absolute ethyl alcohol, acetone and petroleum ether. The addition sequence of the components of the invention has no special requirements.
A crosslinking agent may also be incorporated in the binder component, and may be added before or after the above-mentioned conditioning agent, preferably before the conditioning agent is added. The cross-linking agent is N-N methylene bisacrylamide, and the dosage of the cross-linking agent is 1-20% of the dosage of the component A. The initiator can be added directly or after dissolving in a solvent. The amount of the cross-linking agent is 0 to 20wt%, preferably 2 to 10wt% of the base component of the high molecular polymer. The addition of the cross-linking agent can initiate the cross-linking of the basic component and the regulator, and improve the stability, environmental resistance and mechanical property of the binder. An initiator may also be incorporated into the binder component, preferably at the end of addition, and may be at least one of potassium persulfate, ammonium persulfate, and V-50. The amount of the initiator is 0 to 1wt%, preferably 0.05 to 0.5 wt% of the base polymer component. And (3) adding an initiator, and reacting for 1-8 hours at 60-90 ℃. Thus, the regulator monomer can be initiated to polymerize into a polymer with a certain molecular weight, and the processing rheological property of the adhesive can be improved.
According to the invention, natural plant fibers and graphene with a specific structure are assembled into a local three-dimensional hierarchical pore structure on a specific polymer filter layer material and are used as an interlayer (graphene high-efficiency haze-preventing filter layer material supported by the plant fibers), so that the preparation of a haze-preventing mask with high filtering efficiency, low filtering resistance, peculiar smell removal, rapidness and low cost is realized, and the structure of the mask comprises a macroporous non-woven fabric layer, a breather valve and the like besides the haze-preventing filter layer material.
The filtering efficiency and the airflow resistance of the mask are tested by adopting a TIS-8130 automatic filter material tester.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The following are providedThe exemplary specific process parameters and the like are also only one example of suitable ranges, i.e., those skilled in the art can select from the suitable ranges through the description herein, and are not limited to the specific values illustrated below. In the following examples, the power of the ultrasonic treatment is generally 300W, and the thickness of the polypropylene nonwoven fabric is 80 to 150 μm, unless otherwise specified. The raw materials used in the preparation process of the mask comprise melt-blown cloth (width: 160cm, gram weight (g/m))2): 12g-75g, Yichang Xinlong sanitary materials Co., Ltd.), and needling electrostatic filter cotton (1.5mm thick, 90g/m2Nanjing Baipo textile Co., Ltd.), and a non-woven fabric layer (PP, width 0.1-1.6m, Zhongzhen Zhongzhong filter material non-woven fabric Co., Ltd.).
Production example 1: graphene oxide synthesis by adopting improved Hummers method
The flake graphite is heated in a tube furnace at 1000 ℃ for 2h under the protection of argon to obtain expanded graphite. Adding 1-10g of expanded graphite into a 2000mL big beaker, adding 500-2SO4、50-200mL H3PO4(volume ratio of sulfuric acid to phosphoric acid is 9:1) and 10-80g KMnO4And the color of the solution is green after stirring. The mixture was stirred in a water bath at 30-70 ℃ for 5h, and the color of the solution gradually changed from green to brown. After the reaction is finished, the brown solution is poured into 1000mL of ice water containing 50-200mL of hydrogen peroxide (30%) and stirred, and the solution turns golden yellow immediately. After standing overnight, the supernatant was poured off and the lower solution was centrifuged. Washing with 10% diluted hydrochloric acid (SO removal) at 9500rpm4 2-And unreacted graphite), washing with distilled water until the pH is about 5, and collecting a brown viscous product, namely graphene oxide. The improved Hummers method produces graphene oxide flakes having a single sheet size of 30-50 microns.
Production example 2: reduced graphene oxide prepared by microwave reduction method
A certain amount of graphene oxide in production example 1 was taken, freeze-dried, and subjected to microwave reduction to obtain microwave-reduced graphene oxide. The reduced graphene oxide with the single sheet size of 30-50 microns is prepared by a microwave reduction method.
Production example 3: preparation of low-defect graphene by physical stripping method
A certain amount of the expanded graphite (generally, a precursor for preparing graphene or graphene oxide) in the preparation example 2 is dispersed in a certain amount of deionized water, and a certain amount of a surfactant such as: and carrying out ball milling for a certain time, and carrying out ultrasonic stripping to obtain the low-defect graphene. The physical intercalation is stripped into few-layer graphene with the size of 4-5 microns.
Production example 4: three-dimensional graphene synthesized by hydrothermal method
A certain amount of graphene oxide in production example 1 was prepared to a certain concentration (1-15mg/ml), and a certain amount of a crosslinking agent: such as polyvinyl alcohol, PDMS, PEI and the like as high molecular crosslinking agents or low molecules such as ethylenediamine, amino acids and the like. And transferring the solution into a reaction kettle, reacting for 6-48 hours at the temperature of 100-220 ℃, washing with deionized water and ethanol, and freeze-drying to prepare the three-dimensional graphene. The three-dimensional porous graphene with the pore size distributed in the range of 10-20 microns is prepared by a hydrothermal method.
Example 1
Firstly, 325-mesh graphite powder is selected, graphene oxide is prepared by an improved Hummers method, a 1mg/ml graphene oxide aqueous solution is prepared by ultrasonic and mechanical stirring, then flax is added into the graphene oxide dispersion liquid according to the mass ratio of the graphene oxide to the flax of 1:1, and after 2 hours of high-speed mechanical stirring, 100ml/min) is atomized and sprayed on the polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is about 150 mu m. The filtering layer is used as a mask interlayer to prepare the graphene haze-proof mask (the specific structure of the obtained mask is two layers of macroporous polypropylene non-woven fabrics + filtering layer + electrostatic filter cotton + melt-blown fabric, and if no special description is provided in the following examples and comparative examples, the structure of the mask is the same as that of the mask 1 in the embodiment), the PM2.5 filtering efficiency can reach more than 97%, and the filtering resistance is 95 Pa.
Example 2
Firstly, 325-mesh graphite powder is selected, graphene oxide is prepared by an improved Hummers method, a 2mg/ml graphene oxide aqueous solution is prepared by ultrasonic and mechanical stirring, then flax is added into the graphene oxide dispersion liquid according to the mass ratio of 2:1 of the graphene oxide to the flax, and after the flax is ultrasonically and mechanically stirred at a high speed for 2 hours, the flax is atomized and sprayed on polypropylene non-woven fabrics with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 150 micrometers. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 99%, and the filtering resistance is 104 Pa.
Example 3
Firstly, 325-mesh graphite powder is selected, graphene oxide is prepared by an improved Hummers method, a 4mg/ml graphene oxide aqueous solution is prepared by ultrasonic and mechanical stirring, then the graphene oxide aqueous solution is added into a graphene oxide dispersion liquid according to the mass ratio of 4:1 of graphene oxide to flax, and after the graphene oxide aqueous solution is ultrasonically and mechanically stirred at a high speed for 2 hours, the graphene oxide aqueous solution is atomized and sprayed on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 150 micrometers. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 98%, and the filtering resistance is 120 Pa.
Example 4
Firstly, selecting 1000-mesh graphite powder, preparing graphene oxide by adopting an improved Hummers method, and then preparing three-dimensional porous graphene by using a hydrothermal synthesis method. Dispersing the three-dimensional porous graphene and graphene oxide synthesized by a 325-mesh Hummers method in a water/alcohol mixed solution (the mass ratio of water to alcohol is 6: 1) in a ratio of 1:4 by means of ultrasonic and mechanical stirring to prepare a graphene dispersion liquid of 2mg/ml, then adding needle fibers into the graphene mixed dispersion liquid in a ratio of the mass ratio of graphene (three-dimensional graphene + graphene oxide) to the mass ratio of needle fibers of 1:1, performing ultrasonic and high-speed mechanical stirring for 2 hours, and spraying the mixture on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene anti-haze filter layer material, wherein the thickness of the three-dimensional porous structure layer is 200 microns. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 98%, and the filtering resistance is 110 Pa.
Example 5
Firstly, selecting 1000-mesh graphite powder, preparing graphene oxide by adopting an improved Hummers method, and then preparing three-dimensional porous graphene by using a hydrothermal synthesis method. Dispersing the three-dimensional porous graphene and graphene oxide synthesized by a 325-mesh Hummers method in a water/alcohol mixed solution (the mass ratio of water to alcohol is 6: 1) in a ratio of 1:2 by means of ultrasonic and mechanical stirring to prepare a graphene dispersion liquid of 2mg/ml, then adding needle fibers into the graphene mixed dispersion liquid in a ratio of the mass ratio of graphene (three-dimensional graphene + graphene oxide) to the mass ratio of needle fibers of 1:1, performing ultrasonic and high-speed mechanical stirring for 2 hours, and spraying the mixture on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 150 micrometers. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 99%, and the filtering resistance is 90 Pa.
Example 6
Firstly, 325-mesh graphite powder is selected, graphene oxide is prepared by an improved Hummers method, and then reduced graphene oxide is prepared through steps of low-temperature drying, microwave reduction and the like. Dispersing the reduced graphene oxide and graphene oxide synthesized by a 325-mesh Hummers method in alcohol according to a ratio of 1:4 by means of ultrasonic and mechanical stirring to prepare a graphene dispersion liquid of 2mg/ml, then adding needle fibers into the graphene mixed dispersion liquid according to a mass ratio of the graphene (reduced graphene oxide + graphene oxide) to the needle fibers of 1:1, ultrasonically and mechanically stirring at a high speed for 2 hours, and spraying the mixture on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 120 microns. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 99%, and the filtering resistance is 120 Pa.
Example 7
Firstly, 325-mesh graphite powder is selected, graphene oxide is prepared by an improved Hummers method, and then reduced graphene oxide is prepared through steps of low-temperature drying, microwave reduction and the like. Dispersing the reduced graphene oxide and graphene oxide synthesized by a 325-mesh Hummers method in alcohol according to a ratio of 1:2 by means of ultrasonic and mechanical stirring to prepare a graphene dispersion liquid of 2mg/ml, then adding needle fibers into the graphene mixed dispersion liquid according to a mass ratio of the graphene (reduced graphene oxide + graphene oxide) to the needle fibers of 1:1, ultrasonically and mechanically stirring at a high speed for 2 hours, and spraying the mixture on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 110 microns. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 99%, and the filtering resistance is 112 Pa.
Example 8
Firstly, 325-mesh graphite powder is selected, graphene oxide is prepared by an improved Hummers method, and then reduced graphene oxide is prepared through steps of low-temperature drying, microwave reduction and the like. Dispersing the reduced graphene oxide and graphene oxide synthesized by a 325-mesh Hummers method in alcohol in a ratio of 1:4 by means of ultrasonic and mechanical stirring to prepare a graphene dispersion liquid of 2mg/ml, and then sequentially spraying two fibers in a ratio of the mass ratio of graphene (reduced graphene oxide + graphene oxide) to flax of 4:1 and the mass ratio of graphene (reduced graphene oxide + graphene oxide) to pinus kesiya fibers of 4:1, mechanically stirring at a high speed for 2 hours, and then spraying the fibers on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 180 mu m. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 99%, and the filtering resistance is 85 Pa.
Example 9
Firstly, 325-mesh graphite powder is selected, graphene oxide is prepared by an improved Hummers method, and then reduced graphene oxide is prepared through steps of low-temperature drying, microwave reduction and the like. Dispersing the reduced graphene oxide and graphene oxide synthesized by a 325-mesh Hummers method in alcohol in a ratio of 1:4 by means of ultrasonic and mechanical stirring to prepare a graphene dispersion liquid of 2mg/ml, sequentially adding two fibers into the graphene dispersion liquid in a mass ratio of graphene (reduced graphene oxide + graphene oxide) to flax of 2:1 and a mass ratio of graphene (reduced graphene oxide + graphene oxide) to pinus kesiya fibers of 2:1, mechanically stirring at a high speed for 2 hours, and spraying the mixture on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 150 micrometers. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 99%, and the filtering resistance is 92 Pa.
Example 10
Firstly, 325-mesh graphite powder is selected, and low-defect graphene (few-layer graphene) is prepared in a mechanical stripping mode. Dispersing the low-defect graphene and graphene oxide synthesized by a 325-mesh Hummers method in alcohol in a ratio of 1:4 by means of ultrasonic and mechanical stirring to prepare a graphene dispersion liquid of 2mg/ml, sequentially adding two fibers into the graphene dispersion liquid in a mass ratio of graphene (low-defect graphene + graphene oxide) to flax of 2:1 and a mass ratio of graphene (low-defect graphene + graphene oxide) to pinus sylvestris fibers of 2:1, mechanically stirring at a high speed for 2 hours, and spraying the mixture on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 150 micrometers. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 99%, and the filtering resistance is 82 Pa.
Example 11
Firstly, 325-mesh graphite powder is selected, and the low-defect graphene is prepared in a mechanical stripping mode. Dispersing the low-defect graphene and graphene oxide synthesized by a 325-mesh Hummers method in alcohol in a ratio of 1:2 by means of ultrasonic and mechanical stirring to prepare a graphene dispersion liquid of 2mg/ml, then sequentially adding the two fibers into the graphene dispersion liquid in a mass ratio of graphene (low-defect graphene + graphene oxide) to flax of 2:1 and a mass ratio of graphene (low-defect graphene + graphene oxide) to pinus sylvestris fibers of 2:1, mechanically stirring at a high speed for 2 hours, and spraying the mixture on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 140 mu m. The graphene haze-proof mask can be prepared by taking the filtering layer as a mask interlayer, the PM2.5 filtering efficiency can reach more than 99%, and the filtering resistance is 96 Pa.
Adhesive tape tear test
After the surface of the three-dimensional porous structure layer prepared in examples 1 to 11 was adhered to an adhesive tape (width: 4.5cm, manufactured by the de-tachment group ltd.), the adhesive tape was torn off, and no graphene powder or graphene oxide powder was peeled off from the surface of the three-dimensional porous structure layer. Referring to fig. 4, (a) in fig. 4 is a picture before a tape tearing test, and (b) is a picture of a filter layer material after tearing, and it can be seen from the picture that no graphene powder falls off after tearing.
Example 12
Firstly, selecting 200-mesh graphite powder, preparing graphene oxide by adopting an improved Hummers method, preparing a 2mg/ml graphene oxide aqueous solution by adopting an ultrasonic and mechanical stirring mode, then adding flax into the graphene oxide dispersion liquid according to the mass ratio of the graphene oxide to the flax of 1:3, mechanically stirring at a high speed for 2 hours, and spraying the mixture on a polypropylene non-woven fabric with uniform pore size distribution in an atomizing manner. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the plant fiber self-supporting graphene haze-proof filter layer material, wherein the thickness of the three-dimensional porous structure layer is 200 mu m. With this filter layer as the gauze mask intermediate layer can prepare graphite alkene and prevent haze gauze mask (gained gauze mask concrete structure is that the intermediate level is for preventing the haze filter layer, is one deck static cotton filter from inside to outside in proper order, and one deck melt-blown fabric and two-layer macropore non-woven fabrics), its PM2.5 filtration efficiency can reach 98%, and the filtration resistance is 150 Pa.
Comparative example 1
Firstly, selecting 200-mesh graphite powder, preparing graphene oxide by adopting an improved Hummers method, preparing a 2mg/ml graphene oxide aqueous solution in an ultrasonic and mechanical stirring mode, and directly atomizing and spraying the graphene oxide aqueous solution on a polypropylene non-woven fabric with uniform pore size distribution. And then drying the non-woven fabric at 90 ℃ for 5min to obtain the graphene anti-haze filter layer material. With this filter layer as the gauze mask intermediate layer can prepare graphite alkene and prevent haze gauze mask (gained gauze mask concrete structure is that the intermediate level is for preventing the haze filter layer, is one deck static cotton filter from inside to outside in proper order, and one deck melt-blown fabric and two-layer macropore non-woven fabrics), its PM2.5 filtration efficiency can reach 96%, and the filtration resistance is 135 Pa. After the adhesive tape (the width: 4.5cm, manufactured by the De Li group Co., Ltd.) was adhered to the surface of the haze-proof filter layer of comparative example 1, the adhesive tape was torn, and the graphene powder or graphene oxide powder on the surface of the three-dimensional porous structure layer was significantly peeled off.
Claims (12)
1. The plant fiber self-supporting graphene haze-proof filter layer material is characterized by comprising a high polymer filter layer material and a three-dimensional porous structure layer formed on the surface of the high polymer filter layer material and formed by self-assembling at least one of graphene and graphene oxide and plant fibers, wherein the plant fibers are at least one of pinus khasys, flax, needle leaves, bamboo fibers, bagasse fibers, flax and cellulose fibers; the polymer filter layer material and the three-dimensional porous structure layer also comprise a binder layer, the binder layer is obtained by drying a polymer binder, and the raw material components of the polymer binder comprise a polymer base component, a thickening agent, a regulator, a cross-linking agent, an initiator and a solvent; the high molecular polymer base component comprises at least one of polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinyl acetate, the thickening agent comprises at least one of konjac glucomannan, carboxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose and carboxylated chitosan, the regulator comprises at least one of acrylic acid, acrylamide and methacrylamide, the initiator is at least one of potassium persulfate, ammonium persulfate and azodiisobutyramidine hydrochloride V-50, and the crosslinking agent is N-N methylene bisacrylamide; in the raw material components of the binder, by weight, the content of a high molecular polymer base component is 10-50 wt%, the dosage of a thickening agent is 1-20 wt% of the high molecular polymer base component, the dosage of a regulator is 1-10 wt% of the high molecular polymer base component, the dosage of a crosslinking agent is 0-20 wt% of the high molecular polymer base component, the dosage of an initiator is 0-1 wt% of the high molecular polymer base component, and the balance is a solvent.
2. The plant fiber self-supporting graphene haze-prevention filter layer material according to claim 1, wherein the graphene comprises at least one of three-dimensional graphene and few-layer graphene.
3. The plant fiber self-supporting graphene haze-proof filter layer material according to claim 1, wherein the mass ratio of the plant fibers to the mass of graphene or/and graphene oxide is 3: 1-1: 5.
4. The plant fiber self-supporting graphene haze-proof filter layer material according to claim 3, wherein the mass ratio of the plant fibers to the mass of graphene or/and graphene oxide is 1: 1-1: 4.
5. The plant fiber self-supporting graphene haze-proof filter layer material as claimed in claim 1, wherein the thickness of the three-dimensional porous structure layer is 50-300 μm.
6. The plant fiber self-supporting graphene haze-proof filter layer material according to any one of claims 1-5, wherein the polymer filter layer material is at least one of polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride, polyvinyl chloride and polyvinylidene fluoride, and the thickness of the polymer filter layer material is 80-150 μm.
7. The preparation method of the plant fiber self-supporting graphene haze-proof filter layer material according to any one of claims 1 to 6, wherein the preparation method comprises the following steps:
dispersing plant fibers in a solution containing graphene or/and graphene oxide to obtain a mixed solution;
and spraying the obtained mixed solution on the surface of a polymer filter layer material, and drying to obtain the plant fiber self-supporting graphene anti-haze filter layer material.
8. The preparation method according to claim 7, wherein the concentration of the solution containing graphene or/and graphene oxide is 0.5-15 mg/ml, and the ratio of the mass of the plant fiber to the mass of the graphene or/and graphene oxide is 3: 1-1: 5.
9. The preparation method according to claim 8, wherein the ratio of the mass of the plant fiber to the mass of the graphene or/and graphene oxide is 1: 1-1: 4.
10. The method of claim 7, wherein the parameters of the spray coating include: the spraying speed is 50-200 ml/min.
11. The method according to any one of claims 7 to 10, wherein the drying is carried out at a temperature of 60 to 120 ℃ for 1 to 30 minutes.
12. A mask comprising the plant fiber self-supporting graphene haze-proof filter layer material according to any one of claims 1 to 6.
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| CN111569286A (en) * | 2020-02-08 | 2020-08-25 | 朱鹏飞 | Reusable antivirus mask |
| US20210307428A1 (en) * | 2020-04-03 | 2021-10-07 | Nanotek Instruments Group, Llc | Antiviral filtration element and filtration devices containing same |
| US20210316171A1 (en) * | 2020-04-09 | 2021-10-14 | Nanotek Instruments Group, Llc | Graphitic antiviral filtration element and filtration devices containing same |
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