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CN111111474B - Medium for air filtration - Google Patents

Medium for air filtration Download PDF

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CN111111474B
CN111111474B CN201911342796.8A CN201911342796A CN111111474B CN 111111474 B CN111111474 B CN 111111474B CN 201911342796 A CN201911342796 A CN 201911342796A CN 111111474 B CN111111474 B CN 111111474B
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fiber membrane
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CN111111474A (en
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赵静
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Aishe Environmental Technology Chengdu Co ltd
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Aishe Environmental Technology Chengdu Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • 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
    • B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]

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  • Artificial Filaments (AREA)

Abstract

The invention discloses a medium for air filtration, which is a polymer fiber membrane with the grammage of between 15 and 50 g/cubic meter. The medium for air filtration has the characteristics of small pore diameter, high porosity and good fiber uniformity, can effectively filter oily particles while efficiently filtering dust, and has great potential application advantages in the fields of gas filtration, individual protection and the like.

Description

Medium for air filtration
Technical Field
The present invention relates to a medium for air filtration.
Background
Air is a necessary condition for human survival. For maintaining normal vital functions of human body, about 1.5kg of food and 2kg of water are needed every day, but up to 12kg of air is needed to meet basic survival needs; for ensuring normal production of human society, efficient operation of production activities in the fields of medical health, high-precision electronic equipment, food aseptic packaging and the like is closely related to the air cleanliness.
However, in recent years, the air pollution situation in China is becoming more severe, and especially the PM2.5 (fine particulate matters with aerodynamic diameter below 2.5 μm, also called as fine particulate matters) in the air brings great harm to human health and production life. According to 2016 global urban pollution data released by the world health organization, the city of China occupies 30% in the cities with the average PM2.5 concentration ranked from high to low by 100. In addition, the research of international economic cooperation and development organization finds that the economic loss of China caused by haze pollution is up to 1.4 trillion dollars in 2010.
The invention of application No. 201680044092.0 discloses a variable efficiency filter media. The variable efficiency filter media is a composite media formed from at least two different types of filter media, such as standard efficiency media and high efficiency media. The variable efficiency filter media has at least two different efficiency levels. Different efficiency levels may be distributed over different regions. The filter media types of standard efficiency media and high efficiency media may be spun media, melt blown media, nanofiber media, microglass media, cellulose media, carded staple fiber media, and the like. The variable efficiency filter media may be produced by any of an air-laid or wet-laid process.
The invention of application No. 201280007638.7 discloses a filter media pack having a single layer of a high loft filter media and a single layer of a low loft filter media, the filter media pack characterized by the absence of oil added to the filter media pack, the filter media pack capable of filtering air-borne particulates from an air stream at greater than 94% efficiency at air stream flow rates of between about (100) feet per minute and (3000) feet per minute. Filter assemblies formed from the filter media pack and methods of using the filter assemblies are also disclosed.
The invention of application No. 201280073229.7 relates to a filter media for air filtration. The filter media includes a porous membrane layer and a pre-filter layer having a downstream surface and an upstream surface, wherein the pre-filter layer is disposed to have the downstream surface adjacent to an upstream side of the porous membrane layer. The pre-filter layer comprises a wet laid composite media having a mixture of glass fibers and synthetic fibers. The invention also relates to the use of the filter medium in a gas turbine.
Disclosure of Invention
The invention aims to provide a medium for air filtration, which has the characteristics of small pore diameter, high porosity and good fiber uniformity, and can effectively filter oily particles while efficiently filtering dust.
The invention discloses a medium for air filtration, which is a polymer fiber membrane with the gram weight of between 15 and 50 grams per cubic meter.
The polymer fiber membrane in the invention takes polyacrylonitrile and polyurethane as a high molecular matrix, mainly due to the following considerations: polyacrylonitrile is a polymer obtained by acrylonitrile monomers through free radical polymerization, the structures in a macromolecular chain are generally connected in a head-to-tail mode, the polyacrylonitrile has good chemical stability, is not easy to hydrolyze, resists oxidation and solvents, has good weather resistance and sun resistance, and can effectively prevent gas permeation; the polyurethane is a polymer material containing urethane groups in molecular chains, and is a segmented polymer with alternate soft segments and hard segments, the hard phase is insoluble in the soft phase and forms a discontinuous micro-phase structure, and plays a role of a physical cross-linking point in the soft segment, wherein the unique characteristics are endowed by the micro-phase separation, so that the polyurethane has good mechanical strength, such as high elasticity, tensile strength, tearing strength, wear resistance, impact absorption performance, oil resistance, ozone resistance, heat resistance, hydrolysis resistance and other characteristics.
As one of the preferable technical schemes of the invention, the polymer fiber membrane is a polyacrylonitrile/polyurethane fiber membrane, and is prepared by the following method:
(1) weighing 2-5 g of polyacrylonitrile and 0.3-0.6 g of polyurethane, adding the weighed materials into 25-100 g N, N-dimethylformamide, and stirring the materials on a constant-temperature stirrer for 12-24 hours to obtain a uniform solution;
(2) absorbing the uniform solution obtained in the step (1), and spinning by adopting an electrostatic spinning device to obtain a fiber membrane; and placing the fiber membrane in a vacuum drying oven for vacuum drying to obtain the polyacrylonitrile/polyurethane fiber membrane.
As a second preferred technical scheme of the invention, the polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane fiber membrane, and is prepared by the following method:
(1) weighing 2-5 g of polyacrylonitrile and 0.3-0.6 g of fluorine modified polyurethane, adding the weighed materials into 25-100 g N, N-dimethylformamide, and stirring the materials on a constant-temperature stirrer for 12-24 hours to obtain a uniform solution;
(2) absorbing the uniform solution obtained in the step (1), and spinning by adopting an electrostatic spinning device to obtain a fiber membrane; and (3) placing the fiber membrane in a vacuum drying oven for vacuum drying to obtain the polyacrylonitrile/fluorine modified polyurethane fiber membrane.
As a third preferred technical scheme of the invention, the polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane fiber membrane, and is prepared by the following method:
(1) weighing 2-5 g of polyacrylonitrile, 0.3-0.6 g of fluorine modified polyurethane and 0.3-0.6 g of waterborne polyurethane, adding the weighed materials into 25-100 g N, N-dimethylformamide, and stirring the materials on a constant-temperature stirrer for 12-24 hours to obtain a uniform solution;
(2) absorbing the uniform solution obtained in the step (1), and spinning by adopting an electrostatic spinning device to obtain a fiber membrane; and placing the fiber membrane in a vacuum drying oven for vacuum drying to obtain the polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane fiber membrane.
As a fourth preferred technical scheme of the present invention, the polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane, and is prepared by the following method:
(1) weighing 2-5 g of polyacrylonitrile, 0.3-0.6 g of fluorine modified polyurethane and 0.3-0.6 g of waterborne polyurethane, adding the weighed materials into 25-100 g N, N-dimethylformamide, stirring the materials for 12-24 hours on a constant-temperature stirrer, then adding 3-6 g of methyl hydrogen-containing silicone oil, and stirring the materials for 12-24 hours on the constant-temperature stirrer to obtain a uniform solution;
(2) absorbing the uniform solution obtained in the step (1), and spinning by adopting an electrostatic spinning device to obtain a fiber membrane; and placing the fiber membrane in a vacuum drying oven for vacuum drying to obtain the polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane fiber membrane.
As a fifth preferred technical scheme of the present invention, the polymer fiber membrane is an inorganic material-doped polyacrylonitrile/fluorine-modified polyurethane/aqueous polyurethane/methyl silicone oil fiber membrane, and is prepared by the following method:
(1) weighing 2-5 g of polyacrylonitrile, 0.3-0.6 g of fluorine modified polyurethane and 0.3-0.6 g of waterborne polyurethane, adding the weighed materials into 25-100 g N, N-dimethylformamide, stirring the materials for 12-24 hours on a constant-temperature stirrer, then adding 3-6 g of methyl hydrogen-containing silicone oil, and stirring the materials for 12-24 hours on the constant-temperature stirrer to obtain a uniform solution; adding an inorganic material accounting for 0.5-2% of the weight of the uniform solution into the uniform solution, and performing ultrasonic dispersion for 20-30 minutes to obtain a spinning solution;
(2) absorbing the spinning solution obtained in the step (1), and spinning by adopting an electrostatic spinning device to obtain a fiber membrane; and placing the fiber membrane in a vacuum drying oven for vacuum drying to obtain the polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane.
In the technical scheme, the fluorine modified polyurethane is synthesized by the following steps: putting 25-50 g of 4, 4-diphenylmethane diisocyanate and 20-40 g of N, N-dimethylformamide into a reaction kettle, heating to 45-50 ℃, and stirring for 2-5 minutes; mixing 15-30 g of 2-perfluorooctyl ethyl alcohol and 15-30 g of N, N-dimethylformamide, and heating to 70-80 ℃ to obtain a mixed solution A; adding the mixed solution A into a reaction kettle, and keeping the system temperature at 50-55 ℃ in the adding process; after the addition is finished, reacting for 1-2 hours at the temperature of 50-55 ℃ in a heat preservation way; adding 15-30 g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 58-60 ℃, and carrying out heat preservation reaction at 58-60 ℃ for 1-2 hours; continuously adding 4-8 g of triethylene glycol into the reaction kettle, heating to 65-68 ℃, and reacting for 1-2 hours at 65-68 ℃; mixing 4-9 g of 2-perfluorooctyl ethyl alcohol and 4-9 g of N, N-dimethylformamide, and heating to 75-80 ℃ to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70-75 ℃, and carrying out heat preservation reaction at 70-75 ℃ for 1-2 hours; and (3) terminating the reaction, and drying the mixture obtained by the reaction in vacuum to obtain the fluorine modified polyurethane.
In the technical scheme, the waterborne polyurethane is synthesized by the following steps: adding 40-52 g of toluene diisocyanate into 800-1000 g of polypropylene glycol 2000, heating to 70-75 ℃, and stirring for 10-20 minutes; then naturally cooling to 30-40 ℃, adding 30-49 g of 2, 2-dimethylolpropionic acid and 90-120 g of toluene diisocyanate, and stirring for 50-70 minutes to obtain a prepolymer; adding 3-4.2 g of 1, 4-butanediol into the prepolymer, heating to 70-75 ℃, and shearing and emulsifying at 2000-4000 revolutions per minute for 30-50 minutes to obtain an emulsion; and adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain the waterborne polyurethane.
In the above technical solution, the inorganic material is obtained by the following method: mixing titanium-based oxide and carbide in a mass ratio of 1: (1-5), uniformly mixing, heating to 400-500 ℃, and keeping the temperature at 400-500 ℃ for 2-4 hours to obtain the inorganic material.
The titanium dioxide-based material has good catalytic activity and chemical stability and is widely applied to the field of photocatalysis, but the band gap of titanium dioxide is wider, which causes certain limitation on the photoelectric conversion efficiency of the titanium dioxide-based material. In order to solve the problems, the titanium-based oxide and the carbide are compounded, and the nano-granular titanium-based oxide and the flaky carbide are compounded to form a compound which is tightly combined, so that the separation of electrons and holes is facilitated, and the photocatalytic activity is improved.
Further, the titanium-based oxide is titanium dioxide.
Further, the titanium-based oxide is a ceria-titania composite or a palladium-supported ceria-titania composite.
The preparation process of the cerium dioxide-titanium dioxide compound comprises the following steps: dissolving 3-5 g of tetrabutyl titanate and 0.11-1.1 g of cerium nitrate hexahydrate in 5-10 mL of methanol, then adding 0.25-0.5 mL of hydrochloric acid with the molar concentration of 10mol/L, and stirring for 1-2 hours; heating to 50-60 ℃, adding 0.035-0.07 g of polyoxyethylene, and fully mixing to obtain sol; after vacuum freeze drying, putting the sol in a muffle furnace, heating to 400-500 ℃, and preserving heat for 2 hours at 400-500 ℃; then, continuously heating to 600-700 ℃, and preserving heat for 1-2 hours at 600-700 ℃; and finally, cooling to 30-40 ℃ along with the furnace, and grinding to obtain the product.
In the process of preparing the cerium dioxide-titanium dioxide compound, a sol-gel method is used, so that metal ions can be effectively dispersed to form a network structure, then a vacuum freeze-drying method is adopted to completely store the organic network of colloid, thereby effectively preventing agglomeration and protecting the organization structure from being damaged, not only improving the photocatalytic performance of the compound to a certain extent, but also preventing the agglomeration from causing the reduction of the filtering and mechanical properties of a fiber membrane.
The preparation process of the palladium-supported cerium dioxide-titanium dioxide compound comprises the following steps: dissolving 3-5 g of tetrabutyl titanate and 0.11-1.1 g of cerous nitrate hexahydrate in 5-10 mL of methanol, then adding 0.25-0.5 mL of hydrochloric acid solution of palladium chloride, wherein the molar concentration of the palladium chloride is 0.25mol/L, the molar concentration of hydrogen chloride is 10mol/L, the hydrochloric acid is used for dissolving the palladium chloride and inhibiting hydrolysis of the tetrabutyl titanate, and stirring for 1-2 hours; heating to 50-60 ℃, adding 0.035-0.07 g of polyoxyethylene, and fully mixing to obtain sol; freeze-drying the sol in vacuum, and then placing the sol in a muffle furnace to heat to 400-500 ℃, and preserving the heat for 2 hours at 400-500 ℃; then, continuously heating to 600-700 ℃, and preserving heat for 1-2 hours at 600-700 ℃; and finally, cooling to 30-40 ℃ along with the furnace, and grinding to obtain the product.
According to the invention, palladium is loaded on the cerium dioxide-titanium dioxide composite, noble metal palladium participates in the catalytic reaction of carbon monoxide by introducing crystal lattices, and the reduction of palladium oxide and cerium dioxide is promoted by the stronger coupling action between the carrier cerium dioxide-titanium dioxide composite and the load palladium, so that the capability of catalytic oxidation of carbon monoxide is effectively improved, and meanwhile, the crystal grain size of titanium dioxide can be obviously reduced by embedding the cerium dioxide into a titanium dioxide matrix, which is beneficial to improving the mechanical property and the filtering property of a fiber membrane.
The carbide is one or a mixture of multi-wall carbon nano-tubes and graphite-phase carbon nitride nano-sheets. Preferably, the carbide is multi-walled carbon nanotubes and graphite phase carbon nitride nanosheets which are mixed in a mass ratio of 1: 1, in a mixture of the components.
The medium for air filtration has the characteristics of small pore diameter, high porosity and good fiber uniformity, can effectively filter oily particles while efficiently filtering dust, and has great potential application advantages in the fields of gas filtration, individual protection and the like.
Detailed Description
The raw materials in the examples are as follows:
polyacrylonitrile, weight average molecular weight 13 million, available from the japanese bell jar chemistry, technical grade.
Polyurethane with 11 ten thousand weight average molecular weight and 1.12g/cm density 3 Industrial grade, available from basf polyurethane specialty products limited.
The polytetrahydrofuran ether glycol, specifically PTMG1000, is used, and before use, a vacuum circulating water pump is adopted to remove water under reduced pressure for 2 hours at the temperature of 110 ℃ and the absolute pressure of 0.06 MPa.
4, 4-diphenylmethane diisocyanate, CAS No.: 101-68-8.
2-perfluorooctylethyl alcohol, CAS No.: 678-39-7.
Triethylene glycol, CAS No.: 112-27-6.
Polypropylene glycol 2000, CAS No.: 25322-69-4, before use, vacuum circulating water pump is adopted to remove water under reduced pressure at 105 deg.C and 0.06MPa for 24 hr.
Toluene diisocyanate, CAS No.: 26471-62-5.
2, 2-dimethylolpropionic acid, CAS No.: 4767-03-7.
1, 4-butanediol, CAS No.: 110-63-4.
Triethylamine, CAS number: 121-44-8.
Tetrabutyl titanate, CAS No.: 5593-70-4.
Cerium nitrate hexahydrate, CAS No.: 10294-41-4.
Polyethylene oxide, having a weight average molecular weight of 50 ten thousand, was supplied by Ganbuck New technology, Inc. (Shanghai).
Titanium dioxide, CAS No.: 13463-67-7.
Ammonium thiocyanate, CAS No.: 1762-95-4.
Palladium chloride, CAS No.: 7647-10-1.
Multiwalled carbon nanotubes, available from suzhou carbofeng graphene technologies ltd.
Example 1
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The polymer fiber membrane is a polyacrylonitrile/polyurethane fiber membrane and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile and 0.3g of polyurethane, adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours at a constant temperature on a stirrer at 300 revolutions per minute to obtain a uniform solution;
(2) sucking the uniform solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, the high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours under the conditions of 70 ℃ and 0.06MPa of absolute pressure to obtain the polyacrylonitrile/polyurethane fiber membrane.
Example 2
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane fiber membrane and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile and 0.3g of fluorine modified polyurethane, then adding the polyacrylonitrile and the fluorine modified polyurethane into 25g N, N-dimethylformamide, and stirring the mixture for 24 hours at a constant temperature stirrer at a speed of 300 r/min to obtain a uniform solution;
(2) sucking the uniform solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, the high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours under the conditions of 70 ℃ and 0.06MPa of absolute pressure to obtain the polyacrylonitrile/fluorine modified polyurethane fiber membrane.
The synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 70 ℃ for 1 hour; and (3) terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at the temperature of 60 ℃ and the absolute pressure of 0.06MPa to obtain the fluorine modified polyurethane.
Example 3
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane fiber membrane and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile, 0.3g of fluorine modified polyurethane and 0.6g of waterborne polyurethane, adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours at 300 revolutions per minute on a constant-temperature stirrer to obtain a uniform solution;
(2) sucking the uniform solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, the high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours under the conditions of 70 ℃ and 0.06MPa of absolute pressure to obtain the polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane fiber membrane.
The synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at the temperature of 70 ℃ for 1 hour; and (3) terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at the temperature of 60 ℃ and the absolute pressure of 0.06MPa to obtain the fluorine modified polyurethane.
The waterborne polyurethane comprises the following synthetic steps: adding 52g of toluene diisocyanate into 1000g of polypropylene glycol 2000, heating to 75 ℃ at the speed of 2 ℃/min, and stirring for 20 minutes at the speed of 100 revolutions per minute; then naturally cooling to 30 ℃, adding 49g of 2, 2-dimethylolpropionic acid and 120g of toluene diisocyanate, and stirring for 70 minutes at 100 revolutions per minute to obtain a prepolymer; adding 4.2g of 1, 4-butanediol into the prepolymer, heating to 75 ℃ at the speed of 2 ℃/min, and shearing and emulsifying at the speed of 2000 rpm for 30 minutes to obtain an emulsion; and adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain the waterborne polyurethane.
Example 4
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The medium for air filtration is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane, and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile, 0.3g of fluorine modified polyurethane and 0.6g of waterborne polyurethane, then adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours on a constant-temperature stirrer at 300 revolutions per minute; then 3g of methyl hydrogen-containing silicone oil is added, and the mixture is stirred on a constant-temperature stirrer at 300 revolutions per minute for 12 hours to obtain a uniform solution;
(2) sucking the uniform solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, the high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours at 70 ℃ under the absolute pressure of 0.06MPa to obtain the polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane.
The synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 70 ℃ for 1 hour; and (3) terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at the temperature of 60 ℃ and the absolute pressure of 0.06MPa to obtain the fluorine modified polyurethane.
The waterborne polyurethane comprises the following synthetic steps: adding 52g of toluene diisocyanate into 1000g of polypropylene glycol 2000, heating to 75 ℃ at the speed of 2 ℃/min, and stirring for 20 minutes at the speed of 100 revolutions per minute; then naturally cooling to 30 ℃, adding 49g of 2, 2-dimethylolpropionic acid and 120g of toluene diisocyanate, and stirring for 70 minutes at 100 revolutions per minute to obtain a prepolymer; adding 4.2g of 1, 4-butanediol into the prepolymer, heating to 75 ℃ at the speed of 2 ℃/min, and shearing and emulsifying at the speed of 2000 rpm for 30 minutes to obtain an emulsion; and adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain the waterborne polyurethane.
Example 5
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane doped with inorganic materials, and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile, 0.3g of fluorine modified polyurethane and 0.6g of waterborne polyurethane, then adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours on a constant-temperature stirrer at 300 revolutions per minute; then 3g of methyl hydrogen-containing silicone oil is added, and the mixture is stirred on a constant-temperature stirrer at 300 revolutions per minute for 12 hours to obtain a uniform solution; adding an inorganic material accounting for 1 percent of the weight of the uniform solution into the uniform solution, and performing ultrasonic dispersion for 30 minutes under the conditions of ultrasonic power of 200W and ultrasonic frequency of 40kHz to obtain a spinning solution;
(2) sucking the spinning solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, a high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours at 70 ℃ under the absolute pressure of 0.06MPa to obtain the inorganic material doped polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane.
The synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/min to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 70 ℃ for 1 hour; and (3) terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at the temperature of 60 ℃ and the absolute pressure of 0.06MPa to obtain the fluorine modified polyurethane.
The waterborne polyurethane comprises the following synthetic steps: adding 52g of toluene diisocyanate into 1000g of polypropylene glycol 2000, heating to 75 ℃ at the speed of 2 ℃/min, and stirring for 20 minutes at the speed of 100 revolutions per minute; then naturally cooling to 30 ℃, adding 49g of 2, 2-dimethylolpropionic acid and 120g of toluene diisocyanate, and stirring for 70 minutes at 100 revolutions per minute to obtain a prepolymer; adding 4.2g of 1, 4-butanediol into the prepolymer, heating to 75 ℃ at the speed of 2 ℃/min, and shearing and emulsifying at the speed of 2000 rpm for 30 minutes to obtain an emulsion; and adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain the waterborne polyurethane.
The inorganic material is obtained by the following method: mixing titanium-based oxide and carbide in a mass ratio of 1: 3, uniformly mixing, heating to 400 ℃ at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 2 hours to obtain the inorganic material.
The titanium-based oxide is titanium dioxide.
The carbide is a graphite phase carbon nitride nanosheet, and the preparation process comprises the following steps: and (3) putting 6g of ammonium thiocyanate into a crucible, heating to 550 ℃ at a speed of 10 ℃/min in a muffle furnace, preserving heat for 4 hours at 550 ℃, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50nm to obtain the ammonium thiocyanate.
Example 6
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane doped with inorganic materials, and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile, 0.3g of fluorine modified polyurethane and 0.6g of waterborne polyurethane, then adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours on a constant-temperature stirrer at 300 revolutions per minute; then 3g of methyl hydrogen-containing silicone oil is added, and the mixture is stirred on a constant-temperature stirrer at 300 revolutions per minute for 12 hours to obtain a uniform solution; adding an inorganic material accounting for 1 percent of the weight of the uniform solution into the uniform solution, and performing ultrasonic dispersion for 30 minutes under the conditions of ultrasonic power of 200W and ultrasonic frequency of 40kHz to obtain a spinning solution;
(2) sucking the spinning solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, a high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours at 70 ℃ under the absolute pressure of 0.06MPa to obtain the inorganic material doped polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane.
The synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 70 ℃ for 1 hour; and (3) terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at the temperature of 60 ℃ and the absolute pressure of 0.06MPa to obtain the fluorine modified polyurethane.
The waterborne polyurethane comprises the following synthetic steps: adding 52g of toluene diisocyanate into 1000g of polypropylene glycol 2000, heating to 75 ℃ at the speed of 2 ℃/min, and stirring for 20 minutes at the speed of 100 revolutions per minute; then naturally cooling to 30 ℃, adding 49g of 2, 2-dimethylolpropionic acid and 120g of toluene diisocyanate, and stirring for 70 minutes at 100 revolutions per minute to obtain a prepolymer; adding 4.2g of 1, 4-butanediol into the prepolymer, heating to 75 ℃ at the speed of 2 ℃/min, and shearing and emulsifying at the speed of 2000 rpm for 30 minutes to obtain an emulsion; and adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain the waterborne polyurethane.
The inorganic material is obtained by the following method: mixing titanium-based oxide and carbide in a mass ratio of 1: 3, uniformly mixing, heating to 400 ℃ at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 2 hours to obtain the inorganic material.
The titanium-based oxide is a cerium dioxide-titanium dioxide compound and is obtained by the following method: dissolving 3.4g of tetrabutyl titanate and 0.22g of cerous nitrate hexahydrate in 5mL of methanol, followed by addition of 0.25mL of hydrochloric acid having a molar concentration of 10mol/L and stirring at 80 rpm for 1 hour; then heating to 60 ℃ at the speed of 2 ℃/minute, adding 0.035g of polyoxyethylene, and fully and uniformly mixing to obtain sol; after the sol is frozen and dried in vacuum, the sol is put into a muffle furnace to be heated to 400 ℃ at the speed of 5 ℃/min, and the temperature is kept at 400 ℃ for 2 hours; then continuously heating to 600 ℃ at the speed of 2 ℃/min, and preserving the heat at 600 ℃ for 2 hours; and finally, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50 nm.
The carbide is a graphite phase carbon nitride nanosheet, and the preparation process comprises the following steps: and (3) putting 6g of ammonium thiocyanate into a crucible, heating to 550 ℃ at a speed of 10 ℃/min in a muffle furnace, preserving heat for 4 hours at 550 ℃, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50nm to obtain the ammonium thiocyanate.
Example 7
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane doped with inorganic materials, and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile, 0.3g of fluorine modified polyurethane and 0.6g of waterborne polyurethane, then adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours on a constant-temperature stirrer at 300 revolutions per minute; then 3g of methyl hydrogen-containing silicone oil is added, and the mixture is stirred on a constant-temperature stirrer at 300 revolutions per minute for 12 hours to obtain a uniform solution; adding an inorganic material accounting for 1 percent of the weight of the uniform solution into the uniform solution, and performing ultrasonic dispersion for 30 minutes under the conditions of ultrasonic power of 200W and ultrasonic frequency of 40kHz to obtain a spinning solution;
(2) sucking the spinning solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, a high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours at 70 ℃ under the absolute pressure of 0.06MPa to obtain the inorganic material doped polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane.
The synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 70 ℃ for 1 hour; and (3) terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at the temperature of 60 ℃ and the absolute pressure of 0.06MPa to obtain the fluorine modified polyurethane.
The waterborne polyurethane comprises the following synthetic steps: adding 52g of toluene diisocyanate into 1000g of polypropylene glycol 2000, heating to 75 ℃ at the speed of 2 ℃/min, and stirring for 20 minutes at the speed of 100 revolutions per minute; then naturally cooling to 30 ℃, adding 49g of 2, 2-dimethylolpropionic acid and 120g of toluene diisocyanate, and stirring for 70 minutes at 100 revolutions per minute to obtain a prepolymer; adding 4.2g of 1, 4-butanediol into the prepolymer, heating to 75 ℃ at the speed of 2 ℃/min, and shearing and emulsifying at the speed of 2000 rpm for 30 minutes to obtain an emulsion; and adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain the waterborne polyurethane.
The inorganic material is obtained by the following method: mixing titanium-based oxide and carbide in a mass ratio of 1: 3, uniformly mixing, heating to 400 ℃ at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 2 hours to obtain the inorganic material.
The titanium-based oxide is a palladium-supported cerium dioxide-titanium dioxide compound, and is obtained by the following method: dissolving 3.4g of tetrabutyl titanate and 0.22g of cerous nitrate hexahydrate in 5mL of methanol, followed by addition of 0.25mL of a hydrochloric acid solution of palladium chloride, the molar concentration of palladium chloride being 0.25mol/L and the molar concentration of hydrogen chloride being 10mol/L, the hydrochloric acid serving to dissolve the palladium chloride and inhibit hydrolysis of tetrabutyl titanate, and stirring at 80 rpm for 1 hour; then heating to 60 ℃ at the speed of 2 ℃/minute, adding 0.035g of polyoxyethylene, and fully and uniformly mixing to obtain sol; after the sol is frozen and dried in vacuum, the sol is put into a muffle furnace to be heated to 400 ℃ at the speed of 5 ℃/min, and the temperature is kept at 400 ℃ for 2 hours; then continuously heating to 600 ℃ at the speed of 2 ℃/min, and preserving the heat at 600 ℃ for 2 hours; and finally, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50 nm.
The carbide is a graphite phase carbon nitride nanosheet, and the preparation process comprises the following steps: and (3) putting 6g of ammonium thiocyanate into a crucible, heating to 550 ℃ at a speed of 10 ℃/min in a muffle furnace, preserving heat for 4 hours at 550 ℃, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50nm to obtain the ammonium thiocyanate.
Example 8
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane doped with inorganic materials, and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile, 0.3g of fluorine modified polyurethane and 0.6g of waterborne polyurethane, then adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours on a constant-temperature stirrer at 300 revolutions per minute; then 3g of methyl hydrogen-containing silicone oil is added, and the mixture is stirred on a constant-temperature stirrer at 300 revolutions per minute for 12 hours to obtain a uniform solution; adding an inorganic material accounting for 1 percent of the weight of the uniform solution into the uniform solution, and performing ultrasonic dispersion for 30 minutes under the conditions of ultrasonic power of 200W and ultrasonic frequency of 40kHz to obtain a spinning solution;
(2) sucking the spinning solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, a high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours at 70 ℃ under the absolute pressure of 0.06MPa to obtain the inorganic material doped polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane.
The synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 70 ℃ for 1 hour; and (3) terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at the temperature of 60 ℃ and the absolute pressure of 0.06MPa to obtain the fluorine modified polyurethane.
The synthetic steps of the waterborne polyurethane are as follows: adding 52g of toluene diisocyanate into 1000g of polypropylene glycol 2000, heating to 75 ℃ at the speed of 2 ℃/min, and stirring for 20 minutes at the speed of 100 revolutions per minute; then naturally cooling to 30 ℃, adding 49g of 2, 2-dimethylolpropionic acid and 120g of toluene diisocyanate, and stirring for 70 minutes at 100 revolutions per minute to obtain a prepolymer; adding 4.2g of 1, 4-butanediol into the prepolymer, heating to 75 ℃ at the speed of 2 ℃/min, and shearing and emulsifying at the speed of 2000 rpm for 30 minutes to obtain an emulsion; and adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain the waterborne polyurethane.
The inorganic material is obtained by the following method: mixing titanium-based oxide and carbide in a mass ratio of 1: 3, uniformly mixing, heating to 400 ℃ at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 2 hours to obtain the inorganic material.
The titanium-based oxide is a palladium-supported cerium dioxide-titanium dioxide compound, and is obtained by the following method: dissolving 3.4g of tetrabutyl titanate and 0.22g of cerous nitrate hexahydrate in 5mL of methanol, followed by addition of 0.25mL of a hydrochloric acid solution of palladium chloride, the molar concentration of palladium chloride being 0.25mol/L and the molar concentration of hydrogen chloride being 10mol/L, the hydrochloric acid serving to dissolve the palladium chloride and inhibit hydrolysis of tetrabutyl titanate, and stirring at 80 rpm for 1 hour; then heating to 60 ℃ at the speed of 2 ℃/minute, adding 0.035g of polyoxyethylene, and fully and uniformly mixing to obtain sol; after the sol is frozen and dried in vacuum, the sol is put into a muffle furnace to be heated to 400 ℃ at the speed of 5 ℃/min, and the temperature is kept at 400 ℃ for 2 hours; then continuously heating to 600 ℃ at the speed of 2 ℃/min, and preserving the heat at 600 ℃ for 2 hours; and finally, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50 nm.
The carbide is a multi-wall carbon nano tube, and the particle size is 50 nm.
Example 9
The air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter.
The polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane doped with inorganic materials, and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile, 0.3g of fluorine modified polyurethane and 0.6g of waterborne polyurethane, then adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours on a constant-temperature stirrer at 300 revolutions per minute; then 3g of methyl hydrogen-containing silicone oil is added, and the mixture is stirred on a constant-temperature stirrer at 300 revolutions per minute for 12 hours to obtain a uniform solution; adding an inorganic material accounting for 1 percent of the weight of the uniform solution into the uniform solution, and performing ultrasonic dispersion for 30 minutes under the conditions of ultrasonic power of 200W and ultrasonic frequency of 40kHz to obtain a spinning solution;
(2) sucking the spinning solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, a high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; and (3) placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours at 70 ℃ under the absolute pressure of 0.06MPa to obtain the inorganic material doped polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane.
The synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 70 ℃ for 1 hour; and (3) terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at the temperature of 60 ℃ and the absolute pressure of 0.06MPa to obtain the fluorine modified polyurethane.
The waterborne polyurethane comprises the following synthetic steps: adding 52g of toluene diisocyanate into 1000g of polypropylene glycol 2000, heating to 75 ℃ at the speed of 2 ℃/min, and stirring for 20 minutes at the speed of 100 revolutions per minute; then naturally cooling to 30 ℃, adding 49g of 2, 2-dimethylolpropionic acid and 120g of toluene diisocyanate, and stirring for 70 minutes at 100 revolutions per minute to obtain a prepolymer; adding 4.2g of 1, 4-butanediol into the prepolymer, heating to 75 ℃ at the speed of 2 ℃/min, and shearing and emulsifying at the speed of 2000 rpm for 30 minutes to obtain an emulsion; and adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain the waterborne polyurethane.
The inorganic material is obtained by the following method: mixing titanium-based oxide and carbide in a mass ratio of 1: 3, uniformly mixing, heating to 400 ℃ at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 2 hours to obtain the inorganic material.
The titanium-based oxide is a palladium-supported cerium dioxide-titanium dioxide compound, and is obtained by the following method: dissolving 3.4g of tetrabutyl titanate and 0.22g of cerous nitrate hexahydrate in 5mL of methanol, followed by addition of 0.25mL of a hydrochloric acid solution of palladium chloride, the molar concentration of palladium chloride being 0.25mol/L and the molar concentration of hydrogen chloride being 10mol/L, the hydrochloric acid serving to dissolve the palladium chloride and inhibit hydrolysis of tetrabutyl titanate, and stirring at 80 rpm for 1 hour; then heating to 60 ℃ at the speed of 2 ℃/minute, adding 0.035g of polyoxyethylene, and fully and uniformly mixing to obtain sol; after the sol is frozen and dried in vacuum, the sol is put into a muffle furnace to be heated to 400 ℃ at the speed of 5 ℃/min, and the temperature is kept at 400 ℃ for 2 hours; then continuously heating to 600 ℃ at the speed of 2 ℃/min, and preserving the heat at 600 ℃ for 2 hours; and finally, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50 nm.
The carbide is a multi-walled carbon nanotube and a graphite phase carbon nitride nanosheet in a mass ratio of 1: 1, in a mixture of the components. The preparation process of the graphite phase carbon nitride nanosheet comprises the following steps: and (3) putting 6g of ammonium thiocyanate into a crucible, heating to 550 ℃ at a speed of 10 ℃/min in a muffle furnace, preserving heat for 4 hours at 550 ℃, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50nm to obtain the ammonium thiocyanate.
Effect example 1
The air filtration media of examples 1 to 9 were subjected to atmospheric particulates filtration efficiency tests, and the specific operation method was referred to zhangyang master paper, "research on WPU composite fiber membranes prepared by electrospinning and air filtration performance thereof".
The filter fraction of the air filter device is defined as the percentage value of the amount of dust captured by the filter device to the upstream air dust content, and the measurement of the efficiency fraction of the air filter device specifies a uniform calculation criterion and a criterion for calculating the efficiency fraction, so that a comparison can be performed.
The grading and counting standards are made with reference to GB 122218-8.
The specific test results are shown in table 1.
Table 1 results table of atmospheric particulate matter filtration efficiency
Figure BDA0002332091700000211
Figure BDA0002332091700000221
In the embodiment 2, the fluorine modified polyurethane is introduced into the spinning raw material, so that the spinnability of the fiber is enhanced, the pore size of the fiber membrane is reduced, the filtering performance of the fiber membrane is greatly improved, and a little adhesion exists between the fibers. By adding the water polyurethane into the spinning solution, the viscosity of the spinning solution is reduced, the filtering performance and the mechanical performance of the fiber membrane are slightly reduced, and in example 4, the methyl hydrogen silicone oil is introduced on the basis of example 3, so that the methyl hydrogen silicone oil fills the defective holes on the surface of the fiber, and the water resistance of the material and the integrity of the surface of the fiber membrane are improved.
Effect example 2
The catalytic oxidation properties of the air filtration media of examples 5 to 9 were measured in a quartz tube of a fixed bed (inner diameter of 6.0mm) flow reactor. The amount of the air filtration medium used was 50mg without any pretreatment before use. The medium for air filtration and quartz sand are uniformly mixed and then placed in the middle of a quartz tube, and the volume of reaction gas comprises the following components: 1% of carbon monoxide; 10% of oxygen, 8% of nitrogen and the balance of air. The flow rate of the reaction gas was 72000 mL/(g.h). Before the reaction, high-purity nitrogen is continuously blown into the reaction kettle for 1 hour for full purification, a thermocouple for controlling the reaction temperature is ensured to be positioned at the central position of the air filtering medium, after the reaction gas enters a testing device, the temperature is gradually increased from room temperature to 400 ℃ or until carbon monoxide is completely oxidized, the temperature increase rate is 2 ℃/min, and the carbon monoxide catalytic oxidation activity of the air filtering medium is measured by the lowest temperature when the carbon monoxide is completely converted.
The specific test results are shown in table 2.
TABLE 2 results of catalytic Oxidation Performance
Figure BDA0002332091700000222
Figure BDA0002332091700000231
As can be seen from table 2, in example 7, palladium is supported on a ceria-titania composite, and noble metal palladium participates in a catalytic reaction of carbon monoxide by introducing crystal lattices, and a strong coupling effect between the carrier ceria-titania composite and supported palladium promotes reduction of palladium oxide and ceria, so that the ability of catalytic oxidation of carbon monoxide is effectively improved, and meanwhile, the crystal grain size of titania can be significantly reduced by embedding ceria in a titania matrix, which is beneficial to improving mechanical properties and filtration performance of a fiber membrane.
Effect example 3
The mechanical properties of the air filtration media of examples 1 to 9 were measured, and the specific index was tensile strength. The tensile strength tester is an XQ-1C type tensile strength tester provided by Shanghai Lipu applied science and technology research. Before testing, a CH-12.7-STSX digital display film thickness gauge is adopted to test the thickness of a sample, 20 different point positions are selected on a fiber membrane for testing, and finally, the average value is obtained to be used as the thickness of the air filtering medium fiber membrane. When the tensile test is carried out, the initial tensile length of the medium fiber membrane for air filtration is regulated and controlled to be 10mm, the tensile speed is regulated and controlled to be 10mm/min, the pre-tension is regulated and controlled to be 0.1cN, and the width of a sample strip is regulated and controlled to be 3 cm. Each sample was tested 10 times and the tensile strength was calculated.
The specific test results are shown in table 3.
Table 3 tensile strength results table
Figure BDA0002332091700000232
Figure BDA0002332091700000241
In the process of preparing the ceria-titania composite in embodiment 6 of the present invention, a sol-gel method is used to effectively disperse metal ions to form a network structure, and then a vacuum freeze-drying method is used to completely preserve the organic network of the colloid, thereby effectively preventing agglomeration and protecting the organization structure from being damaged, which not only can improve the photocatalytic performance of the composite to a certain extent, but also can prevent the fiber membrane filtration and the reduction of mechanical properties caused by agglomeration.
It should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments may be appropriately combined to form other embodiments as will be appreciated by those skilled in the art.

Claims (3)

1. Air filtration media characterized in that said air filtration media is a polymeric fiber membrane having a grammage of between 15 grams per cubic meter and 50 grams per cubic meter;
the polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane doped with inorganic materials, and is prepared by the following method:
(1) weighing 2-5 g of polyacrylonitrile, 0.3-0.6 g of fluorine modified polyurethane and 0.3-0.6 g of waterborne polyurethane, adding the weighed materials into 25-100 g N, N-dimethylformamide, stirring the materials for 12-24 hours on a constant-temperature stirrer, then adding 3-6 g of methyl hydrogen-containing silicone oil, and stirring the materials for 12-24 hours on the constant-temperature stirrer to obtain a uniform solution; adding an inorganic material accounting for 0.5-2% of the weight of the uniform solution into the uniform solution, and performing ultrasonic dispersion for 20-30 minutes to obtain a spinning solution;
(2) absorbing the spinning solution obtained in the step (1), and spinning by adopting an electrostatic spinning device to obtain a fiber membrane; placing the fiber membrane in a vacuum drying oven for vacuum drying to obtain the polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane;
the synthetic steps of the fluorine modified polyurethane are as follows: putting 25-50 g of 4, 4-diphenylmethane diisocyanate and 20-40 g of N, N-dimethylformamide into a reaction kettle, heating to 45-50 ℃, and stirring for 2-5 minutes; mixing 15-30 g of 2-perfluorooctyl ethyl alcohol and 15-30 g of N, N-dimethylformamide, and heating to 70-80 ℃ to obtain a mixed solution A; adding the mixed solution A into a reaction kettle, and keeping the system temperature at 50-55 ℃ in the adding process; after the addition is finished, reacting for 1-2 hours at the temperature of 50-55 ℃ in a heat preservation way; adding 15-30 g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 58-60 ℃, and carrying out heat preservation reaction at 58-60 ℃ for 1-2 hours; continuously adding 4-8 g of triethylene glycol into the reaction kettle, heating to 65-68 ℃, and reacting for 1-2 hours at 65-68 ℃; mixing 4-9 g of 2-perfluorooctyl ethyl alcohol and 4-9 g of N, N-dimethylformamide, and heating to 75-80 ℃ to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70-75 ℃, and carrying out heat preservation reaction at 70-75 ℃ for 1-2 hours; terminating the reaction, and drying the mixture obtained by the reaction in vacuum to obtain the fluorine modified polyurethane;
the inorganic material is obtained by the following method: mixing titanium-based oxide and carbide in a mass ratio of 1: (1-5) uniformly mixing, heating to 400-500 ℃, and preserving heat for 2-4 hours at 400-500 ℃ to obtain the inorganic material;
the carbide is a multi-walled carbon nanotube and a graphite phase carbon nitride nanosheet in a mass ratio of 1: 1 in a mixture.
2. The air filtration media of claim 1, wherein the titanium based oxide is titanium dioxide.
3. The air filtration media of claim 1, wherein the air filtration media is a polymer fiber membrane having a grammage of 18 grams per cubic meter;
the polymer fiber membrane is a polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane doped with inorganic materials, and is prepared by the following method:
(1) weighing 2.7g of polyacrylonitrile, 0.3g of fluorine modified polyurethane and 0.6g of waterborne polyurethane, then adding the weighed materials into 25g N, N-dimethylformamide, and stirring the materials for 24 hours on a constant-temperature stirrer at 300 revolutions per minute; then 3g of methyl hydrogen-containing silicone oil is added, and the mixture is stirred on a constant-temperature stirrer at 300 revolutions per minute for 12 hours to obtain a uniform solution; adding an inorganic material accounting for 1 percent of the weight of the uniform solution into the uniform solution, and performing ultrasonic dispersion for 30 minutes under the conditions of ultrasonic power of 200W and ultrasonic frequency of 40kHz to obtain a spinning solution;
(2) sucking the spinning solution obtained in the step (1) by using an injector, spinning by using an electrostatic spinning device, wherein the injection speed is 1mL/h, the receiving distance is 15cm, the rotating speed of a roller is 50 rpm, the moving speed of a sliding table is 100cm/min, a high pressure of 25kV is applied to a nozzle, the environmental temperature is 23 ℃, the relative humidity is 45 ℃, and a fiber membrane with the fiber diameter of 350nm is obtained; placing the fiber membrane in a vacuum drying oven, and carrying out vacuum drying for 12 hours at 70 ℃ under the absolute pressure of 0.06MPa to obtain the inorganic material doped polyacrylonitrile/fluorine modified polyurethane/waterborne polyurethane/methyl silicone oil fiber membrane;
the synthetic steps of the fluorine modified polyurethane are as follows: putting 25g of 4, 4-diphenylmethane diisocyanate and 24g of N, N-dimethylformamide into a reaction kettle, heating to 50 ℃ at the speed of 2 ℃/min, and stirring for 2 min at the speed of 100 r/min; mixing 18g of 2-perfluorooctylethyl alcohol and 16g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution A; dropwise adding the mixed solution A into the reaction kettle at the speed of 4 seconds per drop, and keeping the temperature of the system to be 55 ℃ in the dropwise adding process; after the dropwise addition is finished, the reaction is carried out for 1 hour at the temperature of 55 ℃; adding 15g of polytetrahydrofuran ether glycol into a reaction kettle, heating to 60 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 60 ℃ for 1 hour; continuously adding 4g of triethylene glycol into the reaction kettle, heating to 65 ℃ at the speed of 2 ℃/min, and reacting for 1 hour at the temperature of 65 ℃; mixing 4.5g of 2-perfluorooctylethyl alcohol and 4g of N, N-dimethylformamide, and heating to 80 ℃ at the speed of 2 ℃/minute to obtain a mixed solution B; adding the mixed solution B into a reaction kettle, heating to 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation reaction at 70 ℃ for 1 hour; terminating the reaction, and drying the mixture obtained by the reaction in a vacuum drying oven at 60 ℃ and 0.06MPa of absolute pressure to obtain the fluorine modified polyurethane;
the waterborne polyurethane comprises the following synthetic steps: adding 52g of toluene diisocyanate into 1000g of polypropylene glycol 2000, heating to 75 ℃ at the speed of 2 ℃/min, and stirring for 20 minutes at the speed of 100 revolutions per minute; then naturally cooling to 30 ℃, adding 49g of 2, 2-dimethylolpropionic acid and 120g of toluene diisocyanate, and stirring for 70 minutes at 100 revolutions per minute to obtain a prepolymer; adding 4.2g of 1, 4-butanediol into the prepolymer, heating to 75 ℃ at the speed of 2 ℃/min, and shearing and emulsifying at the speed of 2000 rpm for 30 minutes to obtain an emulsion; adding triethylamine into the emulsion, and adjusting the pH value of the emulsion to 7 to obtain waterborne polyurethane;
the inorganic material is obtained by the following method: mixing titanium-based oxide and carbide in a mass ratio of 1: 3, uniformly mixing, heating to 400 ℃ at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 2 hours to obtain the inorganic material;
the titanium-based oxide is a palladium-supported cerium dioxide-titanium dioxide compound, and is obtained by the following method: dissolving 3.4g of tetrabutyl titanate and 0.22g of cerous nitrate hexahydrate in 5mL of methanol, followed by addition of 0.25mL of a hydrochloric acid solution of palladium chloride, the molar concentration of palladium chloride being 0.25mol/L and the molar concentration of hydrogen chloride being 10mol/L, the hydrochloric acid serving to dissolve the palladium chloride and inhibit hydrolysis of tetrabutyl titanate, and stirring at 80 rpm for 1 hour; then heating to 60 ℃ at the speed of 2 ℃/minute, adding 0.035g of polyoxyethylene, and fully and uniformly mixing to obtain sol; after the sol is frozen and dried in vacuum, the sol is put into a muffle furnace to be heated to 400 ℃ at the speed of 5 ℃/min, and the temperature is kept at 400 ℃ for 2 hours; then continuously heating to 600 ℃ at the speed of 2 ℃/min, and preserving the heat at 600 ℃ for 2 hours; finally, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50nm to obtain the product;
the carbide is a multi-walled carbon nanotube and a graphite phase carbon nitride nanosheet in a mass ratio of 1: 1; the preparation process of the graphite phase carbon nitride nanosheet comprises the following steps: and (3) putting 6g of ammonium thiocyanate into a crucible, heating to 550 ℃ at a speed of 10 ℃/min in a muffle furnace, preserving heat for 4 hours at 550 ℃, cooling to 30 ℃ along with the furnace, and grinding until the particle size is 50nm to obtain the ammonium thiocyanate.
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