CN109954479A - A kind of anti-haze filtering layer of self assembly graphene and its preparation method and application - Google Patents
A kind of anti-haze filtering layer of self assembly graphene and its preparation method and application Download PDFInfo
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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
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0036—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention relates to anti-haze filtering layers of a kind of self assembly graphene and its preparation method and application, and high polymer binder layer and graphene layer including being sequentially formed at macromolecule filtering layer material surface, the material of the graphene layer includes graphene or/and graphene oxide；For the high polymer binder layer by obtaining after being carried on the high polymer binder drying of macromolecule filtering layer material surface, the raw material components of the high polymer binder include high molecular polymer basic components, thickener, regulator, crosslinking agent, initiator and solvent.
Description
Technical field
The present invention relates to anti-haze filtering layers of a kind of self assembly graphene and its preparation method and application, belong to adsorbent material neck
Domain.
Background technique
With the development of modern industry, a large amount of discharges etc. of a large amount of uses of fossil fuel, industrial waste gas and vehicle exhaust
A series of atmosphere polluting problem is caused, different degrees of haze weather all occur in the more and more cities of China, this is right
The life of the mankind and health cause serious threat.The main harm ingredient of haze is PM 2.5, it refers to size
At 2.5 microns and the solid particulate matter below being suspended in atmosphere.These small particulate matters can be directly entered human body respiration
System and blood circulation system cause a series of diseases such as asthma, pulmonary tuberculosis, heart disease etc., while being carried on PM2.5 micronic dust
Harmful toxic matter can cause human poisoning, improve lung cancer morbidity rate, influence development of fetus etc., cause greatly to endanger to human society
Evil.Wearing haze-proof mask is a kind of effective means for protecting human health.However most of so-called anti-haze mouths currently on the market
Cover can not effectively stop the finely ground particles such as PM2.5, and permanent wearing masks will make it generate peculiar smell, influence entirety
Comfort.
Graphene is a kind of hexagonal honeycomb shape two-dimensional material being made of carbon atom, and theoretical specific surface area is up to
(2630m2/ g), the assembling of laminated structure, which is piled up, can form porous structure, conducive to the blocking and absorption of molecule.Meanwhile it grinding
Study carefully discovery graphene and can be not only inserted by the cell membrane to bacterium and cut, can also extract phospholipid molecule on cell membrane in turn
It destroys cell membrane and kills bacterium, thus it has great application space in anti-haze, sterilization, dust removal field.Specially
CN104525107A report it is a kind of prepare three-dimensional sponge shape graphene as the method for anti-haze filter material using hydro-thermal method, however should
Method utilizes hydro-thermal method, and relative energy consumption is higher, while prepared three-dimensional sponge shape graphene mechanical strength is poor, filters as mask
Material will easily be compressed in actual use and destroy, and performance is lost.In addition, the macromolecule filtering layer material graphene is easy to fall off,
The secondary hazards of graphene powder are caused to human body.Patent CN105266238A is by composite antibacterial object graphene oxide-tannic acid-
Nano-silver loaded does not have preferable anti-haze performance on non-woven fabrics, can achieve preferable antibacterial effect.
Summary of the invention
Based on the above issues, the purpose of the present invention is to provide a kind of efficient PM2.5 filter efficiency, low respiratory resistance, together
When also have both removing peculiar smell, cheap, simple process has both anti-haze filtering layer of certain anti-microbial property and preparation method thereof and answers
With.
On the one hand, the present invention provides a kind of anti-haze filtering layers of atomization self assembly graphene, including are sequentially formed at macromolecule
The high polymer binder layer and graphene layer of filtering layer material surface, the material of the graphene layer include graphene or/and oxidation
Graphene；
The high polymer binder layer is described by obtaining after being carried on the high polymer binder drying of macromolecule filtering layer material surface
The raw material components of high polymer binder include high molecular polymer basic components, thickener, regulator, crosslinking agent, initiator and
Solvent；The high molecular polymer basic components include polyacrylic acid, polyacrylamide, polyvinyl alcohol, in polyvinyl acetate
At least one, the thickener includes that konjaku glucomannan, carboxymethyl cellulose, hydroxypropyl methyl cellulose, ethoxy are fine
Dimension element, at least one of carboxyl chitosan, the regulator include acrylic acid, acrylamide, in Methacrylamide extremely
Few one kind, the initiator are at least one of potassium peroxydisulfate, ammonium persulfate and azo-bis-isobutyrate hydrochloride V-50, described
Crosslinking agent is N-N methylene-bisacrylamide；Wherein by weight, in the raw material components of the binder, high molecular polymer
The content of basic components is 10~50wt%, and the dosage of thickener is 1~20wt% of high molecular polymer basic components, is adjusted
Agent dosage is 1~10wt% of high molecular polymer basic components, and the dosage of crosslinking agent is the 0 of high molecular polymer basic components
~20wt%, the dosage of initiator are 0~1wt% of high molecular polymer basic components, and surplus is solvent.
The present invention selects specific high polymer binder layer, and (raw material components of the high polymer binder remove high molecular polymerization
It further include thickener, regulator, the high molecular polymer basic components include polypropylene except object basic components and solvent
At least one of acid, polyacrylamide, polyvinyl alcohol, polyvinyl acetate, the thickener include konjaku glucomannan, carboxylic
At least one of methylcellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose and carboxyl chitosan, regulator are propylene
At least one of acid, acrylamide, Methacrylamide.In addition to this, it may also include friendship described in crosslinking agent and/or initiator
Connection agent is N-N methylene-bisacrylamide, and the initiator is at least one of potassium peroxydisulfate, ammonium persulfate, V-50) and stone
Black alkene layer material (graphene or/and graphene oxide) is used as the anti-haze filtering layer of self assembly graphene, wherein the high score of above-mentioned restriction
Contain in sub- binder there are many oxygen-containing functional group (comprising particular functional groups such as carboxyl, hydroxyl, epoxy group, amide groups), it can be with table
The graphene oxide that functionalization group (hydroxyl, carboxyl, carbonyl, epoxy group etc.) is contained in face is assembled, while can also be with stone
Black alkene and three-dimensional grapheme construct Local Porous structure jointly so that graphene oxide/graphene preferably with macromolecule filtering layer
Material adherency is got up.Meanwhile it is feasible at gel-like structure after high polymer binder drying, also there is certain taste removal and prevent spy
Determine the function that structure graphite alkene piece falls off.
Preferably, the molecular weight of the high molecular polymer basic components is 1000~6000.
Preferably, the weight percentage of the high molecular polymer basic components is 20~40wt%；The thickener
Dosage be high molecular polymer basic components 2~10%；The dosage of the regulator is high molecular polymer basic components
2~10wt%；The dosage of the crosslinking agent is 2~10wt% of high molecular polymer basic components, the use of the initiator
Amount is 0.05~0.5wt% of high molecular polymer basic components.
Preferably, the solvent includes at least one of deionized water, dehydrated alcohol, acetone, petroleum ether, preferably go
Ionized water.
Preferably, the macromolecule filtering layer material is polypropylene, polytetrafluoroethylene (PTFE), polyethylene, Kynoar, polychlorostyrene second
Alkene at least one of gathers inclined fluorine vinyl chloride.
Preferably, the macromolecule filtering layer material with a thickness of 80~300 μm, preferably 80~150 μm.Wherein macromolecule
Filtering layer material can be non-woven fabric-like or melt-blown cloth-like.
On the other hand, the present invention also provides a kind of preparation methods of above-mentioned anti-haze filtering layer of self assembly graphene, comprising:
Macromolecule filtering layer material surface is dispersed by high polymer binder；
The macromolecule that load has high polymer binder is scattered in after being atomized containing the dispersion liquid of graphene or/and graphene oxide
Filtering layer material surface, then through drying, the atomized anti-haze filtering layer of self assembly graphene.
Preferably, the concentration of the dispersion liquid containing graphene or/and graphene oxide is 0.5~15mg/ml.Also,
Preferably, the volume ratio of the high polymer binder and the dispersion liquid containing graphene or/and graphene oxide be 1:(0.5~
2)。
Preferably, the temperature of the drying is 60~120 DEG C, the time is 0.5~10 minute.
In another aspect, the present invention also provides a kind of masks comprising the above-mentioned atomization anti-haze filtering layer of self assembly graphene.
Beneficial effects of the present invention:
GO atomization, which is assembled in load, to be had on the macromolecule filtering layer material of high polymer binder, and it is more can both to have realized that graphene was assembled into
Pore structure reaches anti-haze purpose, and can achieve the purpose that remove peculiar smell by the high polymer binder of gelation.Adjustment oxidation stone
Black alkene solution concentration, agglomerant concentration and dosage etc. come adjust the knot size in hole, density degree so regulate and control PM2.5 filter efficiency and
Mask respiratory resistance realizes the preparation of efficiently anti-haze taste removal mask.The method of the invention, it is simple for process, equipment is wanted
Ask lower, prepared filtering layer can effectively filter particulate contaminants in the air such as PM2.5, and PM2.5 filter efficiency is reachable
99% or more, respiratory resistance is smaller, filtration resistance down to 80-130Pa, while have both it is certain eliminate the unusual smell and antibacterial ability, can be real
Existing large-scale promotion production.
Detailed description of the invention
Fig. 1 is graphene oxide solution figure in embodiment 5；
Fig. 2 is high polymer binder solution figure prepared by embodiment 5；
Fig. 3 is the Structure Figure of the macromolecule filtering layer material of spraying graphene oxide sheet prepared by embodiment 5, wherein (a) is
The macro surface figure of anti-haze filtering layer (b) is schemed for the SEM of anti-haze filtering layer；
Fig. 4, which is that embodiment 5 is prepared, is atomized self assembly graphene haze-proof mask pictorial diagram.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention is prepared into using the self assembly effect building Local Porous structure of graphene oxide and high polymer binder
To a kind of anti-haze filtering layer of graphene for being atomized self assembly, and then realize the high efficiency filter of PM2.5.Specifically, by graphene mist
It is sprayed at after change on the macromolecule filtering layer material for being coated with high polymer binder, through being dried, graphene and macromolecule are bonded
Agent is assembled into local porous structure.Using the macromolecule filtering layer material as interlayer of mask, filtration efficiency, low filter can be constructed
Hinder, eliminate the unusual smell, having both the haze-proof mask of certain anti-microbial property.
In the present invention, the anti-haze filtering layer of atomization self assembly graphene includes being sequentially formed at macromolecule filtering layer material surface
Graphene layer and high polymer binder layer, the material of the graphene layer includes graphene or/and graphene oxide；The height
Molecular binder layer after being carried on the high polymer binder drying of macromolecule filtering layer material surface by obtaining.The raw material group of binder
Divide includes high molecular polymer basic components, thickener, regulator, crosslinking agent, initiator and solvent.Wherein, the macromolecule
Polymer base component includes at least one of polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl acetate.It is described
Thickener includes konjaku glucomannan, carboxymethyl cellulose, carboxyl chitosan, hydroxypropyl methyl cellulose, hydroxyethyl cellulose
At least one of.Wherein by weight, in the raw material components of the binder, the content of high molecular polymer basic components is
10~50wt%, preferably 20~40wt%.The dosage of thickener is the 1~20% of high molecular polymer basic components, preferably
For.The dosage of regulator is the 1~10wt%, preferably 2~10wt% of high molecular polymer basic components.The polyphosphazene polymer
The molecular weight for closing object basic components can be 1000~6000.Surplus is solvent.The solvent include deionized water, dehydrated alcohol,
At least one of acetone, petroleum ether, preferably deionized water.The crosslinking agent includes acrylic acid, acrylamide, metering system
At least one of amide, N-N methylene-bisacrylamide, the initiator are potassium peroxydisulfate, ammonium persulfate, two isobutyl of azo
At least one of amidine hydrochloride V-50.The dosage of crosslinking agent is 0~20wt% of high molecular polymer basic components, preferably
2~10wt%.The dosage of initiator is the 0~1wt%, preferably 0.05~0.5wt% of high molecular polymer basic components.This
In invention, the graphene layer material therefor may include aperture be distributed in 10-20 micron range three-dimensional porous graphene, size
4-5 microns of few layer of graphene, monolithic size 30-50 microns redox graphene, monolithic size is at 30-50 microns
At least one of graphene oxide etc..
Illustrate to following exemplary the preparation method of haze-proof mask binder provided by the invention.
Specifically, first high molecular polymer basic components can be first dissolved in partial solvent, is then carrying out binder
Preparation.For example, the high molecular polymer basic components of 5~50wt% (preferably 30~50wt% or 5~40wt%) will be contained
Solution be dissolved in the solvent, the thickener, regulator, crosslinking agent and initiator is added；20 are stirred at 25~90 DEG C
Minute to 8 hours, obtains the haze-proof mask binder.Specifically, by the poly- of a certain concentration (such as 10%-50%))
One or both of acrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl acetate solution is with certain proportion, in certain temperature
Formation Polymer Solution in certain solvent is slowly dissolved under degree (25 DEG C -90 DEG C), and (concentration of Polymer Solution can be 5%-
40%).Wherein, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl acetate molecular weight be 1000-6000.Again plus
Enter one or both of a certain amount of konjaku glucomannan, carboxylated cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose
The above mixture, or these regulators are dissolved in certain solvent, then is added slowly in above-mentioned Polymer Solution, it stirs
(mixing time is 0.5-8h (preferably 0.5-6 hours), and temperature is 25-90 DEG C) for a period of time, until the mixing for forming uniform is molten
Liquid, as haze-proof mask binder.The konjaku glucomannan, carboxylated cellulose, hydroxypropyl methyl cellulose, ethoxy are fine
The dosage of dimension element is the 1%-20% of above-mentioned regulator dosage.Selected solvent is deionized water, dehydrated alcohol, acetone, stone
The mixture of one or more of oily ether solvent.The addition sequence of each component of the present invention is without particular/special requirement.
Can also the introducing crosslinked agent in binder component, crosslinking agent can be added before or after above-mentioned regulator, excellent
It is selected in front of regulator is added and is added.The crosslinking agent is N-N methylene-bisacrylamide, and dosage is middle component A dosage
1%~10%.Initiator can be directly added into, or be added after being dissolved in certain solvent.The dosage of initiator is polyphosphazene polymer
Close the 0~1% of object basic components.Crosslinking agent is added, the viscosity of binder, mechanical property, stability and durability can be promoted.
Initiator can be at least one of potassium peroxydisulfate, ammonium persulfate, V-50.The dosage of initiator is high molecular polymer base set
0~1%, preferably 0.05~0.5% divided.After initiator is added, reacted 1~8 hour at 60~90 DEG C.Thus, it is possible to draw
The polymerization for sending out regulator small molecule monomer, improves the rheological performance of the binder.
Preparation method is simple for the anti-haze filtering layer of atomization self assembly graphene of the present invention, and production cost is low, filtering
Effect is good, it can be achieved that large-scale production.Illustrate to following exemplary the anti-haze filtering layer of atomization self assembly graphene provided by the invention
Preparation method.
By graphene or/graphene oxide ultrasonic disperse, in certain solvent, (selected solvent is deionized water, anhydrous second
The mixture of one or more of alcohol, acetone, petroleum ether solvent) in, it obtains and contains graphene or/and graphene oxide
Solution.The ultrasonic time is 0.5~4h.Concentration containing graphene or/and graphene oxide solution is 0.5mg/ml-
15mg/ml.Above-mentioned graphene or/and graphene oxide can be the low defect graphene of physics removing, improved Hummers legal system
One or more mixtures of standby graphene oxide, three-dimensional porous graphene, microwave reduction graphene oxide.It is described
Specific structure graphene is using the synthesis such as improved Hummers method, hydro-thermal method, solvent-thermal method or template.Prepare above-mentioned oxidation
It is the graphite composite powder of 200-10000 mesh that graphene or/and graphene raw material, which select mesh number,.
The high polymer binder with specific function group is uniformly coated with or sprayed on macromolecule filtering layer material, then
Layer assembly (such as the mode of assembling is spraying etc.) is in height after being atomized containing the dispersion liquid of graphene or/and graphene oxide
On molecule filtering layer material, then filtering layer is obtained after drying, can be used as interlayer of mask, can be prepared by graphene haze-proof mask.It is described
The parameter of spraying includes: spray rate 50~120ml/ minutes.The high polymer binder and contain graphene, three-dimensional grapheme
Or/and the volume ratio of the dispersion liquid of graphene oxide is 1:(0.5~2).Mask PM2.5 filter efficiency is up to 99% or more,
Filtration resistance is 75~135Pa.Macromolecule bonding, which can be coated with or be atomized, to be carried on macromolecule filtering layer material.Drying temperature be 60 DEG C~
120 DEG C, drying time is 0.5~10 minute.Above-mentioned macromolecule filtering layer material is polypropylene, polytetrafluoroethylene (PTFE), polyethylene, gathers partially
Vinyl fluoride, polyvinyl chloride, the non-woven fabrics for gathering inclined fluorine vinyl chloride etc. or one or more of fusion spray cloth mixed layer.
The present invention tests the filter efficiency of mask PM2.5 and gas-flow resistance is all made of the automatic filtrate tester of TIS-8130.
The example of self assembly graphene haze-proof mask preparation method is atomized as one, method and step is as follows: (1) will be special
The graphene ultrasonic disperse of structure is determined in certain solvent, obtains graphene dispersing solution；(2) by the high score containing particular functional group
Sub- binder is uniformly carried on macromolecule filtering layer material；It (3) will be uniform after specific structure graphene dispersing solution atomization in (1)
It is assembled in macromolecule filtering layer material surface in (2), forms haze filter layer；(4) macromolecule filtering layer material in (3) is placed in centainly
At a temperature of dry a period of time, the functionalization group of specific structure graphene and the oxygen-containing functional group of high polymer binder pass through layer
Layer self assembly and form Local Porous separation layer, and then load be made have the filtering interlayer of graphene.(5) by preparation in (4)
Filtering material is as interlayer of mask, and in conjunction with non-woven fabrics, electrostatic filter pulp and fusion spray cloth can prepare graphene haze-proof mask.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.Raw materials used graphite is 200- in following embodiments
The graphite composite powder of 10000 mesh.It is described in mask preparation process it is raw materials used include fusion spray cloth (it is wide: 160cm, grammes per square metre (g/ ㎡):
12g-75g, Xin Long hygienic material Co., Ltd, Yichang City), (1.5mm is thick, 90g/m2, hundred friend of Nanjing weaving for needle thorn electrostatic filter pulp
Materials Co., Ltd), nonwoven layer (PP, wide 0.1-1.6m, Zhongfang Filtering-Material Non-Woven Fabric Co., Ltd.).
Production Example 1: the preparation for the high polymer binder that concentration is 40%
Firstly, taking molecular weight 3000, the polyacrylic acid solution 150ml of concentration 50% is stirred and is slowly added to 100ml deionization
Water is stirred continuously to polyacrylic acid is completely dissolved at room temperature, and 5g acrylamide is then taken to be added in above-mentioned solution, stirs to complete
Dissolution forms uniform solution, then 2.5g konjaku glucomannan is slowly added in above-mentioned solution, stirs 30 minutes at 25 DEG C, to
After konjaku glucomannan adequately dissolves, 0.5g potassium peroxydisulfate is dissolved in a certain amount of deionized water (10ml), is slowly added dropwise
Into above-mentioned solution, continue to be uniformly mixed, 0.5gN-N methylene-bisacrylamide is then dissolved in a certain amount of deionized water
Be added drop-wise in (10ml) in above-mentioned solution, be warming up to 85 DEG C, be stirred to react 1 hour just clear, mixed uniformly binder
Solution.Binder solution 40g is taken to be added in 60g (60ml) deionized water, 25 DEG C of stirrings are until it is completely dissolved to clear
Mixed solution.
Production Example 2: the preparation for the high polymer binder that concentration is 20%
The preparation method for preparing binder is same as above.Binder solution 20g is taken to be added in 80g (80ml) deionized water, 25 DEG C are stirred
Mix until its be completely dissolved to clear mixed solution be 20% high polymer binder solution.
Production Example 3: the preparation for the high polymer binder that concentration is 10%
The preparation method for preparing binder is same as above.Binder solution 10g is taken to be added in 90g (90ml) deionized water, 25 DEG C are stirred
Mix until its be completely dissolved to clear mixed solution be 10% high polymer binder solution.
Production Example 4: graphene oxide is synthesized using improved Hummers method
Under the protection of argon gas, by crystalline flake graphite in tube furnace 1000 DEG C of heating 2h to obtain expanded graphite.1-10g is expanded
Graphite is added in 2000mL large beaker, and the dense H of 500-1000mL is added2SO4、50-200mL H3PO4(the volume ratio of sulfuric acid and phosphoric acid
For 9:1) and 10-80g KMnO4, green is presented in solution colour after stirring.Mixture is reacted in 30-70 DEG C of stirred in water bath
5h, solution colour is gradually from green to brown.To which after reaction, brown solution is poured into containing 50-200mL hydrogen peroxide
(30%) it in 1000mL ice water and stirs, solution immediately becomes golden yellow at this time.It stands overnight, then falls supernatant liquor
Fall, lower layer's solution carries out centrifugal treating.Under the revolving speed of 9500rpm, by 10% dilute hydrochloric acid washing (removal SO4 2-And it is not anti-
The graphite answered), distillation water washing until pH is about 5, collect viscous brown shape product, i.e. graphene oxide.Improved Hummers
Sheet graphene oxide of the monolithic size that method is prepared as at 30-50 microns.
Production Example 5: Microwave reduction method prepares redox graphene
The graphene oxide in a certain amount of Production Example 4 is taken, after freeze-dried, microwave reduction can be obtained by microwave reduction
Graphene oxide.Redox graphene of the monolithic size that Microwave reduction method is prepared as at 30-50 microns.
Production Example 6: physics stripping method prepares low defect graphene
A certain amount of expanded graphite is taken, is scattered in a certain amount of deionized water, certain surface activating agent is added such as: cetyl sulphur
Sour sodium, cetyl trimethylammonium bromide, polyvinylpyrrolidone etc., through certain time ball milling, and ultrasound is peelable obtains
Low defect graphene.Physical method intercalation stripping obtains few layer graphene of the size at 4-5 microns.
Production Example 7: the three-dimensional grapheme of hydro-thermal method synthesis
The graphene oxide in a certain amount of Production Example 1 is taken, a certain concentration (1-15mg/ml) is configured to, a certain amount of crosslinking agent is added:
Such as macromolecule crosslink agent polyvinyl alcohol, PDMS, PEI or low molecule such as ethylenediamine, amino acid etc..Above-mentioned solution is transferred to reaction
It in kettle, at 100-220 DEG C, reacts 6-48 hours, with deionized water and ethanol washing, then freeze-dried can prepare three-dimensional
Graphene.Hydro-thermal method preparation is the three-dimensional porous graphene that aperture is distributed in 10-20 micron range.
Embodiment 1
Firstly, choosing 200 mesh graphite powders, graphene oxide is prepared using improved Hummers method, and stir by ultrasound and machinery
The mode mixed prepares the graphene oxide water solution of 4mg/ml.Then the high polymer binder solution for being 40% by 100ml concentration)
It uniformly sprays on polypropylene non-woven fabric (wide 24.5cm), then glues 50ml graphene oxide solution atomizing spraying in load
On the polypropylene non-woven fabric for tying agent.The non-woven fabrics is dried into 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material.By the filter
Layer combine with fusion spray cloth, electrostatic filter pulp, non-woven layer (middle layer be anti-haze filtering layer, be successively from inside outwards one layer quiet
Electrofiltration cotton, one layer of fusion spray cloth and two layers of macropore non-woven fabrics.If following embodiment 2-9 are without specified otherwise, Respirator structure and this reality
It is identical to apply example 1), graphene haze-proof mask can be made, PM2.5 filter efficiency is up to 97% or more, filtration resistance 128Pa.
Embodiment 2
Firstly, choosing 200 mesh graphite powders, graphene oxide is prepared using improved Hummers method, and stir by ultrasound and machinery
The mode mixed prepares the graphene oxide water solution of 4mg/ml.Then 100ml concentration is uniform for 20% high polymer binder
Be coated on polypropylene non-woven fabric, then will 50ml graphene oxide hold liquid mist after uniformly spray in being coated with binder
On non-woven fabrics.The non-woven fabrics is dried into 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material.By the filtering layer and fusion spray cloth,
Electrostatic filter pulp, non-woven layer combine, and can be made graphene haze-proof mask, PM2.5 filter efficiency up to 97% with
On, filtration resistance 105Pa.
Embodiment 3
Firstly, choosing 200 mesh graphite powders, graphene oxide is prepared using improved Hummers method, and stir by ultrasound and machinery
The mode mixed prepares the graphene oxide water solution of 6mg/ml.Then 100ml concentration is uniform for 20% high polymer binder
Be coated on polypropylene non-woven fabric, then will 50ml graphene oxide hold liquid mist after uniformly spray in being coated with binder
On non-woven fabrics.The non-woven fabrics is dried into 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material.By the filtering layer and fusion spray cloth,
Electrostatic filter pulp, non-woven layer combine, and can be made graphene haze-proof mask, PM2.5 filter efficiency up to 97% with
On, filtration resistance 125Pa.
Embodiment 4
Firstly, choosing the three-dimensional grapheme of hydro-thermal method synthesis and the graphene oxide of improved Hummers method synthesis, 1 was pressed:
4 ratio, and the graphene aqueous solution of 2mg/ml is prepared in ultrasound and churned mechanically mode.Then it is by 100ml concentration
10% high polymer binder is uniformly sprayed in polypropylene melt spraying, then will 50ml graphene hold it is uniform after liquid mist
It is sprayed on the fusion spray cloth for being coated with binder.The non-woven fabrics is dried into 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material.
The filtering layer is combined with fusion spray cloth, electrostatic filter pulp, non-woven layer, graphene haze-proof mask, PM2.5 mistake can be made
Efficiency is filtered up to 98% or more, filtration resistance 90Pa.
Embodiment 5
Firstly, choosing the three-dimensional grapheme of hydro-thermal method synthesis and the graphene oxide of improved Hummers method synthesis, 1 was pressed:
2 ratio, and the graphene aqueous solution of 2mg/ml is prepared in ultrasound and churned mechanically mode.Then it is by 100ml concentration
10% high polymer binder is uniformly sprayed in polypropylene melt spraying, then holds 100ml graphene after liquid mist uniformly
Be sprayed on the fusion spray cloth for being coated with binder.The non-woven fabrics is dried into 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material
Material.The filtering layer is combined with fusion spray cloth, electrostatic filter pulp, non-woven layer, graphene haze-proof mask can be made,
PM2.5 filter efficiency is up to 99% or more, filtration resistance 98Pa.
Embodiment 6
Firstly, choosing 325 mesh graphite powders, improved Hummers method synthesis graphene oxide and physics removing legal system is respectively adopted
Standby low defect graphene.By graphene oxide and physics removing graphene with the ratio of 4:1, and in ultrasound and churned mechanically side
Formula is configured to the graphene aqueous solution of 2mg/ml.Then by 100ml concentration be 10% high polymer binder uniformly spray in
In polypropylene melt spraying, uniformly spray after 100ml graphene is then held liquid mist on the fusion spray cloth for being coated with binder.It will
The non-woven fabrics dry 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material.By the filtering layer and fusion spray cloth, electrostatic filter pulp, nothing
Woven fabric combines layer by layer, and graphene haze-proof mask can be made, and PM2.5 filter efficiency is up to 96% or more, filtration resistance
84Pa。
Embodiment 7
Firstly, choosing 325 mesh graphite powders, improved Hummers method synthesis graphene oxide and physics removing legal system is respectively adopted
Standby low defect graphene.By graphene oxide and physics removing graphene with the ratio of 2:1, and in ultrasound and churned mechanically side
Formula is configured to the graphene aqueous solution of 2mg/ml.Then by 100ml concentration be 10% high polymer binder uniformly spray in
In polypropylene melt spraying, uniformly spray after 100ml graphene is then held liquid mist on the fusion spray cloth for being coated with binder.It will
The non-woven fabrics dry 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material.By the filtering layer and fusion spray cloth, electrostatic filter pulp, nothing
Woven fabric combines layer by layer, and graphene haze-proof mask can be made, and PM2.5 filter efficiency is up to 96% or more, filtration resistance
80Pa。
Embodiment 8
Firstly, choosing 325 mesh graphite powders, improved Hummers method synthesis graphene oxide and microwave reduction legal system is respectively adopted
Standby redox graphene.By graphene oxide and the redox graphene of Microwave reduction method preparation with the ratio of 4:1, and
Ultrasonic and churned mechanically mode is configured to the graphene aqueous solution of 2mg/ml.Then the macromolecule for being 10% by 100ml concentration
Binder is uniformly sprayed in polypropylene melt spraying, is then held 100ml graphene and is uniformly sprayed after liquid mist in being coated with
On the fusion spray cloth of binder.The non-woven fabrics is dried into 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material.By the filtering layer with
Fusion spray cloth, electrostatic filter pulp, non-woven layer combine, and graphene haze-proof mask can be made, and PM2.5 filter efficiency is reachable
98% or more, filtration resistance 92Pa.
Embodiment 9
Firstly, choosing 325 mesh graphite powders, improved Hummers method synthesis graphene oxide and microwave reduction legal system is respectively adopted
Standby redox graphene.By graphene oxide and the graphene of Microwave reduction method preparation with the ratio of 2:1, and in ultrasound and machine
The mode of tool stirring is configured to the graphene aqueous solution of 2mg/ml.Then 100ml concentration is equal for 10% high polymer binder
Even is sprayed in polypropylene melt spraying, then will 100ml graphene hold liquid mist after uniformly spray in being coated with binder
On fusion spray cloth.The non-woven fabrics is dried into 3min under the conditions of 90 DEG C, obtains macromolecule filtering layer material.By the filtering layer and fusion spray cloth,
Electrostatic filter pulp, non-woven layer combine, and can be made graphene haze-proof mask, PM2.5 filter efficiency up to 96% with
On, filtration resistance 95Pa.
Claims (10)
1. a kind of anti-haze filtering layer of self assembly graphene, which is characterized in that including being sequentially formed at macromolecule filtering layer material surface
High polymer binder layer and graphene layer, the material of the graphene layer include graphene or/and graphene oxide；
The high polymer binder layer is described by obtaining after being carried on the high polymer binder drying of macromolecule filtering layer material surface
The raw material components of high polymer binder include high molecular polymer basic components, thickener, regulator, crosslinking agent, initiator and
Solvent；The high molecular polymer basic components include polyacrylic acid, polyacrylamide, polyvinyl alcohol, in polyvinyl acetate
At least one, the thickener includes that konjaku glucomannan, carboxymethyl cellulose, hydroxypropyl methyl cellulose, ethoxy are fine
Dimension element, at least one of carboxyl chitosan, the regulator include acrylic acid, acrylamide, in Methacrylamide extremely
Few one kind, the initiator are at least one of potassium peroxydisulfate, ammonium persulfate and azo-bis-isobutyrate hydrochloride V-50, described
Crosslinking agent is N-N methylene-bisacrylamide；Wherein by weight, in the raw material components of the binder, high molecular polymer
The content of basic components is 10~50wt%, and the dosage of thickener is 1~20wt% of high molecular polymer basic components, regulator
Dosage is 1~10wt% of high molecular polymer basic components, the dosage of crosslinking agent be high molecular polymer basic components 0~
20 wt%, the dosage of initiator are 0~1wt% of high molecular polymer basic components, and surplus is solvent.
2. the anti-haze filtering layer of self assembly graphene according to claim 1, which is characterized in that the high molecular polymer basis
The molecular weight of component is 1000~6000.
3. the anti-haze filtering layer of self assembly graphene according to claim 1 or 2, which is characterized in that the high molecular polymer
The weight percentage of basic components is 20~40 wt%；The dosage of the thickener is the 2 of high molecular polymer basic components
~10%；The dosage of the regulator is 2~10wt% of high molecular polymer basic components；The dosage of the crosslinking agent is high score
2~10wt% of sub- polymer base component；The dosage of the initiator be high molecular polymer basic components 0.05~
0.5wt%。
4. the anti-haze filtering layer of self assembly graphene according to any one of claim 1-3, which is characterized in that the solvent packet
Include at least one of deionized water, dehydrated alcohol, acetone, petroleum ether, preferably deionized water.
5. the anti-haze filtering layer of atomization self assembly graphene described in any one of -4 according to claim 1, which is characterized in that the height
Molecule filtering layer material is polypropylene, polytetrafluoroethylene (PTFE), polyethylene, Kynoar, polyvinyl chloride, gathers in inclined fluorine vinyl chloride extremely
Few one kind.
6. the anti-haze filtering layer of self assembly graphene according to any one of claims 1-5, which is characterized in that the macromolecule
Filtering layer material with a thickness of 80~300 μm.
7. a kind of preparation method of the anti-haze filtering layer of the self assembly graphene as described in any one of claim 1-6, which is characterized in that
Include:
Macromolecule filtering layer material surface is dispersed by high polymer binder；
The macromolecule that load has high polymer binder is scattered in after being atomized containing the dispersion liquid of graphene or/and graphene oxide
Filtering layer material surface, then through drying, obtain the anti-haze filtering layer of self assembly graphene.
8. preparation method according to claim 7, which is characterized in that described containing graphene or/and graphene oxide
The concentration of dispersion liquid is 0.5~15 mg/ml.
9. preparation method according to claim 7 or 8, which is characterized in that the temperature of the drying is 60~120 DEG C, when
Between be 0.5~10 minute.
10. a kind of mask comprising the anti-haze filtering layer of self assembly graphene of any of claims 1-6.
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