CN104194461B - Modified graphene and preparation method thereof, and water-based antistatic epoxy floor paint and preparation method thereof - Google Patents
Modified graphene and preparation method thereof, and water-based antistatic epoxy floor paint and preparation method thereof Download PDFInfo
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- CN104194461B CN104194461B CN201410400503.8A CN201410400503A CN104194461B CN 104194461 B CN104194461 B CN 104194461B CN 201410400503 A CN201410400503 A CN 201410400503A CN 104194461 B CN104194461 B CN 104194461B
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Abstract
The invention relates to a modified graphene and a preparation method thereof, and a water-based antistatic epoxy floor paint and a preparation method thereof. A linear compound with hydroxy and epoxy terminal groups is utilized to modify the graphene, and the modified graphene is used in the water-based epoxy floor paint, thereby greatly enhancing the antistatic capacity of the paint. The performance testing indicates that the surface resistance of the water-based antistatic epoxy floor paint is 2.5*10<4>-2.7*10<5> ohm.
Description
Technical field
The present invention relates to anti-static coatings technical field, more particularly to a kind of modified graphene and preparation method thereof, and
A kind of aqueous antistatic epoxy floor paint and preparation method thereof.
Background technology
Floor paint was invented in 1934 by Germany, mainly by various differences such as oil plant, tree material, color, solvents
Many end production process such as material is blended, dissolving, dispersion are fabricated by, can be divided into ornamental floor paint, heavy antisepsis floor paint,
Resistance to heavily loaded floor paint etc., the features such as it has beautiful, true, attractive in appearance, wear-resisting, waterproof, anti-corrosion.Wherein, epoxide terrace paint due to
Relatively broad application is obtained with good water solubility.
With the development and production of modern science and technology, increasing factory building and workshop propose to floor paint and eliminate quiet
The tired requirement of electrodeposition, this causes that the status of antistatic epoxy floor paint becomes increasingly conspicuous.But antistatic floor in the market
The antistatic performance of paint is very limited, far from meeting use requirement.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of modified graphene and preparation method thereof, with
And a kind of aqueous antistatic epoxy floor paint and preparation method thereof, it is raw material with modified graphene prepared by the present invention, prepare
Aqueous antistatic epoxy floor paint there is excellent antistatic performance.
The invention provides a kind of preparation method of modified graphene, including：
By Graphene and straight chain compound in the presence of quaternary ammonium salt, reaction obtains modified graphene；
The straight chain compound is the straight chain compound of two end groups respectively hydroxyl and epoxy radicals.
Preferably, the mass ratio of the Graphene and straight chain compound is 1：(0.1~10).
Preferably, the straight chain compound is the C of two end groups respectively hydroxyl and epoxy radicals3~20Straight chain compound.
Preferably, the reaction is carried out in organic solvent.
Preferably, the reaction is ultrasonic reaction, and the temperature of the reaction is 60 DEG C~80 DEG C, and the time of the reaction is
2h~8h.
Preferably, the Graphene is porous graphene.
Preferably, the Graphene is prepared in accordance with the following methods：
1), in the presence of catalyst, biomass carbon source is carried out into catalytic treatment, obtains the first intermediate product, it is described to urge
One or more in the chlorate of agent including manganese, iron compound, cobalt class compound and nickel class compound；
2), under conditions of protective gas, after first intermediate product is warming up into second temperature from the first temperature
Insulation, obtains the second intermediate product, and first temperature is 20 DEG C~40 DEG C, and the second temperature is 300 DEG C~400 DEG C；
3), under conditions of protective gas, after second intermediate product is warming up into the 3rd temperature from second temperature
Insulation, obtains the 3rd intermediate product；3rd temperature is 800 DEG C~900 DEG C；
4), under conditions of protective gas, after the 3rd intermediate product is warming up into the 4th temperature from the 3rd temperature
Insulation, obtains the 4th intermediate product, and the 4th temperature is 1100 DEG C~1300 DEG C；
5), under conditions of protective gas, by the 4th intermediate product from the 4th greenhouse cooling to the 5th temperature after
Insulation, obtains porous graphene, and the 5th temperature is 900 DEG C~1000 DEG C.
Preferably, the biomass carbon source be cellulose and lignin in one or two.
Preferably, the biomass carbon source is porous cellulose.
Preferably, the preparation method of the porous cellulose is comprised the following steps：
A), biomass resource is hydrolyzed in acid, lignocellulosic is obtained, the biomass resource include plant and
One or more in agriculture and forestry organic waste material；
B), the lignocellulosic is processed, porous cellulose is obtained, the treatment includes acid treatment, salt treatment
Or organic solvent treatment.
Preferably, the step B) in salt treatment method for acid sulfite process process or alkali sulfite process at
Reason.
Present invention also offers a kind of modified graphene, reacted under the catalysis of quaternary ammonium salt by Graphene and straight chain compound
Obtain；
The straight chain compound is the straight chain compound of two end groups respectively hydroxyl and epoxy radicals.
Preferably, the Graphene is porous graphene.
Preferably, the mass ratio of the Graphene and straight chain compound is 1：(0.1~10).
Preferably, the straight chain compound is the C of two end groups respectively hydroxyl and epoxy radicals3~20Straight chain compound.
Present invention also offers a kind of aqueous antistatic epoxy floor paint, including：
Component A：
40wt%~60wt% aqueous epoxy resins,
0.1wt%~1wt% modified graphenes,
20wt%~30wt% graphite,
The auxiliary agent of surplus,
The modified graphene is modified graphene prepared by above-mentioned preparation method, or above-mentioned modified graphene；
B component：
50wt%~70wt% amine waterborne curing agents,
1wt%~2wt% coalescents,
10wt%~60wt% water,
5wt%~3wt% defoamers；
The amine waterborne curing agent, coalescents, water and defoamer total amount are 100%；
The amino active hydrogen of the B combinations and the epoxy radicals mol ratio of component A are 1:1.
Preferably, the auxiliary agent includes：
2wt%~5wt% reactive diluents,
5wt%~10wt% toughener,
10wt%~15wt% mill bases,
0.1wt%~0.3wt% dispersants,
0.1wt%~0.3wt% wetting agents,
0.1wt%~0.3wt% levelling agents.
Present invention also offers a kind of preparation method of above-mentioned aqueous antistatic epoxy floor paint, including：
A) modified graphene is mixed with graphite, aqueous epoxy resins and auxiliary agent, component A is obtained；
B) amine waterborne curing agent, coalescents, defoamer and water are mixed, B component is obtained；
By B component and component A according to amino active hydrogen and epoxy radicals mol ratio 1:1 ratio mixing, obtains aqueous anti-quiet
Electric epoxy flooring coating；
The step A), B) without sequencing.
Compared with prior art, the present invention is respectively the straight chain compound of hydroxyl and epoxy radicals to Graphene using two end groups
It is modified, then modified Graphene is applied in aqueous epoxy floor coating, substantially increases the antistatic of coating
Ability.Performance test shows that the sheet resistance of aqueous antistatic epoxy floor paint prepared by the present invention is 2.5 × 104~2.7
×105Between Ω.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the Raman spectrum of the Graphene that the embodiment of the present invention 4 is obtained；
Fig. 2 is the transmission electron microscope picture of the Graphene that the embodiment of the present invention 4 is obtained；
Fig. 3 is the transmission electron microscope picture of the Graphene that the embodiment of the present invention 4 is obtained；
Fig. 4 is the transmission electron microscope picture of the Graphene that the embodiment of the present invention 4 is obtained；
Fig. 5 is the transmission electron microscope picture of the Graphene that the embodiment of the present invention 4 is obtained.
Specific embodiment
The invention provides a kind of preparation method of modified graphene, including：
By Graphene and straight chain compound in the presence of quaternary ammonium salt, reaction obtains modified graphene；
The straight chain compound is the straight chain compound of two end groups respectively hydroxyl and epoxy radicals.
The present invention is respectively hydroxyl using two end groups and the straight chain compound of epoxy radicals is modified to Graphene, then will
Modified Graphene is applied in aqueous epoxy floor coating, substantially increases the anti-static ability of coating.Performance test table
Bright, the sheet resistance of aqueous antistatic epoxy floor paint prepared by the present invention is 2.5 × 104Ω~2.7 × 105Between Ω.
In the present invention, specifically limited, preferably porous graphene is had no to the Graphene, more preferably based on biomass
Material is the porous graphene of raw material production.Its preparation method is preferably：
1), in the presence of catalyst, biomass carbon source is carried out into catalytic treatment, obtains the first intermediate product, it is described to urge
One or more in the chlorate of agent including manganese, iron compound, cobalt class compound and nickel class compound；
2), under conditions of protective gas, after first intermediate product is warming up into second temperature from the first temperature
Insulation, obtains the second intermediate product, and first temperature is 20 DEG C~40 DEG C, and the second temperature is 300 DEG C~400 DEG C；
3), under conditions of protective gas, after second intermediate product is warming up into the 3rd temperature from second temperature
Insulation, obtains the 3rd intermediate product；3rd temperature is 800 DEG C~900 DEG C；
4), under conditions of protective gas, after the 3rd intermediate product is warming up into the 4th temperature from the 3rd temperature
Insulation, obtains the 4th intermediate product, and the 4th temperature is 1100 DEG C~1300 DEG C；
5), under conditions of protective gas, by the 4th intermediate product from the 4th greenhouse cooling to the 5th temperature after
Insulation, obtains porous graphene, and the 5th temperature is 900 DEG C~1000 DEG C.
Biomass carbon source is carried out catalytic treatment by the present invention in the presence of catalyst, obtains the first intermediate product, described
One or more in the chlorate of catalyst including manganese, iron compound, cobalt class compound and nickel class compound.The present invention is excellent
Choosing is mixed catalyst and biomass carbon source, obtains the first intermediate product.The present invention is to the method for the mixing without spy
Different limitation, it is using hybrid technology scheme well known to those skilled in the art, the catalyst and the stirring of biomass carbon source is equal
It is even.In the present invention, the temperature of the mixing is preferably 20 DEG C~180 DEG C, more preferably 50 DEG C~150 DEG C, most preferably
It is 80 DEG C~120 DEG C.In the present invention, the time of the mixing be preferably 2 hours~10 hours, more preferably 5 hours~7 is small
When.
In the present invention, the catalyst includes chloride, iron compound, cobalt class compound and the nickel class compound of manganese
In one or more, preferably one kind in the chloride of manganese, iron compound, cobalt class compound and nickel class compound.
In the present invention, the chloride of the manganese is preferably manganese chloride.In the present invention, the iron compound preferably includes the chlorination of iron
One or more in salt, the cyanide of iron and iron content hydrochlorate, more preferably iron chloride, frerrous chloride, ferric nitrate, nitric acid are sub-
Iron, ferric sulfate, ferrous sulfate, the potassium ferricyanide, potassium ferrocyanide and three oxalic acid close one or more in potassium ferrite.In the present invention
In, the cobalt class compound includes the chlorate of cobalt and containing one or more in cobaltatess, more preferably cobalt chloride, nitric acid
One or more in cobalt, cobaltous sulfate and cobalt acetate.In the present invention, the nickel class compound preferably include nickel chlorate and
Containing one or more in nickelate, more preferably one or more in nickel chloride, nickel nitrate, nickel sulfate and nickel acetate.
In the present invention, the catalyst is preferably iron chloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, iron cyanogen
Change potassium, potassium ferrocyanide, three oxalic acid and close potassium ferrite, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, nickel chloride, nickel nitrate, sulfuric acid
One or more in nickel and nickel acetate.The present invention originates without special limitation to the catalyst, using this area skill
The catalyst of mentioned kind known to art personnel, can be bought by market and obtained.
In the present invention, the biomass carbon source is preferably one or two in cellulose and lignin；More preferably
Cellulose；Most preferably porous cellulose.In the present invention, the preparation method of the porous cellulose preferably includes following step
Suddenly：
A), biomass resource is hydrolyzed in acid, lignocellulosic is obtained, the biomass resource includes plant
With one or more in agriculture and forestry organic waste material；
B), the lignocellulosic is processed, porous cellulose is obtained, the treatment includes acid treatment, salt treatment
Or organic solvent treatment.
Preferably in acid be hydrolyzed biomass resource by the present invention, obtains lignocellulosic, the biomass resource bag
Include one or more in plant and agriculture and forestry organic waste material.In the present invention, the temperature of the hydrolysis is preferably 90 DEG C~180 DEG C,
More preferably 120 DEG C~150 DEG C.In the present invention, the time of the hydrolysis be preferably 10min~10h, more preferably 1h~
8h, most preferably 3h~6h.
In the present invention, the acid of the hydrolysis is preferably in sulfuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid, phosphoric acid and acetic acid
One or more, more preferably sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid or acetic acid, most preferably sulfuric acid, nitric acid or hydrochloric acid.In this hair
In bright, the consumption of acid is preferably the 3wt%~20wt% of the biomass resource in the hydrolysis, and more preferably 5wt%~
15wt%, most preferably 8wt%~12wt%.
In the present invention, the biomass resource is preferably agriculture and forestry organic waste material, more preferably cornstalk, corncob, sorghum
One or more in bar, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk and reed, most preferably corncob.
After obtaining lignocellulosic, the present invention is preferably processed the lignocellulosic, obtains porous cellulose, institute
Stating treatment includes the treatment of acid treatment, salt treatment or organic solvent；The lignocellulosic is more preferably carried out salt treatment by the present invention,
Obtain porous cellulose.In the present invention, the method for the salt treatment is preferably acid sulfite process treatment or alkaline sulfurous
The treatment of hydrochlorate method.In the present invention, the pH value in the acid sulphite process processing procedure be preferably 1~7, more preferably 2~
5, most preferably 3~4.In the present invention, the temperature of acid sulfite process treatment is preferably 70 DEG C~180 DEG C, more excellent
Elect 90 DEG C~150 DEG C, most preferably 100 DEG C~120 DEG C as.In the present invention, the time of the acid sulfite process treatment
Preferably 1 hour~6 hours, more preferably 2 hours~5 hours, most preferably 3 hours~4 hours.
In the present invention, the acid in the acid sulfite process treatment is preferably sulfuric acid.In the present invention, the acidity
The consumption of acid is preferably the 4wt%~30wt%, more preferably 8wt% of the lignocellulosic in sulphite process processing procedure
~25wt%, most preferably 10wt%~20wt%.In the present invention, weight hundred sour in the acid sulfite process treatment
Dividing specific concentration preferably makes liquid-solid ratio be (2~20):1, more preferably (4~16):1, most preferably (8~12):1.
In the present invention, the sulphite in acid sulfite process treatment be preferably calcium sulfite, magnesium sulfite,
Sodium sulfite or ammonium sulfite, more preferably magnesium sulfite or sodium sulfite.The present invention is to acid sulfite process treatment
During the consumption of sulphite there is no special limitation, using sulfite pulping mistake well known to those skilled in the art
The consumption of journey sulfite salt.
In the present invention, the pH value in the alkaline sulfurous method processing procedure is preferably 7~14, more preferably 8~13,
Most preferably 9~12.In the present invention, the temperature of the alkali sulfite process treatment is preferably 70 DEG C~180 DEG C, more preferably
It is 90 DEG C~150 DEG C, most preferably 100 DEG C~120 DEG C.In the present invention, the time of the alkali sulfite process treatment is excellent
Elect as 1 hour~6 hours, more preferably 2 hours~5 hours, most preferably 3 hours~4 hours.
In the present invention, the alkali in the alkali sulfite process treatment is preferably calcium hydroxide, NaOH, hydroxide
Ammonium or magnesium hydroxide, more preferably NaOH or magnesium hydroxide.In the present invention, the alkali sulfite process processing procedure
The consumption of middle alkali is preferably the 4wt%~30wt% of the lignocellulosic, more preferably 8wt%~25wt%, most preferably
10wt%~20wt%.In the present invention, the weight percent concentration of alkali preferably makes liquid in the alkali sulfite process treatment
Gu than being (2~20):1, more preferably (4~16):1, most preferably (8~12):1.
In the present invention, the sulphite in alkali sulfite process treatment be preferably calcium sulfite, magnesium sulfite,
Sodium sulfite or ammonium sulfite, more preferably magnesium sulfite or sodium sulfite.The present invention is to alkali sulfite process treatment
During the consumption of sulphite there is no special limitation, using sulfite pulping process well known to those skilled in the art
The consumption of sulfite salt.
After obtaining porous cellulose, the present invention preferably also includes：
The porous cellulose is carried out into bleaching.
The present invention does not have special limitation to the method for the bleaching, using bleaching well known to those skilled in the art
Technical scheme.In the present invention, the method for the bleaching is preferably total chlorine free bleaching, more preferably hydrogen peroxide bleaching.This
Invention does not have special limitation to the concentration of the hydrogen peroxide, using the hydrogen peroxide of typical concentrations.In the present invention, it is described
The quality of hydrogen peroxide is preferably the 1%~10% of the porous cellulose quality, more preferably 2%~8%.In the present invention,
The bleaching temperature of the hydrogen peroxide bleaching is preferably 60 DEG C~130 DEG C, more preferably 80 DEG C~100 DEG C；The hydrogen peroxide bleaching
Bleaching time be preferably 1h~10h, more preferably 2h~8h.
In the present invention, the mass ratio of the catalyst and biomass carbon source is preferably (0.01~2):1, more preferably
(0.1~1):1, most preferably (0.3~0.8):1.In the present invention, the temperature of the catalytic treatment is preferably 20 DEG C~180
DEG C, more preferably 50 DEG C~150 DEG C, most preferably 80 DEG C~120 DEG C.In the present invention, the time of the catalytic treatment is preferred
It is 2 hours~10 hours, more preferably 5 hours~7 hours.
After the biomass carbon source is carried out into catalytic treatment, the biomass after the catalytic treatment that the present invention will preferably be obtained
Carbon source is dried, and obtains the first intermediate product.In the present invention, the temperature of the biomass carbon source after the drying catalytic treatment
Preferably 70 DEG C~120 DEG C, more preferably 90 DEG C~100 DEG C.In the present invention, the water content of first intermediate product is preferred
＜ 10wt%, more preferably ＜ 5wt%.
After obtaining the first intermediate product, the present invention under conditions of protective gas, by first intermediate product from the
One temperature is incubated after being warming up to second temperature, obtains the second intermediate product；First temperature is 20 DEG C~40 DEG C, described second
Temperature is 300 DEG C~400 DEG C.In the present invention, first intermediate product is warming up to the intensification of second temperature from the first temperature
Speed is preferably 5 DEG C/min~20 DEG C/min, more preferably 10 DEG C/min~15 DEG C/min.In the present invention, first temperature
Degree is preferably 25 DEG C~35 DEG C, more preferably 28 DEG C~32 DEG C.In the present invention, the second temperature is preferably 320 DEG C~380
DEG C, more preferably 340 DEG C~360 DEG C.In the present invention, after first intermediate product is warming up to second temperature from the first temperature
Soaking time be preferably 4 hours~8 hours, more preferably 5 hours~6 hours.
In the present invention, the protective gas is preferably one or more in nitrogen and inert gas, more preferably
Nitrogen.In the present invention, the intake of the protective gas is preferably 200mL/min~800mL/min, more preferably
400mL/min~600mL/min.
After obtaining the second intermediate product, the present invention under conditions of protective gas, by second intermediate product from the
Two temperature are incubated after being warming up to the 3rd temperature, obtain the 3rd intermediate product；3rd temperature is 800 DEG C~900 DEG C.In this hair
In bright, the heating rate that second intermediate product is warming up to the 3rd temperature from second temperature be preferably 20 DEG C/min~50 DEG C/
Min, more preferably 30 DEG C/min~40 DEG C/min.In the present invention, the 3rd temperature is preferably 820 DEG C~880 DEG C, more excellent
Elect 840 DEG C~860 DEG C as.In the present invention, second intermediate product is warming up to the insulation after the 3rd temperature from second temperature
Time is preferably 3.5 hours~7 hours, more preferably 5 hours~6 hours.
In the present invention, the species and intake of the protective gas and protective gas described in above-mentioned technical proposal
Species is consistent with intake, will not be repeated here.In the present invention, the protective gas can with described in above-mentioned technical proposal
Protective gas it is identical, it is also possible to it is different.
After obtaining the 3rd intermediate product, the present invention under conditions of protective gas, by the 3rd intermediate product from the
Three temperature are incubated after being warming up to the 4th temperature, obtain the 4th intermediate product；4th temperature is 1100 DEG C~1300 DEG C.At this
In invention, the heating rate that the 3rd intermediate product is warming up to the 4th temperature from the 3rd temperature is preferably 50 DEG C/min~60
DEG C/min, more preferably 54 DEG C/min~58 DEG C/min.In the present invention, the 4th temperature is preferably 1150 DEG C~1250
DEG C, more preferably 1200 DEG C.In the present invention, the 3rd intermediate product is warming up to the insulation after the 4th temperature from the 3rd temperature
Time is preferably 6 hours~8 hours, more preferably 7 hours.
In the present invention, the species and intake of the protective gas and protective gas described in above-mentioned technical proposal
Species is consistent with intake, will not be repeated here.In the present invention, the protective gas can with described in above-mentioned technical proposal
Protective gas it is identical, it is also possible to it is different.
After obtaining the 4th intermediate product, the present invention under conditions of protective gas, by the 4th intermediate product from the
It is incubated after four greenhouse coolings to the 5th temperature, obtains porous graphene；5th temperature is 900 DEG C~1000 DEG C.In this hair
In bright, the 4th intermediate product from the 4th greenhouse cooling to the rate of temperature fall of the 5th temperature be preferably 30 DEG C/min~50 DEG C/
Min, more preferably 35 DEG C/min~45 DEG C/min.In the present invention, the 5th temperature is preferably 920 DEG C~980 DEG C, more excellent
Elect 940 DEG C~960 DEG C as.In the present invention, the insulation after the 4th intermediate product is from the 4th greenhouse cooling to the 5th temperature
Time is preferably 2 hours~4 hours, more preferably 3 hours.
In the present invention, the species and intake of the protective gas and protective gas described in above-mentioned technical proposal
Species is consistent with intake, will not be repeated here.In the present invention, the protective gas can with described in above-mentioned technical proposal
Protective gas it is identical, it is also possible to it is different.
After the completion of 4th isothermal holding, the present invention preferably carries out the product that the 4th isothermal holding is obtained cold
But, porous graphene is obtained.In the present invention, 100 DEG C of the preferred ＜ of the temperature of the cooling, more preferably 20 DEG C~60 DEG C, most
Preferably 30 DEG C~40 DEG C.The present invention carries out the cooling preferably under conditions of protective gas.In the present invention, the guarantor
The species and intake of shield property gas are consistent with the species and intake of protective gas described in above-mentioned technical proposal, herein no longer
Repeat.In the present invention, the protective gas can be identical with the protective gas described in above-mentioned technical proposal, it is also possible to no
Together.In the present invention, the method for the cooling is preferably natural cooling.
After the completion of the cooling, the cooled product that the present invention will preferably be obtained is washed, and obtains porous graphene.At this
In invention, the method for the washing is preferably：
The cooled product is carried out into the first washing in alkaline aqueous solution, the first washed product is obtained；
First washed product is carried out into the second washing in acidic aqueous solution, the second washed product is obtained；
Second washed product is carried out into the 3rd washing in water, porous graphene is obtained.
The cooled product is preferably carried out the first washing by the present invention in alkaline solution, obtains the first washed product.
In the present invention, the mass concentration of the alkaline aqueous solution is preferably 3%~55%, more preferably 10%~40%, most preferably
20%~30%.In the present invention, the temperature of first washing is preferably 60 DEG C~120 DEG C, more preferably 80 DEG C~100
℃.In the present invention, the time of first washing be preferably 4 hours~24 hours, more preferably 8 hours~16 hours, most
Preferably 10 hours~14 hours.In the present invention, the alkaline aqueous solution is preferably sodium hydrate aqueous solution or ammoniacal liquor.
After obtaining the first washed product, first washed product is preferably carried out second by the present invention in acidic aqueous solution
Washing, obtains the second washed product.In the present invention, the mass concentration of the acidic aqueous solution is preferably 4%~10%, more excellent
Elect 6%~8% as.In the present invention, the temperature of second washing is preferably 70 DEG C~150 DEG C, more preferably 90 DEG C~120
℃.In the present invention, the time of second washing be preferably 4 hours~24 hours, more preferably 8 hours~16 hours, most
Preferably 10 hours~14 hours.In the present invention, the acidic aqueous solution is preferably aqueous hydrochloric acid solution.
After obtaining the second washed product, second washed product is preferably carried out the 3rd washing by the present invention in water, is obtained
To porous graphene.In the present invention, the water is preferably distilled water.The present invention is not special to the method for the described 3rd washing
Limitation, it is described 3rd washing after obtain neutral porous graphene.
After the completion of the washing, the washed product that the present invention will preferably be obtained is dried, and obtains porous graphene.This hair
The bright method to the drying washed product does not have special limitation, using dry technology scheme well known to those skilled in the art
.
The porous graphene that above method is prepared has preferable electric conductivity, and lamella is thin, Sp2Hydridization degree
It is high.
Then the application is carried out using the straight chain compound that two end groups are respectively hydroxyl and epoxy radicals to the Graphene for preparing
It is modified, hydroxyl is introduced in Graphene.
Specifically, by Graphene and straight chain compound in the presence of quaternary ammonium salt, reaction obtains modified graphene.
In the present invention, the straight chain compound is preferably the C of two end groups respectively hydroxyl and epoxy radicals3~20Straight chain chemical combination
Thing, more preferably two end groups are respectively the C of hydroxyl and epoxy radicals5~15Straight chain compound, more preferably two end groups are respectively hydroxyl
The C of base and epoxy radicals5~10Straight chain compound, most preferably epoxy prapanol, epoxy butanol or epoxy octanol.
The quaternary ammonium salt is preferably 4 bromide, tetramethyl ammonium chloride, TMAH, tetramethyl iodate
Ammonium, tetraethylammonium bromide, etamon chloride, tetraethyl ammonium fluoride (hydrate), tetraethyl ammonium iodide iodide, tetrapropyl bromine
Change ammonium, 4-propyl ammonium chloride, tetrapropyl ammonium iodide, TBAB, tetrabutylammonium chloride, tetrabutyl ammonium fluoride, iodate four
Butyl ammonium, bromination tetrahexyl ammonium, tricaprylylmethylammchloride chloride, two hardening tallow alkyl dimethyl ammonium acetates, hexadecyl
Trimethyl ammonium, hexadecyltrimethylammonium chloride, benzyltrimethylammonium bromide, zephiran chloride trimethyl ammonium, bromination benzyl three
Ethyl ammonium, benzyltriethylammonium chloride, any one or more in bromination benzyl tributyl ammonium and benzyl tributyl ammonium chloride,
Or preferably phenyltrimethylammonium bromide, chlorination phenyltrimethyammonium, trioctylphosphine acetic acid esters, CTAB
Deng four ethyl phosphonium bromide Phosphonium, 4-butyl-phosphonium ammonium bromide, 4-butyl phosphonium chloride, four butyl phosphonium iodides, 4-butyl-phosphonium acetate, four benzene
Base phosphonium bromide, tributyl methyl phosphonium iodide, tributyl n-octyl ammonium bromide, hexadecyl tributyl phosphonium ammonium, tributyl allyl
Base phosphoric acid ammonium bromide, three Ethylbenzyl phosphonium chlorides, tributyl benzyl base Phosphonium, trioctylphosphine ethyl phosphonium bromide ammonium, the phenyl-bromide Phosphonium of first base three,
Methyl triphenyl phosphonium chloride, second base triphenyl phosphonium bromide, in second base triphenyl phosphonium iodide and the phenyl-bromide Phosphonium of n-propyl three
Any one or a few, or preferably butyl triphenyl phosphonium bromide, methoxymethyl triphenylphosphonium phosphonium chloride and benzyl triphen
Any one or a few in Ji phosphonium chlorides.More preferably, benzyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyl three
Ethyl phosphonium bromide ammonium, benzyltriethylammoinium chloride, benzyl tributyl ammonium bromide, benzyl tributyl ammonium chloride, phenyl trimethicone bromination
Ammonium, phenyl trimethicone ammonium chloride, tri-n-octyl methyl ammonium chloride, San Ethylbenzyl phosphonium chlorides, tributyl Bian Ji Phosphonium or trioctylphosphine second
Base ammonium bromide.
In the present invention, the mass ratio of the Graphene and straight chain compound is preferably 1：(0.1~10), more preferably 1：
(0.3~5), most preferably 1：(0.5~3)；The consumption of the quaternary ammonium salt is preferably the 0.1wt%~1wt% of Graphene, more excellent
Elect 0.3wt%~0.5wt% as.
The reaction is preferably carried out in organic solvent.It is organic that the organic solvent is preferably alcohol organic solvent, ketone
Solvent or sulfone class organic solvent；The alcohol organic solvent is preferably methyl alcohol, ethanol, normal propyl alcohol, isopropanol, allyl alcohol, positive fourth
Alcohol, isobutanol, n-amyl alcohol, cyclopentanol, isoamyl alcohol, n-hexyl alcohol, cyclohexanol, n-heptanol, secondary butanol, tertiary butyl alcohol, neopentyl alcohol,
Phenmethylol, benzhydrol, triphenylcarbinol, ethylene glycol, 1,3-PD, Glycerin, Erythritol, 1,2,3,
4,5- pentitols, 1,2,3,4,5,6- hexitols, 1,2,3,4,5,6,7- volemitols, the alcohol of hexamethylene -1,2,3,4,5,6- six and
Any one or more in 2- (2- propyl group) -5- methyl-cyclohexyl alkane -1- alcohol；The ketone compounds are preferably acetone, fourth
Ketone, pentanone, methyl iso-butyl ketone (MIBK), cyclopropanone, cyclohexanone, cyclopentanone, Benzophenone, acetophenone, propiophenone, phenyl propyl ketone and diacetyl
In any one or a few；The sulfone class organic solvent is preferably appointing in dimethyl sulfoxide (DMSO), dimethyl sulfone and diphenyl sulfone
Anticipate one or more.
The present invention is to the mode of the reaction and is not limited, as long as Graphene can be made to be reacted i.e. with straight chain compound
Can.Preferably, the reaction is ultrasonic reaction, and the temperature of the reaction is 60 DEG C~80 DEG C, time of the reaction for 2h~
8h；It is furthermore preferred that the method using ultrasound is segmented, 60 DEG C first~70 DEG C ultrasonic reaction 1h~3h, then 70 DEG C~80 DEG C surpass
Phonoresponse 1h~5h.
The present invention addition sequence of the Graphene, straight chain compound and quaternary ammonium salt is had no it is specifically limited, can be simultaneously
Add, it is also possible to be dividedly in some parts, preferably first disperse graphene in organic solvent, be subsequently adding straight chain compound and quaternary ammonium
Salt.
After reaction terminates, product is purified, it is preferred that filter and wash removing excess of solvent, obtain modified graphite
Alkene.
The invention also discloses a kind of modified graphene, reacted in the presence of quaternary ammonium salt by Graphene and straight chain compound
Obtain；The straight chain compound is the straight chain compound of two end groups respectively hydroxyl and epoxy radicals.
Contain hydroxyl and carboxyl in the modified graphene surface of preparation.
Preferably, the Graphene is porous graphene.
The preparation method of the porous graphene is identical with the preparation method of above-mentioned porous graphene, will not be repeated here.
In the present invention, the mass ratio of the Graphene and straight chain compound is preferably 1：(0.1~10), more preferably 1：
(0.3~5), most preferably 1：(0.5~3)；The consumption of the quaternary ammonium salt is preferably the 0.1wt%~1wt% of Graphene, more excellent
Elect 0.3wt%~0.5wt% as.
The straight chain compound is preferably the C of two end groups respectively hydroxyl and epoxy radicals3~20Straight chain compound, more preferably
The C of hydroxyl and epoxy radicals is respectively for two end groups5~15Straight chain compound, more preferably two end groups are respectively hydroxyl and epoxy radicals
C5~10Straight chain compound, most preferably epoxy prapanol, epoxy butanol or epoxy octanol.
Present invention also offers a kind of aqueous antistatic epoxy floor paint, including：
Component A：
40wt%~60wt% aqueous epoxy resins,
0.1wt%~1wt% modified graphenes,
20wt%~30wt% graphite,
The auxiliary agent of surplus,
The modified graphene is modified graphene prepared by above-mentioned preparation method, or above-mentioned modified graphene；
B component：
50wt%~70wt% amine waterborne curing agents,
1wt%~2wt% coalescents,
10wt%~60wt% water,
3wt%~5wt% defoamers；
The amine waterborne curing agent, coalescents, water and defoamer total amount are 100%；
The amino active hydrogen of the B combinations and the epoxy radicals mol ratio of component A are 1:1.
Wherein, the aqueous epoxy resins be preferably glycol-modified bisphenol-A that epoxide equivalent is 200~250g/eq or
Bisphenol F aqueous epoxy resins.
The particle diameter of the graphite is preferably 100nm~500nm, more preferably 150nm~300nm；The aperture of the graphite
Below preferably 500 mesh, more preferably 200 mesh~400 mesh.
The present invention auxiliary agent is had no it is specifically limited, can for those skilled in the art prepare aqueous epoxy floor apply
The auxiliary agent commonly used during material.
Currently preferred, the auxiliary agent includes：
2wt%~5wt% reactive diluents,
5wt%~10wt% toughener,
10wt%~15wt% mill bases,
0.1wt%~0.3wt% dispersants,
0.1wt%~0.3wt% wetting agents,
0.1wt%~0.3wt% levelling agents.
Wherein, the reactive diluent is multifunctional aliphatic epoxy, preferably BDDE, second
Hexanediol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, 1,6- hexanediol diglycidyl ethers,
Neopentylglycol diglycidyl ether, hydrogenated bisphenol A glycidol ether or trihydroxymethylpropanyltri diglycidyl ether；The toughener
Preferably PPG of the degree of functionality between 3~6, more preferably degree of functionality is 3 or 4 PPG；The color
Slurry can be suitable for the conventional mill base of aqueous epoxy floor coating, the preferably aqueous color paste of 5 μm~8 μm of fineness；Described point
Powder can be suitable for the conventional dispersant of aqueous epoxy floor coating, preferably molecular weight between 1000~10000 alkane
Epoxide styrene oxide polyethers phosphate；The wetting agent can be the wetting agent suitable for aqueous epoxy floor coating routine,
Preferably molecular weight between 500~5000 Siloxane-Oxyalkylene Copolymers；The levelling agent can be suitable for water-base epoxy ground
The conventional levelling agent of level ground coating, preferably BYK-333 levelling agents, BYK-381 levelling agents or BYK-DYNWET800 levelling agents.
In component B, the aqueous amine curing agent be preferably 150~250mg of amine value KOH/g, 25 DEG C of viscosity 10000~
The modified polyamide waterborne curing agent of 30000mPa s；The coalescents are preferably alkoxide Watery film-fomer, more preferably
Propylene glycol monomethyl ether, propylene glycol monobutyl ether or glycol monoethyl ether；The defoamer can be to be applied suitable for aqueous epoxy floor
Expect conventional defoamer, preferably German enlightening Foamex825 high, Foamex810, Airex962, Airex920,
Airex900。
Present invention also offers a kind of preparation method of above-mentioned aqueous antistatic epoxy floor paint, including：
A) modified graphene is mixed with graphite, aqueous epoxy resins and auxiliary agent, component A is obtained；
B) amine waterborne curing agent, coalescents, defoamer and water are mixed, B component is obtained；
By B component and component A according to amino active hydrogen and epoxy radicals mol ratio 1:1 ratio mixing, obtains aqueous anti-quiet
Electric epoxy flooring coating；
The step A), B) without sequencing.
The modified graphene is preferably (0.1~1) with the weight ratio of graphite, aqueous epoxy resins：(20~30)：(40
~60)；The weight of the amine waterborne curing agent, coalescents, defoamer and water is than being preferably (50~70)：(1~2)：(10
~60)：(3~5).
The auxiliary agent is preferably included：Reactive diluent, toughener, mill base, dispersant, wetting agent, levelling agent, its weight ratio
Preferably (2~5)：(5~10)：(10~15)：(0.1~0.3)：(0.1~0.3)：(0.1~0.3), more preferably (3~
4)：(6~8)：(11~13)：(0.15~0.25)：(0.15~0.25)：(0.15~0.25).
Specifically, it is first that modified graphene is soluble in water with graphite ultrasound, water-base epoxy is added, high-speed stirred treats stone
Black alkene is dispersed open after, add auxiliary agent, obtain component A.
Added water after amine waterborne curing agent, coalescents, defoamer are mixed and high-speed stirred is to uniform solution, obtain B
Component.
By component B and component A according to amino active hydrogen and epoxy radicals mol ratio 1:1 ratio mixing, you can obtain aqueous
Antistatic epoxy floor paint.
Performance test is carried out to it, is as a result shown, the sheet resistance of the coating of preparation is 2.5 × 104Ω~2.7 × 105Ω
Between.
It can be seen that, the present invention is respectively hydroxyl using two end groups and the straight chain compound of epoxy radicals is modified to Graphene,
Then modified Graphene is applied in aqueous epoxy floor coating, substantially increases the anti-static ability of coating.
In order to further illustrate the present invention, a kind of modified graphene and its system provided the present invention with reference to embodiment
A kind of Preparation Method, and aqueous antistatic epoxy floor paint and preparation method thereof is described in detail.
Embodiment 1
At 90 DEG C, corncob is carried out the hydrolysis of 10min in sulfuric acid, obtain lignocellulosic, the matter of the sulfuric acid
Measure is the 3% of the corncob quality；
At 70 DEG C, the acid sulfite process treatment of 1 hour is carried out to the lignocellulosic, obtain porous fibre
Element, the pH value in the acid sulfite process processing procedure is 1, and acid is sulfuric acid, and sulphite is magnesium sulfite, the sulfuric acid
Quality be the 4% of the lignocellulosic quality, liquid-solid ratio is 2:1.
The porous cellulose that will be obtained carries out hydrogen peroxide bleaching, and the quality of the hydrogen peroxide is the porous cellulose quality
5%, the bleaching temperature of the hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
Embodiment 2
At 180 DEG C, corncob is carried out the hydrolysis of 10h in nitric acid, obtain lignocellulosic, the quality of the nitric acid
It is the 20% of the corncob quality；
At 180 DEG C, the acid sulfite process treatment of 6 hours is carried out to the lignocellulosic, obtain porous fibre
Element, the pH value in the acid sulfite process processing procedure is 7, and acid is sulfuric acid, and sulphite is sodium sulfite, the sulfuric acid
Quality be the 30% of the lignocellulosic quality, liquid-solid ratio is 20:1.
The porous cellulose is carried out into hydrogen peroxide bleaching, the quality of the hydrogen peroxide is the porous cellulose quality
5%, the bleaching temperature of the hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
Embodiment 3
At 130 DEG C, corncob is carried out the hydrolysis of 5h in hydrochloric acid, obtain lignocellulosic, the quality of the hydrochloric acid
It is the 10% of the corncob quality；
At 120 DEG C, the acid sulfite process treatment of 4 hours is carried out to the lignocellulosic, obtain porous fibre
Element, the pH value in the acid sulfite process processing procedure is 3, and acid is sulfuric acid, and sulphite is ammonium sulfite, the sulfuric acid
Quality be the 18% of the lignocellulosic quality, liquid-solid ratio is 10:1.
The porous cellulose is carried out into hydrogen peroxide bleaching, the quality of the hydrogen peroxide is the porous cellulose quality
5%, the bleaching temperature of the hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
Embodiment 4
The porous cellulose and manganese chloride that embodiment 1 is obtained, stirring carries out catalytic treatment for 2 hours at 20 DEG C, described
The mass ratio of manganese chloride and porous cellulose is 0.01：1；Product after the catalytic treatment that will be obtained is dried at 70 DEG C, is obtained
First intermediate product of the water content less than 10wt%.
First intermediate product is placed in retort, with the gas intake of 200mL/min in the carbide furnace
Nitrogen is passed through as protection gas, first intermediate product is warming up to 300 DEG C from 25 DEG C with the speed of 5 DEG C/min, insulation 4 is small
When, obtain the second intermediate product；Second intermediate product is warming up to 800 DEG C from 300 DEG C with the speed of 20 DEG C/min, is protected
Temperature 3.5 hours, obtains the 3rd intermediate product；3rd intermediate product is warming up to the speed of 50 DEG C/min from 800 DEG C
1100 DEG C, 6 hours are incubated, obtain the 4th intermediate product；By the 4th intermediate product with the speed of 30 DEG C/min from 1100 DEG C
900 DEG C are cooled to, 2 hours are incubated；The 4th intermediate product after the cooling is cooled to 60 DEG C.
At 60 DEG C, by the 4th intermediate product after above-mentioned cooling in the sodium hydrate aqueous solution that mass concentration is 3%
Washing 4 hours, obtains the first washed product；At 70 DEG C, by first washed product in the hydrochloric acid water that mass concentration is 4%
Washed 4 hours in solution, obtain the second washed product；Dried after second washed product is washed with distilled water into neutrality,
Obtain Graphene.
The Graphene that the embodiment of the present invention 4 is prepared carries out Raman spectrum test, test result as shown in figure 1, Fig. 1
It is the Raman spectrum of the Graphene that the embodiment of the present invention 4 is obtained, as shown in Figure 1, the method that the embodiment of the present invention 4 is provided is prepared into
The Graphene Sp for arriving2Hydridization degree is high.Transmissioning electric mirror test is carried out to the Graphene that the embodiment of the present invention 4 is prepared, is tested
As shown in Fig. 2~Fig. 5, Fig. 2~Fig. 5 is the transmission electron microscope picture of Graphene that the embodiment of the present invention 4 is obtained to result, by Fig. 2~
The lamella of the Graphene that the method that Fig. 5 can be seen that the offer of the embodiment of the present invention 4 is prepared is relatively thin, is many below 10 layers
Hole Graphene.Using conducting performance test instrument, the electric conductivity of the porous graphene that the test embodiment of the present invention 4 is prepared is surveyed
Test result is that the electric conductivity of the porous graphene that the method that the embodiment of the present invention 4 is provided is prepared is 40000S/m.
Embodiment 5
The porous cellulose and ferric nitrate that embodiment 2 is prepared, stirred at 180 DEG C is carried out at catalysis for 10 hours
The mass ratio of reason, the ferric nitrate and porous cellulose is 2：1；Product after the catalytic treatment that will be obtained is dried at 120 DEG C,
Obtain first intermediate product of the water content less than 5wt%.
First intermediate product is placed in retort, with the gas intake of 800mL/min in the carbide furnace
Argon gas is passed through as protection gas, first intermediate product is warming up to 400 DEG C, insulation 8 from 20 DEG C with the speed of 20 DEG C/min
Hour, obtain the second intermediate product；Second intermediate product is warming up to 900 DEG C from 400 DEG C with the speed of 50 DEG C/min, is protected
Temperature 7 hours, obtains the 3rd intermediate product；3rd intermediate product is warming up to 1300 with the speed of 60 DEG C/min from 900 DEG C
DEG C, 8 hours are incubated, obtain the 4th intermediate product；By the 4th intermediate product with the speed of 50 DEG C/min from 1300 DEG C of coolings
To 1000 DEG C, 4 hours are incubated；The 4th intermediate product after the cooling is cooled to 20 DEG C.
At 120 DEG C, by the 4th intermediate product after above-mentioned cooling in the sodium hydrate aqueous solution that mass concentration is 55%
Middle washing 24 hours, obtains the first washed product；In mass concentration it is 10% by first washed product at 150 DEG C
Washed 24 hours in aqueous hydrochloric acid solution, obtain the second washed product；Second washed product is washed with distilled water to neutrality
After dry, obtain Graphene.
According to the method described in embodiment 4, the Graphene that the embodiment of the present invention 5 is obtained is detected, testing result is,
The Graphene Sp that the method that the embodiment of the present invention 5 is provided is prepared2Hydridization degree is high；The lamella of Graphene is relatively thin, at 10 layers
Hereinafter, it is porous graphene；The electric conductivity of porous graphene is 38000S/m.
Embodiment 6
The porous cellulose and cobaltous sulfate that embodiment 3 is prepared, stirring carries out catalytic treatment in 5 hours at 50 DEG C,
The mass ratio of the cobaltous sulfate and porous cellulose is 0.1：1；Product after the catalytic treatment that will be obtained is dried at 90 DEG C, is obtained
The first intermediate product to water content less than 8wt%.
First intermediate product is placed in retort, with the gas intake of 400mL/min in the carbide furnace
Nitrogen is passed through as protection gas, first intermediate product is warming up to 320 DEG C, insulation 5 from 40 DEG C with the speed of 10 DEG C/min
Hour, obtain the second intermediate product；Second intermediate product is warming up to 820 DEG C from 320 DEG C with the speed of 30 DEG C/min, is protected
Temperature 5 hours, obtains the 3rd intermediate product；3rd intermediate product is warming up to 1150 with the speed of 54 DEG C/min from 820 DEG C
DEG C, 7 hours are incubated, obtain the 4th intermediate product；By the 4th intermediate product with the speed of 35 DEG C/min from 1150 DEG C of coolings
To 920 DEG C, 3 hours are incubated；The 4th intermediate product after the cooling is cooled to 30 DEG C.
At 80 DEG C, the 4th intermediate product after above-mentioned cooling is washed 8 hours in the ammoniacal liquor that mass concentration is 10%,
Obtain the first washed product；At 90 DEG C, first washed product is washed in the aqueous hydrochloric acid solution that mass concentration is 6%
8 hours, obtain the second washed product；Dried after second washed product is washed with distilled water into neutrality, obtain Graphene.
According to the method described in embodiment 4, the Graphene that the embodiment of the present invention 6 is obtained is detected, testing result is,
The Graphene Sp that the method that the embodiment of the present invention 6 is provided is prepared2Hydridization degree is high；The lamella of Graphene is relatively thin, at 10 layers
Hereinafter, it is porous graphene；The electric conductivity of porous graphene is 39000S/m.
Embodiment 7
Porous graphene prepared by 10g embodiments 4 adds ultrasonic dissolution in 50g ethanol, is subsequently adding 5g epoxy prapanols
With, successively in 60 DEG C of ultrasound 2h, in 80 DEG C of ultrasound 4h, desolventizing washing afterwards is obtained after 0.03g tetramethyl ammonium chloride ultrasonic dissolutions
Modified graphene 15g.
Under rotating speed 2000r/min, the poly ethyldiol modified bisphenol-A aqueous epoxy resins of 150g are sequentially added, 1.5g is above-mentioned
The modified graphene of preparation, 15g trimethylolpropanes epoxy, 15g polyethylene glycol 200s, 30g fineness are 6 μm of bright red aqueous color
Slurry, the alkoxy styrene oxide polyethers phosphonate dispersants that 0.1g molecular weight is 3000, the polyethers of 0.3g molecular weight 1000 change
Property polysiloxanes wetting agent, 0.3gBYK-333 levelling agents, 60g graphite and 100g deionized waters stir evenly prepared component A.
Add 50g deionized waters after 60gAradur435,1g propylene glycol monomethyl ether coalescents, 4gFoamex810 are mixed
And high-speed stirred, mixing speed is 4000r/min, to uniform solution is mixed into, obtains B component.
It is 1 that B component and component A are pressed into amino active hydrogen and epoxy radicals mol ratio:Film is consolidated after 1 ratio is well mixed
Change, obtain aqueous antistatic epoxy floor paint, performance detection is carried out to it, the results are shown in Table 1, table 1 be the embodiment of the present invention and
The electrical property result of coating prepared by comparative example collects.
Embodiment 8
Porous graphene prepared by 10g embodiments 5 adds ultrasonic dissolution in 60g acetone, is subsequently adding 10g epoxy butanol
With, successively in 60 DEG C of ultrasound 2h, in 80 DEG C of ultrasound 4h, desolventizing washing afterwards is obtained after 0.05g tetramethyl ammonium chloride ultrasonic dissolutions
Modified graphene 20g.
Under rotating speed 2500r/min, the poly ethyldiol modified bisphenol-A aqueous epoxy resins of 150g are sequentially added, 1.5g is above-mentioned
The modified graphene of preparation, 15g hydrogenated bisphenol A epoxies, 15g PEG400s, 30g fineness be 6 μm big red water-based color paste,
0.1g molecular weight be 3000 alkoxy styrene oxide polyethers phosphonate dispersants, 0.3g molecular weight 1000 it is polyether-modified poly-
Polysiloxane wetting agents, 0.3gBYK-333 levelling agents, 70g graphite and 150g deionized waters stir evenly prepared component A.
Add 70g deionizations after 70gAradur435,1.5g propylene glycol monomethyl ether coalescents, 4g Foamex810 are mixed
Simultaneously high-speed stirred, to uniform solution, obtains B component to water.
It is 1 that B component and component A are pressed into amino active hydrogen and epoxy radicals mol ratio:Film is consolidated after 1 ratio is well mixed
Change, obtain aqueous antistatic epoxy floor paint, performance detection is carried out to it, the results are shown in Table 1, table 1 be the embodiment of the present invention and
The electrical property result of coating prepared by comparative example collects.
Embodiment 9
Porous graphene prepared by 15g embodiments 6 adds ultrasonic dissolution in 50gDMSO, is subsequently adding 10g epoxy octanols
With, successively in 60 DEG C of ultrasound 2h, in 80 DEG C of ultrasound 4h, desolventizing is washed afterwards after 0.045g tetramethyl ammonium chloride ultrasonic dissolutions
To modified graphene 20g.
Under rotating speed 3000r/min, the poly ethyldiol modified bisphenol-A aqueous epoxy resins of 150g, the above-mentioned systems of 2g are sequentially added
Standby modified graphene, 15g trimethylolpropanes epoxy, 20g polyethylene glycol 200s, 30g fineness be 5 μm big red water-based color paste,
0.1g molecular weight be 3000 alkoxy styrene oxide polyethers phosphonate dispersants, 0.3g molecular weight 1000 it is polyether-modified poly-
Polysiloxane wetting agents, 0.3gBYK-333 levelling agents, 60g graphite and 150g deionized waters stir evenly prepared component A.
Add 60g deionized waters after 70gAradur435,1g propylene glycol monobutyl ether coalescents, 5g Airex962 are mixed
And high-speed stirred is to uniform solution, B component is obtained.
It is 1 that B component and component A are pressed into amino active hydrogen and epoxy radicals mol ratio:Film is consolidated after 1 ratio is well mixed
Change, obtain aqueous antistatic epoxy floor paint, performance detection is carried out to it, the results are shown in Table 1, table 1 be the embodiment of the present invention and
The electrical property result of coating prepared by comparative example collects.
Comparative example 1
Under rotating speed 2000r/min, the poly ethyldiol modified bisphenol-A aqueous epoxy resins of 150g, 1.5g graphite are sequentially added
Alkene, 15g trimethylolpropanes epoxy, 15g polyethylene glycol 200s, 30g fineness be 5 μm big red water-based color paste, 0.3g molecular weight be
6000 alkoxy styrene oxide polyethers phosphonate dispersants, the Siloxane-Oxyalkylene Copolymers of 0.3g molecular weight 2000,
0.3gBYK-381 levelling agents, 60g graphite and 120g deionized waters stir evenly prepared component A.
Add 50g deionized waters after 60gAradur435,1g propylene glycol monobutyl ether coalescents, 4g Airex962 are mixed
And high-speed stirred is to uniform solution, B component is obtained.
It is 1 that B component and component A are pressed into amino active hydrogen and epoxy radicals mol ratio:Film is consolidated after 1 ratio is well mixed
Change, obtain aqueous antistatic epoxy floor paint, performance detection is carried out to it, the results are shown in Table 1, table 1 be the embodiment of the present invention and
The electrical property result of coating prepared by comparative example collects.
The electrical property result of coating prepared by the embodiment of the present invention of table 1 and comparative example collects
From above-described embodiment and comparative example, the present invention is respectively the straight chain chemical combination of hydroxyl and epoxy radicals using two end groups
Thing is modified to Graphene, and then modified Graphene is applied in aqueous epoxy floor coating, substantially increases painting
The anti-static ability of material.The anti-static coatings of preparation are particularly well-suited to the extremely sensitive electronic instrument of electrostatic, integrated circuit etc.
The application of the workshop and storage area of electronic element.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (16)
1. a kind of preparation method of modified graphene, including：
By Graphene and straight chain compound in the presence of quaternary ammonium salt, reaction obtains modified graphene；
The straight chain compound is the straight chain compound of two end groups respectively hydroxyl and epoxy radicals；
The Graphene is porous graphene；
The reaction is ultrasonic reaction, and the temperature of the reaction is 60 DEG C~80 DEG C, and the time of the reaction is 2h~8h.
2. preparation method according to claim 1, it is characterised in that the mass ratio of the Graphene and straight chain compound is
1：(0.1~10).
3. preparation method according to claim 1, it is characterised in that the straight chain compound is respectively hydroxyl for two end groups
With the C of epoxy radicals3~20Straight chain compound.
4. preparation method according to claim 1, it is characterised in that the reaction is carried out in organic solvent.
5. preparation method according to claim 1, it is characterised in that the Graphene is prepared in accordance with the following methods：
1), in the presence of catalyst, biomass carbon source is carried out into catalytic treatment, obtains the first intermediate product, the catalyst
It is one or more in the chlorate of manganese, iron compound, cobalt class compound and nickel class compound；
2), under conditions of protective gas, it is incubated after first intermediate product is warming up into second temperature from the first temperature,
The second intermediate product is obtained, first temperature is 20 DEG C~40 DEG C, and the second temperature is 300 DEG C~400 DEG C；
3), under conditions of protective gas, it is incubated after second intermediate product is warming up into the 3rd temperature from second temperature,
Obtain the 3rd intermediate product；3rd temperature is 800 DEG C~900 DEG C；
4), under conditions of protective gas, it is incubated after the 3rd intermediate product is warming up into the 4th temperature from the 3rd temperature,
The 4th intermediate product is obtained, the 4th temperature is 1100 DEG C~1300 DEG C；
5), under conditions of protective gas, by the 4th intermediate product from the 4th greenhouse cooling to the 5th temperature after be incubated,
Porous graphene is obtained, the 5th temperature is 900 DEG C~1000 DEG C.
6. preparation method according to claim 5, it is characterised in that during the biomass carbon source is cellulose and lignin
One or two.
7. preparation method according to claim 6, it is characterised in that the biomass carbon source is porous cellulose.
8. preparation method according to claim 7, it is characterised in that the preparation method of the porous cellulose includes following
Step：
A), biomass resource is hydrolyzed in acid, lignocellulosic is obtained, the biomass resource is that plant and agricultural are useless
One or more in gurry；
B), the lignocellulosic is processed, porous cellulose is obtained, it is described to be processed as acid treatment, salt treatment or organic
Solvent treatment.
9. preparation method according to claim 8, it is characterised in that the step B) in the method for salt treatment be acid sub-
Sulfate process treatment or alkali sulfite process treatment.
10. a kind of modified graphene, is reacted in the presence of quaternary ammonium salt by Graphene and straight chain compound and obtained；
The straight chain compound is the straight chain compound of two end groups respectively hydroxyl and epoxy radicals；
The reaction is ultrasonic reaction, and the temperature of the reaction is 60 DEG C~80 DEG C, and the time of the reaction is 2h~8h.
11. modified graphenes according to claim 10, it is characterised in that the Graphene is porous graphene.
12. modified graphenes according to claim 10, it is characterised in that the quality of the Graphene and straight chain compound
Than being 1：(0.1~10).
13. modified graphenes according to claim 10, it is characterised in that the straight chain compound is respectively for two end groups
The C of hydroxyl and epoxy radicals3~20Straight chain compound.
A kind of 14. aqueous antistatic epoxy floor paints, including：
Component A：
40wt%~60wt% aqueous epoxy resins,
0.1wt%~1wt% modified graphenes,
20wt%~30wt% graphite,
The auxiliary agent of surplus,
The modified graphene that the modified graphene is prepared for the preparation method described in claim 1~9, or claim 10 institute
The modified graphene stated；
B component：
50wt%~70wt% amine waterborne curing agents,
1wt%~2wt% coalescents,
10wt%~60wt% water,
5wt%~3wt% defoamers；
The amine waterborne curing agent, coalescents, water and defoamer total amount are 100%；
The amino active hydrogen of the B component is 1 with the epoxy radicals mol ratio of component A:1.
15. coating according to claim 14, it is characterised in that the auxiliary agent includes：
2wt%~5wt% reactive diluents,
5wt%~10wt% toughener,
10wt%~15wt% mill bases,
0.1wt%~0.3wt% dispersants,
0.1wt%~0.3wt% wetting agents,
0.1wt%~0.3wt% levelling agents.
The preparation method of the aqueous antistatic epoxy floor paint described in a kind of 16. claims 14, including：
A) modified graphene is mixed with graphite, aqueous epoxy resins and auxiliary agent, component A is obtained；
B) amine waterborne curing agent, coalescents, defoamer and water are mixed, B component is obtained；
By B component and component A according to amino active hydrogen and epoxy radicals mol ratio 1:1 ratio mixing, obtains aqueous antistatic ring
Oxygen floor coatings；
The step A), B) without sequencing.
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| CN106554696A (en) * | 2015-09-25 | 2017-04-05 | 青岛瑞利特新材料科技有限公司 | A kind of Graphene antistatic aqueous epoxy floor paint |
| CN105543993B (en) * | 2016-01-13 | 2018-03-30 | 济南圣泉集团股份有限公司 | A kind of graphene is modified mill base, preparation method and its usage |
| CN106010126B (en) * | 2016-07-19 | 2018-05-04 | 河北晨阳工贸集团有限公司 | A kind of graphene-based anti-static and abrasion-resistant bicomponent epoxy resin coating |
| CN109259389A (en) * | 2018-08-07 | 2019-01-25 | 道晟拉链科技（太仓）有限公司 | A kind of efficient electrostatic prevention zipper |
| KR20240027790A (en) * | 2021-07-02 | 2024-03-04 | 에보니크 오퍼레이션즈 게엠베하 | Polyalkylene oxides as dispersants for graphene materials |
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| CN103466613A (en) * | 2013-10-11 | 2013-12-25 | 中南林业科技大学 | Method for preparing graphene from lignin |
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Denomination of invention: Modified graphene and preparation method thereof Effective date of registration: 20181228 Granted publication date: 20170524 Pledgee: China Co truction Bank Corp Ji'nan Zhangqiu sub branch Pledgor: Shengquan Group Co., Ltd., Ji'nan City Registration number: 2018370000239 |