CN104194461A - 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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- CN104194461A CN104194461A CN201410400503.8A CN201410400503A CN104194461A CN 104194461 A CN104194461 A CN 104194461A CN 201410400503 A CN201410400503 A CN 201410400503A CN 104194461 A CN104194461 A CN 104194461A
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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 Antistatic Paint technical field, relate in particular 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 is invented in 1934 by Germany the earliest, mainly formed through many end production process manufactures such as mixing, dissolving, dispersions by multiple different substancess such as oil plant, tree material, color, solvents, can be divided into ornamental floor paint, heavy anticorrosion floor paint, resistance to heavily loaded floor paint etc., it has beautiful, true, attractive in appearance, wear-resisting, waterproof, the feature such as anticorrosion.Wherein, epoxide terrace paint is applied owing to having good water-soluble acquisition comparatively widely.
Along with development and the production of modern science and technology, increasing factory building and workshop have proposed to eliminate the requirement of accumulation of static electricity to floor paint, and this becomes increasingly conspicuous the status of antistatic epoxy floor paint.But the antistatic performance of antistatic floor paint is in the market very limited, far can not meet service requirements.
Summary 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, and a kind of aqueous antistatic epoxy floor paint and preparation method thereof, the modified graphene of preparing taking the present invention is raw material, and the aqueous antistatic epoxy floor paint of preparation has excellent antistatic performance.
The preparation method who the invention provides a kind of modified graphene, comprising:
By Graphene and straight chain compound, under the effect of quaternary ammonium salt, reaction obtains modified graphene;
Described straight chain compound is the straight chain compound that two end groups are respectively hydroxyl and epoxy group(ing).
Preferably, the mass ratio of described Graphene and straight chain compound is 1:(0.1～10).
Preferably, described straight chain compound is the C that two end groups are respectively hydroxyl and epoxy group(ing)
3～20straight chain compound.
Preferably, described reaction is carried out in organic solvent.
Preferably, described reaction is ultrasonic reaction, and the temperature of described reaction is 60 DEG C～80 DEG C, and the time of described reaction is 2h～8h.
Preferably, described Graphene is porous graphene.
Preferably, described Graphene is prepared in accordance with the following methods:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain porous graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
Preferably, described biomass carbon source is one or both in Mierocrystalline cellulose and xylogen.
Preferably, described biomass carbon source is porous cellulose.
Preferably, the preparation method of described porous cellulose comprises the following steps:
A), biomass resource is hydrolyzed in acid, obtain lignocellulose, described biomass resource comprises one or more in plant and agriculture and forestry organic waste material;
B), described lignocellulose is processed, obtain porous cellulose, described processing comprises that acid treatment, salt processes or organic solvent processing.
Preferably, described step B) in the method for salt processing be that acid sulfite process is processed or alkali sulfite process processing.
The present invention also provides a kind of modified graphene, is reacted and obtains under the catalysis of quaternary ammonium salt by Graphene and straight chain compound;
Described straight chain compound is the straight chain compound that two end groups are respectively hydroxyl and epoxy group(ing).
Preferably, described Graphene is porous graphene.
Preferably, the mass ratio of described Graphene and straight chain compound is 1:(0.1～10).
Preferably, described straight chain compound is the C that two end groups are respectively hydroxyl and epoxy group(ing)
3～20straight chain compound.
The present invention also provides a kind of aqueous antistatic epoxy floor paint, comprising:
A component:
40wt%～60wt% aqueous epoxy resins,
0.1wt%～1wt% modified graphene,
20wt%～30wt% graphite,
The auxiliary agent of surplus,
Described modified graphene is modified graphene prepared by above-mentioned preparation method, or above-mentioned modified graphene;
B component:
50wt%～70wt% amine waterborne curing agent,
1wt%～2wt% film coalescence aid,
10wt%～60wt% water,
5wt%～3wt% defoamer;
Described amine waterborne curing agent, film coalescence aid, water and defoamer total amount are 100%;
The amino reactive hydrogen of described B combination and the epoxy group(ing) mol ratio of A component are 1:1.
Preferably, described auxiliary agent comprises:
2wt%～5wt% reactive thinner,
5wt%～10wt% toughner,
10wt%～15wt% mill base,
0.1wt%～0.3wt% dispersion agent,
0.1wt%～0.3wt% wetting agent,
0.1wt%～0.3wt% flow agent.
The present invention also provides a kind of preparation method of above-mentioned aqueous antistatic epoxy floor paint, comprising:
A) modified graphene is mixed with graphite, aqueous epoxy resins and auxiliary agent, obtain A component;
B) amine waterborne curing agent, film coalescence aid, defoamer and water are mixed, obtain B component;
B component and A component are mixed with the ratio of epoxy group(ing) mol ratio 1:1 according to amino reactive hydrogen, obtain aqueous antistatic epoxy floor paint;
Described steps A), B) there is no a sequencing.
Compared with prior art, the straight chain compound that the present invention adopts two end groups to be respectively hydroxyl and epoxy group(ing) carries out modification to Graphene, then the Graphene after modification is applied in aqueous epoxy floor coating, has greatly improved the anti-static ability of coating.Performance test shows, the surface resistivity of aqueous antistatic epoxy floor paint prepared by the present invention is 2.5 × 10
4～2.7 × 10
5between Ω.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, other accompanying drawing can also be provided according to the accompanying drawing providing.
Fig. 1 is the Raman spectrum of the Graphene that obtains of the embodiment of the present invention 4;
Fig. 2 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4;
Fig. 3 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4;
Fig. 4 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4;
Fig. 5 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4.
Embodiment
The preparation method who the invention provides a kind of modified graphene, comprising:
By Graphene and straight chain compound, under the effect of quaternary ammonium salt, reaction obtains modified graphene;
Described straight chain compound is the straight chain compound that two end groups are respectively hydroxyl and epoxy group(ing).
The straight chain compound that the present invention adopts two end groups to be respectively hydroxyl and epoxy group(ing) carries out modification to Graphene, then the Graphene after modification is applied in aqueous epoxy floor coating, has greatly improved the anti-static ability of coating.Performance test shows, the surface resistivity of aqueous antistatic epoxy floor paint prepared by the present invention is 2.5 × 10
4Ω～2.7 × 10
5between Ω.
In the present invention, described Graphene be there is no to particular restriction, be preferably porous graphene, the porous graphene that is more preferably raw material production based on biological material.Its preparation method is preferably:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain porous graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
The present invention, under the effect of catalyzer, carries out catalytic treatment by biomass carbon source, obtains the first intermediate product, and described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese.The present invention preferably mixes catalyzer and biomass carbon source, obtains the first intermediate product.The present invention does not have special restriction to the method for described mixing, adopts hybrid technology scheme well known to those skilled in the art, and described catalyzer and biomass carbon source are stirred.In the present invention, the temperature of described mixing is preferably 20 DEG C～180 DEG C, more preferably 50 DEG C～150 DEG C, most preferably is 80 DEG C～120 DEG C.In the present invention, the time of described mixing is preferably 2 hours～and 10 hours, more preferably 5 hours～7 hours.
In the present invention, described catalyzer comprises one or more in muriate, iron compound, cobalt compounds and the nickel compounds of manganese, is preferably the one in muriate, iron compound, cobalt compounds and the nickel compounds of manganese.In the present invention, the muriate of described manganese is preferably Manganous chloride tetrahydrate.In the present invention, described iron compound preferably includes one or more in prussiate and the iron content hydrochlorate of chlorate, iron of iron, and more preferably iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash and three oxalic acid close one or more in potassium ferrite.In the present invention, described cobalt compounds comprises the chlorate of cobalt and contains one or more in cobaltates, more preferably one or more in cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol and cobaltous acetate.In the present invention, described nickel compounds preferably includes the chlorate of nickel and contains one or more in nickelate, more preferably one or more in nickelous chloride, nickelous nitrate, single nickel salt and nickelous acetate.In the present invention, described catalyzer is preferably iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid and closes one or more in potassium ferrite, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt and nickelous acetate.The present invention does not have special restriction to the source of described catalyzer, adopts the catalyzer of mentioned kind well known to those skilled in the art, can be bought and be obtained by market.
In the present invention, described biomass carbon source is preferably one or both in Mierocrystalline cellulose and xylogen; More preferably Mierocrystalline cellulose; Most preferably be porous cellulose.In the present invention, the preparation method of described porous cellulose preferably includes following steps:
A), biomass resource is hydrolyzed in acid, obtain lignocellulose, described biomass resource comprises one or more in plant and agriculture and forestry organic waste material;
B), described lignocellulose is processed, obtain porous cellulose, described processing comprises that acid treatment, salt processes or organic solvent processing.
The present invention is preferably hydrolyzed biomass resource in acid, obtains lignocellulose, and described biomass resource comprises one or more in plant and agriculture and forestry organic waste material.In the present invention, the temperature of described hydrolysis is preferably 90 DEG C～180 DEG C, more preferably 120 DEG C～150 DEG C.In the present invention, the time of described hydrolysis is preferably 10min～10h, and more preferably 1h～8h, most preferably is 3h～6h.
In the present invention, the acid of described hydrolysis is preferably one or more in sulfuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid, phosphoric acid and acetic acid, and more preferably sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid or acetic acid, most preferably is sulfuric acid, nitric acid or hydrochloric acid.In the present invention, in described hydrolysis, the consumption of acid is preferably the 3wt%～20wt% of described biomass resource, and more preferably 5wt%～15wt%, most preferably is 8wt%～12wt%.
In the present invention, described biomass resource is preferably agriculture and forestry organic waste material, and more preferably one or more in corn stalk, corn cob, kaoliang stalk, beet pulp, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk and reed, most preferably are corn cob.
Obtain after lignocellulose, the present invention preferably processes described lignocellulose, obtains porous cellulose, and described processing comprises acid treatment, salt processing or organic solvent processing; The present invention more preferably carries out salt processing by described lignocellulose, obtains porous cellulose.In the present invention, the method for described salt processing is preferably acid sulfite process processing or alkali sulfite process processing.In the present invention, the pH value in described acid sulphite process treating processes is preferably 1～7, and more preferably 2～5, most preferably be 3～4.In the present invention, the temperature of described acid sulfite process processing is preferably 70 DEG C～180 DEG C, more preferably 90 DEG C～150 DEG C, most preferably is 100 DEG C～120 DEG C.In the present invention, the time of described acid sulfite process processing is preferably 1 hour～and 6 hours, more preferably 2 hours～5 hours, most preferably be 3 hours～4 hours.
In the present invention, the acid in described acid sulfite process processing is preferably sulfuric acid.In the present invention, in described acid sulfite process treating processes, the consumption of acid is preferably the 4wt%～30wt% of described lignocellulose, and more preferably 8wt%～25wt%, most preferably is 10wt%～20wt%.In the present invention, described acid sulfite process process in the weight percent concentration of acid preferably to make liquid-solid ratio be (2～20): 1, more preferably (4～16): 1, most preferably be (8～12): 1.
In the present invention, the sulphite in described acid sulfite process processing is preferably calcium sulfite, magnesium sulfite, S-WAT or ammonium sulphite, more preferably magnesium sulfite or S-WAT.The present invention does not have special restriction to the consumption of sulphite in described acid sulfite process treating processes, adopts the consumption of sulphite in sulfite pulping process well known to those skilled in the art.
In the present invention, the pH value in described alkaline sulfurous method treating processes is preferably 7～14, and more preferably 8～13, most preferably be 9～12.In the present invention, the temperature of described alkali sulfite process processing is preferably 70 DEG C～180 DEG C, more preferably 90 DEG C～150 DEG C, most preferably is 100 DEG C～120 DEG C.In the present invention, the time of described alkali sulfite process processing is preferably 1 hour～and 6 hours, more preferably 2 hours～5 hours, most preferably be 3 hours～4 hours.
In the present invention, the alkali in described alkali sulfite process processing is preferably calcium hydroxide, sodium hydroxide, ammonium hydroxide or magnesium hydroxide, more preferably sodium hydroxide or magnesium hydroxide.In the present invention, in described alkali sulfite process treating processes, the consumption of alkali is preferably the 4wt%～30wt% of described lignocellulose, and more preferably 8wt%～25wt%, most preferably is 10wt%～20wt%.In the present invention, described alkali sulfite process process in the weight percent concentration of alkali preferably to make liquid-solid ratio be (2～20): 1, more preferably (4～16): 1, most preferably be (8～12): 1.
In the present invention, the sulphite in described alkali sulfite process processing is preferably calcium sulfite, magnesium sulfite, S-WAT or ammonium sulphite, more preferably magnesium sulfite or S-WAT.The present invention does not have special restriction to the consumption of sulphite in described alkali sulfite process treating processes, adopts the consumption of sulphite in sulfite pulping process well known to those skilled in the art.
Obtain after porous cellulose, the present invention preferably also comprises:
Described porous cellulose is carried out to bleaching.
The present invention does not have special restriction to the method for described bleaching, adopts bleaching technology scheme well known to those skilled in the art.In the present invention, the method for described bleaching is preferably total chlorine free bleaching (TCF), more preferably hydrogen peroxide bleaching.The present invention does not have special restriction to the concentration of described hydrogen peroxide, adopts the hydrogen peroxide of typical concentrations.In the present invention, the quality optimization of described hydrogen peroxide is 1%～10% of described porous cellulose quality, more preferably 2%～8%.In the present invention, the bleaching temperature of described hydrogen peroxide bleaching is preferably 60 DEG C～130 DEG C, more preferably 80 DEG C～100 DEG C; The bleaching time of described hydrogen peroxide bleaching is preferably 1h～10h, more preferably 2h～8h.
In the present invention, the mass ratio of described catalyzer and biomass carbon source is preferably (0.01～2): 1, and more preferably (0.1～1): 1, most preferably be (0.3～0.8): 1.In the present invention, the temperature of described catalytic treatment is preferably 20 DEG C～180 DEG C, more preferably 50 DEG C～150 DEG C, most preferably is 80 DEG C～120 DEG C.In the present invention, the time of described catalytic treatment is preferably 2 hours～and 10 hours, more preferably 5 hours～7 hours.
Described biomass carbon source is carried out after catalytic treatment, and the present invention is preferably dried the biomass carbon source after the catalytic treatment obtaining, and obtains the first intermediate product.In the present invention, the temperature of the biomass carbon source after dry described catalytic treatment is preferably 70 DEG C～120 DEG C, more preferably 90 DEG C～100 DEG C.In the present invention, the preferred < 10wt% of the water content of described the first intermediate product, more preferably < 5wt%.
Obtain after the first intermediate product, the present invention, under the condition of protective gas, is incubated described the first intermediate product from the first temperature is warming up to the second temperature, obtains the second intermediate product; Described the first temperature is 20 DEG C～40 DEG C, and described the second temperature is 300 DEG C～400 DEG C.In the present invention, the temperature rise rate that described the first intermediate product is warming up to the second temperature from the first temperature is preferably 5 DEG C/min～20 DEG C/min, more preferably 10 DEG C/min～15 DEG C/min.In the present invention, described the first temperature is preferably 25 DEG C～35 DEG C, more preferably 28 DEG C～32 DEG C.In the present invention, described the second temperature is preferably 320 DEG C～380 DEG C, more preferably 340 DEG C～360 DEG C.In the present invention, the soaking time of described the first intermediate product from the first temperature is warming up to the second temperature be preferably 4 hours～and 8 hours, more preferably 5 hours～6 hours.
In the present invention, described protective gas is preferably one or more in nitrogen and rare gas element, more preferably nitrogen.In the present invention, the intake of described protective gas is preferably 200mL/min～800mL/min, more preferably 400mL/min～600mL/min.
Obtain after the second intermediate product, the present invention, under the condition of protective gas, is incubated described the second intermediate product from the second temperature is warming up to the 3rd temperature, obtains the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C.In the present invention, the temperature rise rate that described the second intermediate product is warming up to the 3rd temperature from the second temperature is preferably 20 DEG C/min～50 DEG C/min, more preferably 30 DEG C/min～40 DEG C/min.In the present invention, described the 3rd temperature is preferably 820 DEG C～880 DEG C, more preferably 840 DEG C～860 DEG C.In the present invention, the soaking time of described the second intermediate product from the second temperature is warming up to the 3rd temperature be preferably 3.5 hours～and 7 hours, more preferably 5 hours～6 hours.
In the present invention, the kind of described protective gas is consistent with kind and the intake of protective gas described in technique scheme with intake, does not repeat them here.In the present invention, described protective gas can be identical with the protective gas described in technique scheme, also can be different.
Obtain after the 3rd intermediate product, the present invention, under the condition of protective gas, is incubated described the 3rd intermediate product from the 3rd temperature is warming up to the 4th temperature, obtains the 4th intermediate product; Described the 4th temperature is 1100 DEG C～1300 DEG C.In the present invention, the temperature rise rate that described 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, described the 4th temperature is preferably 1150 DEG C～1250 DEG C, more preferably 1200 DEG C.In the present invention, the soaking time of described the 3rd intermediate product from the 3rd temperature is warming up to the 4th temperature be preferably 6 hours～and 8 hours, more preferably 7 hours.
In the present invention, the kind of described protective gas is consistent with kind and the intake of protective gas described in technique scheme with intake, does not repeat them here.In the present invention, described protective gas can be identical with the protective gas described in technique scheme, also can be different.
Obtain after the 4th intermediate product, the present invention, under the condition of protective gas, is incubated described the 4th intermediate product from the 4th greenhouse cooling to the five temperature, obtains porous graphene; Described the 5th temperature is 900 DEG C～1000 DEG C.In the present invention, described the 4th intermediate product is preferably 30 DEG C/min～50 DEG C/min from the rate of temperature fall of the 4th greenhouse cooling to the five temperature, more preferably 35 DEG C/min～45 DEG C/min.In the present invention, described the 5th temperature is preferably 920 DEG C～980 DEG C, more preferably 940 DEG C～960 DEG C.In the present invention, the soaking time of described the 4th intermediate product from the 4th greenhouse cooling to the five temperature be preferably 2 hours～and 4 hours, more preferably 3 hours.
In the present invention, the kind of described protective gas is consistent with kind and the intake of protective gas described in technique scheme with intake, does not repeat them here.In the present invention, described protective gas can be identical with the protective gas described in technique scheme, also can be different.
After described the 4th insulation is finished dealing with, the product that the present invention preferably obtains described the 4th insulation processing carries out cooling, obtains porous graphene.In the present invention, 100 DEG C of the preferred < of described cooling temperature,, most preferably are 30 DEG C～40 DEG C by more preferably 20 DEG C～60 DEG C.The present invention preferably carries out described cooling under the condition of protective gas.In the present invention, the kind of described protective gas is consistent with kind and the intake of protective gas described in technique scheme with intake, does not repeat them here.In the present invention, described protective gas can be identical with the protective gas described in technique scheme, also can be different.In the present invention, described cooling method is preferably naturally cooling.
After described cooling completing, the present invention preferably washs the cooled product obtaining, and obtains porous graphene.In the present invention, the method for described washing is preferably:
Described cooled product is carried out in alkaline aqueous solution to the first washing, obtain the first washed product;
Described the first washed product is carried out to the second washing in acidic aqueous solution, obtain the second washed product;
Described the second washed product is carried out to the 3rd washing in water, obtain porous graphene.
The present invention preferably carries out described cooled product the first washing in basic solution, obtains the first washed product.In the present invention, the mass concentration of described alkaline aqueous solution is preferably 3%～55%, and more preferably 10%～40%, most preferably be 20%～30%.In the present invention, the temperature of described the first washing is preferably 60 DEG C～120 DEG C, more preferably 80 DEG C～100 DEG C.In the present invention, described first washing time be preferably 4 hours～24 hours, more preferably 8 hours～16 hours, most preferably be 10 hours～14 hours.In the present invention, described alkaline aqueous solution is preferably aqueous sodium hydroxide solution or ammoniacal liquor.
Obtain after the first washed product, the present invention preferably carries out the second washing by described the first washed product in acidic aqueous solution, obtains the second washed product.In the present invention, the mass concentration of described acidic aqueous solution is preferably 4%～10%, and more preferably 6%～8%.In the present invention, the temperature of described the second washing is preferably 70 DEG C～150 DEG C, more preferably 90 DEG C～120 DEG C.In the present invention, described second washing time be preferably 4 hours～24 hours, more preferably 8 hours～16 hours, most preferably be 10 hours～14 hours.In the present invention, described acidic aqueous solution is preferably aqueous hydrochloric acid.
Obtain after the second washed product, the present invention preferably carries out the 3rd washing by described the second washed product in water, obtains porous graphene.In the present invention, described water is preferably distilled water.The present invention does not have special restriction to the method for described the 3rd washing, after described the 3rd washing, obtains neutral porous graphene.
After described washing completes, the present invention is preferably dried the washed product obtaining, and obtains porous graphene.The present invention does not have special restriction to the method for dry described washed product, adopts dry technology scheme well known to those skilled in the art.
The porous graphene that above method prepares has good conductivity, and lamella is thin, Sp
2hydridization degree is high.
Then the straight chain compound that the application adopts two end groups to be respectively hydroxyl and epoxy group(ing) carries out modification to the Graphene of preparation, introduces hydroxyl in Graphene.
Concrete, by Graphene and straight chain compound, under the effect of quaternary ammonium salt, reaction obtains modified graphene.
In the present invention, described straight chain compound is preferably two end groups and is respectively the C of hydroxyl and epoxy group(ing)
3～20straight chain compound, more preferably two end groups are respectively the C of hydroxyl and epoxy group(ing)
5～15straight chain compound, more preferably two end groups are respectively the C of hydroxyl and epoxy group(ing)
5～10straight chain compound, most preferably be R-GLYCIDOL, epoxy butanols or epoxy octanol.
Described quaternary ammonium salt is preferably 4 bromide, tetramethyl ammonium chloride, Tetramethylammonium hydroxide, Tetramethylammonium iodide, tetraethylammonium bromide, etamon chloride, tetraethyl ammonium fluoride (hydrate), tetraethyl ammonium iodide iodide, 4-propyl bromide, 4-propyl ammonium chloride, tetrapropyl ammonium iodide, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutyl ammonium fluoride, tetrabutylammonium iodide, bromination tetrahexyl ammonium, tricaprylylmethylammchloride chloride, two sclerosis tallow alkyl dimethyl ammonium acetates, cetrimonium bromide, Varisoft 300, benzyltrimethylammonium bromide, zephiran chloride trimethyl ammonium, bromination benzyl triethyl ammonium, benzyltriethylammonium chloride, any one in bromination benzyl tributyl ammonium and benzyl tributyl ammonium chloride or multiple, or be preferably phenyl trimethylammonium bromide, chlorination phenyltrimethyammonium, trioctylphosphine acetic ester, CTAB etc., tetrem base phosphonium bromide, , 4-butyl-phosphonium brometo de amonio, 4-butyl phosphonium chloride, , four butyl phosphonium iodides, 4-butyl-phosphonium acetate, 4-phenyl phosphonium bromide, tributyl-methyl phosphonium phosphonium iodide, tributyl n-octyl bromination ammonium, hexadecyl tributyl phosphonium ammonium, tributyl allyl group phosphoric acid brometo de amonio, three Ethylbenzyl chlorination Phosphonium, tributyl Bian Ji Phosphonium, trioctylphosphine ethyl brometo de amonio, first base three phenyl phosphonium bromides, methyl triphenyl phosphonium chloride, Yi base triphenyl phosphonium bromide, any one or a few in second base triphenyl phosphonium iodide and n-propyl three phenyl phosphonium bromides, or be preferably butyl triphenyl phosphonium bromide, any one or a few in methoxymethyl triphenyl phosphonium chloride and Bian base triphenyl phosphonium chloride.More preferably, benzyltrimethylammonium bromide, benzyl trimethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyl tributyl brometo de amonio, benzyl tributyl ammonium chloride, phenyl trimethylammonium bromide, phenyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, three Ethylbenzyl chlorination Phosphonium, tributyl benzyl base Phosphonium or trioctylphosphine ethyl brometo de amonio.
In the present invention, the mass ratio of described Graphene and straight chain compound is preferably 1:(0.1～10), more preferably 1:(0.3～5), most preferably be 1:(0.5～3); The consumption of described quaternary ammonium salt is preferably the 0.1wt%～1wt% of Graphene, more preferably 0.3wt%～0.5wt%.
Described reaction is preferably carried out in organic solvent.Described organic solvent is preferably alcohol organic solvent, organic solvent of ketone or sulfone class organic solvent, described alcohol organic solvent is preferably methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl carbinol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, cyclopentanol, primary isoamyl alcohol, n-hexyl alcohol, hexalin, n-Heptyl alcohol, secondary butanols, tertiary butyl alcohol, neopentyl alcohol, phenylcarbinol, benzhydrol, trityl alcohol, ethylene glycol, 1, ammediol, 1, 2, 3-glycerol, 1, 2, 3, 4-butantetraol, 1, 2, 3, 4, 5-pentitol, 1, 2, 3, 4, 5, 6-hexan-hexol, 1, 2, 3, 4, 5, 6, 7-volemitol, hexanaphthene-1, 2, 3, 4, 5, any one in 6-six alcohol and 2-(2-propyl group)-5-methyl-cyclohexyl alkane-1-alcohol or multiple, described ketone compounds is preferably any one or a few in acetone, butanone, pentanone, methyl iso-butyl ketone (MIBK), cyclopropanone, pimelinketone, cyclopentanone, benzophenone, methyl phenyl ketone, Propiophenone, phenyl propyl ketone and dimethyl diketone, described sulfone class organic solvent is preferably any one or a few in dimethyl sulfoxide (DMSO), dimethyl sulfone and sulfobenzide.
Mode the indefinite of the present invention to described reaction, as long as can make Graphene react with straight chain compound.Preferably, described reaction is ultrasonic reaction, and the temperature of described reaction is 60 DEG C～80 DEG C, and the time of described reaction is 2h～8h; Preferred, adopt the ultrasonic method of segmentation, first 60 DEG C～70 DEG C ultrasonic reaction 1h～3h, then 70 DEG C～80 DEG C ultrasonic reaction 1h～5h.
The present invention there is no particular restriction to the addition sequence of described Graphene, straight chain compound and quaternary ammonium salt, can add simultaneously, also can add in batches, preferably first Graphene is scattered in organic solvent, then adds straight chain compound and quaternary ammonium salt.
After reaction finishes, product is purified, preferred, filter and wash and remove unnecessary solvent, obtain modified graphene.
The invention also discloses a kind of modified graphene, react and obtain under the effect of quaternary ammonium salt by Graphene and straight chain compound; Described straight chain compound is the straight chain compound that two end groups are respectively hydroxyl and epoxy group(ing).
Hydroxyl and carboxyl are contained in the modified graphene surface of preparation.
Preferably, described Graphene is porous graphene.
The preparation method of described porous graphene is identical with the preparation method of above-mentioned porous graphene, does not repeat them here.
In the present invention, the mass ratio of described Graphene and straight chain compound is preferably 1:(0.1～10), more preferably 1:(0.3～5), most preferably be 1:(0.5～3); The consumption of described quaternary ammonium salt is preferably the 0.1wt%～1wt% of Graphene, more preferably 0.3wt%～0.5wt%.
Described straight chain compound is preferably two end groups and is respectively the C of hydroxyl and epoxy group(ing)
3～20straight chain compound, more preferably two end groups are respectively the C of hydroxyl and epoxy group(ing)
5～15straight chain compound, more preferably two end groups are respectively the C of hydroxyl and epoxy group(ing)
5～10straight chain compound, most preferably be R-GLYCIDOL, epoxy butanols or epoxy octanol.
The present invention also provides a kind of aqueous antistatic epoxy floor paint, comprising:
A component:
40wt%～60wt% aqueous epoxy resins,
0.1wt%～1wt% modified graphene,
20wt%～30wt% graphite,
The auxiliary agent of surplus,
Described modified graphene is modified graphene prepared by above-mentioned preparation method, or above-mentioned modified graphene;
B component:
50wt%～70wt% amine waterborne curing agent,
1wt%～2wt% film coalescence aid,
10wt%～60wt% water,
3wt%～5wt% defoamer;
Described amine waterborne curing agent, film coalescence aid, water and defoamer total amount are 100%;
The amino reactive hydrogen of described B combination and the epoxy group(ing) mol ratio of A component are 1:1.
Wherein, described aqueous epoxy resins is preferably glycol-modified dihydroxyphenyl propane or the Bisphenol F aqueous epoxy resins that epoxy equivalent (weight) is 200～250g/eq.
The particle diameter of described graphite is preferably 100nm～500nm, more preferably 150nm～300nm; The aperture of described graphite is preferably below 500 orders, more preferably 200 order～400 orders.
The present invention there is no particular restriction to described auxiliary agent, can be those skilled in the art's conventional auxiliary agent in the time preparing aqueous epoxy floor coating.
The present invention is preferred, and described auxiliary agent comprises:
2wt%～5wt% reactive thinner,
5wt%～10wt% toughner,
10wt%～15wt% mill base,
0.1wt%～0.3wt% dispersion agent,
0.1wt%～0.3wt% wetting agent,
0.1wt%～0.3wt% flow agent.
Wherein, described reactive thinner is multifunctional aliphatic epoxy, be preferably 1,4-butanediol diglycidyl ether, ethylene glycol diglycidylether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, Hydrogenated Bisphenol A glycidyl ether or trihydroxymethylpropanyltri diglycidyl ether; Described toughner is preferably the polyether glycol of functionality between 3～6, and more preferably functionality is 3 or 4 polyether glycol; Described mill base can, for being applicable to the mill base of aqueous epoxy floor coating routine, be preferably the aqueous color paste of fineness 5 μ m～8 μ m; Described dispersion agent can be for being applicable to the dispersion agent of aqueous epoxy floor coating routine, is preferably molecular weight between 1000～10000 alkoxyl group Styrene oxide 98min. polyethers phosphoric acid salt; Described wetting agent can be for being applicable to the wetting agent of aqueous epoxy floor coating routine, is preferably molecular weight between 500～5000 Siloxane-Oxyalkylene Copolymers; Described flow agent can, for being applicable to the flow agent of aqueous epoxy floor coating routine, be preferably BYK-333 flow agent, BYK-381 flow agent or BYK-DYNWET800 flow agent.
In B component, described aqueous amine solidifying agent is preferably the modified polyamide waterborne curing agent of amine value 150～250mg KOH/g, 25 DEG C of viscosity 10000～30000mPa s; Described film coalescence aid is preferably alkoxide Watery film-fomer, more preferably propylene glycol monomethyl ether, propylene glycol monobutyl ether or ethylene glycol monomethyl ether; Described defoamer can, for being applicable to the defoamer of aqueous epoxy floor coating routine, be preferably Foamex825, Foamex810, Airex962, Airex920, Airex900 that German enlightening is high.
The present invention also provides a kind of preparation method of above-mentioned aqueous antistatic epoxy floor paint, comprising:
A) modified graphene is mixed with graphite, aqueous epoxy resins and auxiliary agent, obtain A component;
B) amine waterborne curing agent, film coalescence aid, defoamer and water are mixed, obtain B component;
B component and A component are mixed with the ratio of epoxy group(ing) mol ratio 1:1 according to amino reactive hydrogen, obtain aqueous antistatic epoxy floor paint;
Described steps A), B) there is no a sequencing.
The weight ratio of described modified graphene and graphite, aqueous epoxy resins is preferably (0.1～1): (20～30): (40～60); The weight ratio of described amine waterborne curing agent, film coalescence aid, defoamer and water is preferably (50～70): (1～2): (10～60): (3～5).
Described auxiliary agent preferably includes: reactive thinner, toughner, mill base, dispersion agent, wetting agent, flow agent, its weight ratio is 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).
Concrete, first by ultrasonic soluble in water to modified graphene and graphite, then adding water-base epoxy, high-speed stirring, after graphene uniform scatter, adds auxiliary agent, obtains A component.
The also high-speed stirring that adds water after amine waterborne curing agent, film coalescence aid, defoamer mixing, to uniform solution, is obtained to B component.
B component and component A are mixed with the ratio of epoxy group(ing) mol ratio 1:1 according to amino reactive hydrogen, can obtain aqueous antistatic epoxy floor paint.
It is carried out to performance test, and result shows, the surface resistivity of the coating of preparation is 2.5 × 10
4Ω～2.7 × 10
5between Ω.
Visible, the straight chain compound that the present invention adopts two end groups to be respectively hydroxyl and epoxy group(ing) carries out modification to Graphene, then the Graphene after modification is applied in aqueous epoxy floor coating, has greatly improved the anti-static ability of coating.
In order to further illustrate the present invention, below in conjunction with embodiment, to a kind of modified graphene provided by the invention and preparation method thereof, and a kind of aqueous antistatic epoxy floor paint and preparation method thereof is described in detail.
Embodiment 1
At 90 DEG C, corn cob is carried out in sulfuric acid to the hydrolysis of 10min, obtain lignocellulose, the quality of described sulfuric acid is 3% of described corn cob quality;
At 70 DEG C, described lignocellulose is carried out to the acid sulfite process processing of 1 hour, obtain porous cellulose, pH value in described acid sulfite process treating processes is 1, acid is sulfuric acid, sulphite is magnesium sulfite, and the quality of described sulfuric acid is 4% of described lignocellulose quality, and liquid-solid ratio is 2:1.
The porous cellulose obtaining is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
Embodiment 2
At 180 DEG C, corn cob is carried out in nitric acid to the hydrolysis of 10h, obtain lignocellulose, the quality of described nitric acid is 20% of described corn cob quality;
At 180 DEG C, described lignocellulose is carried out to the acid sulfite process processing of 6 hours, obtain porous cellulose, pH value in described acid sulfite process treating processes is 7, acid is sulfuric acid, sulphite is S-WAT, and the quality of described sulfuric acid is 30% of described lignocellulose quality, and liquid-solid ratio is 20:1.
Described porous cellulose is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
Embodiment 3
At 130 DEG C, corn cob is carried out in hydrochloric acid to the hydrolysis of 5h, obtain lignocellulose, the quality of described hydrochloric acid is 10% of described corn cob quality;
At 120 DEG C, described lignocellulose is carried out to the acid sulfite process processing of 4 hours, obtain porous cellulose, pH value in described acid sulfite process treating processes is 3, acid is sulfuric acid, sulphite is ammonium sulphite, and the quality of described sulfuric acid is 18% of described lignocellulose quality, and liquid-solid ratio is 10:1.
Described porous cellulose is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
Embodiment 4
The porous cellulose that embodiment 1 is obtained and Manganous chloride tetrahydrate stir and within 2 hours, carry out catalytic treatment at 20 DEG C, and the mass ratio of described Manganous chloride tetrahydrate and porous cellulose is 0.01:1; Product after the catalytic treatment obtaining is dry at 70 DEG C, obtain first intermediate product of water content lower than 10wt%.
Described the first intermediate product is placed in to charring furnace, gas intake using 200mL/min passes into nitrogen as protection gas in described carbide furnace, described the first intermediate product is warming up to 300 DEG C with the speed of 5 DEG C/min from 25 DEG C, is incubated 4 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 800 DEG C with the speed of 20 DEG C/min from 300 DEG C, is incubated 3.5 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1100 DEG C with the speed of 50 DEG C/min from 800 DEG C, is incubated 6 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 900 DEG C with the speed of 30 DEG C/min from 1100 DEG C, is incubated 2 hours; The 4th intermediate product after described cooling is cooled to 60 DEG C.
At 60 DEG C, in the aqueous sodium hydroxide solution that is 3% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 4 hours, obtain the first washed product; At 70 DEG C, in the aqueous hydrochloric acid that is 4% in mass concentration by described the first washed product, wash 4 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
The Graphene that the embodiment of the present invention 4 is prepared carries out Raman spectrum test, and as shown in Figure 1, Fig. 1 is the Raman spectrum of the Graphene that obtains of the embodiment of the present invention 4 to test result, as shown in Figure 1, and the Graphene Sp that the method that the embodiment of the present invention 4 provides prepares
2hydridization degree is high.The Graphene that the embodiment of the present invention 4 is prepared carries out transmissioning electric mirror test, test result is as shown in Fig. 2～Fig. 5, Fig. 2～Fig. 5 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4, can be found out by Fig. 2～Fig. 5, the lamella of the Graphene that the method that the embodiment of the present invention 4 provides prepares is thinner, below 10 layers, it is porous graphene.Adopt conducting performance test instrument, the electroconductibility of the porous graphene that the test embodiment of the present invention 4 prepares, test result is that the conductivity of the porous graphene that the method that the embodiment of the present invention 4 provides prepares is 40000S/m.
Embodiment 5
The porous cellulose that embodiment 2 is prepared and iron nitrate stir and within 10 hours, carry out catalytic treatment at 180 DEG C, and the mass ratio of described iron nitrate and porous cellulose is 2:1; Product after the catalytic treatment obtaining is dry at 120 DEG C, obtain first intermediate product of water content lower than 5wt%.
Described the first intermediate product is placed in to charring furnace, gas intake using 800mL/min passes into argon gas as protection gas in described carbide furnace, described the first intermediate product is warming up to 400 DEG C with the speed of 20 DEG C/min from 20 DEG C, is incubated 8 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 900 DEG C with the speed of 50 DEG C/min from 400 DEG C, is incubated 7 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1300 DEG C with the speed of 60 DEG C/min from 900 DEG C, is incubated 8 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 1000 DEG C with the speed of 50 DEG C/min from 1300 DEG C, is incubated 4 hours; The 4th intermediate product after described cooling is cooled to 20 DEG C.
At 120 DEG C, in the aqueous sodium hydroxide solution that is 55% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 24 hours, obtain the first washed product; At 150 DEG C, in the aqueous hydrochloric acid that is 10% in mass concentration by described the first washed product, wash 24 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
According to the method described in embodiment 4, the Graphene that the embodiment of the present invention 5 is obtained detects, and detected result is, the Graphene Sp that the method that the embodiment of the present invention 5 provides prepares
2hydridization degree is high; The lamella of Graphene is thinner, below 10 layers, is porous graphene; The conductivity of porous graphene is 38000S/m.
Embodiment 6
The porous cellulose that embodiment 3 is prepared and rose vitriol stir and within 5 hours, carry out catalytic treatment at 50 DEG C, and the mass ratio of described rose vitriol and porous cellulose is 0.1:1; Product after the catalytic treatment obtaining is dry at 90 DEG C, obtain first intermediate product of water content lower than 8wt%.
Described the first intermediate product is placed in to charring furnace, gas intake using 400mL/min passes into nitrogen as protection gas in described carbide furnace, described the first intermediate product is warming up to 320 DEG C with the speed of 10 DEG C/min from 40 DEG C, is incubated 5 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 820 DEG C with the speed of 30 DEG C/min from 320 DEG C, is incubated 5 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1150 DEG C with the speed of 54 DEG C/min from 820 DEG C, is incubated 7 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 920 DEG C with the speed of 35 DEG C/min from 1150 DEG C, is incubated 3 hours; The 4th intermediate product after described cooling is cooled to 30 DEG C.
At 80 DEG C, in the ammoniacal liquor that is 10% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 8 hours, obtain the first washed product; At 90 DEG C, in the aqueous hydrochloric acid that is 6% in mass concentration by described the first washed product, wash 8 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
According to the method described in embodiment 4, the Graphene that the embodiment of the present invention 6 is obtained detects, and detected result is, the Graphene Sp that the method that the embodiment of the present invention 6 provides prepares
2hydridization degree is high; The lamella of Graphene is thinner, below 10 layers, is porous graphene; The conductivity of porous graphene is 39000S/m.
Embodiment 7
Porous graphene prepared by 10g embodiment 4 adds ultrasonic dissolution in 50g ethanol, then add after 5g R-GLYCIDOL and 0.03g tetramethyl ammonium chloride ultrasonic dissolution successively at 60 DEG C of ultrasonic 2h, at 80 DEG C of ultrasonic 4h, desolventizing washing afterwards obtains modified graphene 15g.
Under rotating speed 2000r/min, add successively the poly ethyldiol modified dihydroxyphenyl propane aqueous epoxy resins of 150g, the modified graphene of the above-mentioned preparation of 1.5g, 15g TriMethylolPropane(TMP) epoxy, 15g Macrogol 200,30g fineness are that Siloxane-Oxyalkylene Copolymers wetting agent, 0.3gBYK-333 flow agent, 60g graphite and the 100g deionized water of the large red water-based color paste of 6 μ m, alkoxyl group Styrene oxide 98min. polyethers phosphoric acid salt dispersion agent that 0.1g molecular weight is 3000,0.3g molecular weight 1000 stirs evenly and make A component.
60gAradur435,1g propylene glycol monomethyl ether film coalescence aid, 4gFoamex810 are added to 50g deionized water high-speed stirring after mixing, and stirring velocity is 4000r/min, to being mixed into uniform solution, obtains B component.
The ratio that is 1:1 in amino reactive hydrogen and epoxy group(ing) mol ratio by B component and A component mixes rear curing of coating, obtain aqueous antistatic epoxy floor paint, it is carried out to Performance Detection, the results are shown in Table 1, table 1 is that the electrical property result of the coating prepared of the embodiment of the present invention and comparative example gathers.
Embodiment 8
Porous graphene prepared by 10g embodiment 5 adds ultrasonic dissolution in 60g acetone, then add after 10g epoxy butanols and 0.05g tetramethyl ammonium chloride ultrasonic dissolution successively at 60 DEG C of ultrasonic 2h, at 80 DEG C of ultrasonic 4h, desolventizing washing afterwards obtains modified graphene 20g.
Under rotating speed 2500r/min, add successively the poly ethyldiol modified dihydroxyphenyl propane aqueous epoxy resins of 150g, the modified graphene of the above-mentioned preparation of 1.5g, 15g Hydrogenated Bisphenol A epoxy, 15g poly(oxyethylene glycol) 400,30g fineness are that Siloxane-Oxyalkylene Copolymers wetting agent, 0.3gBYK-333 flow agent, 70g graphite and the 150g deionized water of the large red water-based color paste of 6 μ m, alkoxyl group Styrene oxide 98min. polyethers phosphoric acid salt dispersion agent that 0.1g molecular weight is 3000,0.3g molecular weight 1000 stirs evenly and make A component.
By adding 70g deionized water high-speed stirring after 70gAradur435,1.5g propylene glycol monomethyl ether film coalescence aid, 4g Foamex810 mixing to uniform solution, obtain B component.
The ratio that is 1:1 in amino reactive hydrogen and epoxy group(ing) mol ratio by B component and A component mixes rear curing of coating, obtain aqueous antistatic epoxy floor paint, it is carried out to Performance Detection, the results are shown in Table 1, table 1 is that the electrical property result of the coating prepared of the embodiment of the present invention and comparative example gathers.
Embodiment 9
Porous graphene prepared by 15g embodiment 6 adds ultrasonic dissolution in 50gDMSO, then add after 10g epoxy octanol and 0.045g tetramethyl ammonium chloride ultrasonic dissolution successively at 60 DEG C of ultrasonic 2h, at 80 DEG C of ultrasonic 4h, desolventizing washing afterwards obtains modified graphene 20g.
Under rotating speed 3000r/min, add successively the poly ethyldiol modified dihydroxyphenyl propane aqueous epoxy resins of 150g, the modified graphene of the above-mentioned preparation of 2g, 15g TriMethylolPropane(TMP) epoxy, 20g Macrogol 200,30g fineness are that Siloxane-Oxyalkylene Copolymers wetting agent, 0.3gBYK-333 flow agent, 60g graphite and the 150g deionized water of the large red water-based color paste of 5 μ m, alkoxyl group Styrene oxide 98min. polyethers phosphoric acid salt dispersion agent that 0.1g molecular weight is 3000,0.3g molecular weight 1000 stirs evenly and make A component.
By adding 60g deionized water high-speed stirring after 70gAradur435,1g propylene glycol monobutyl ether film coalescence aid, 5g Airex962 mixing to uniform solution, obtain B component.
The ratio that is 1:1 in amino reactive hydrogen and epoxy group(ing) mol ratio by B component and A component mixes rear curing of coating, obtain aqueous antistatic epoxy floor paint, it is carried out to Performance Detection, the results are shown in Table 1, table 1 is that the electrical property result of the coating prepared of the embodiment of the present invention and comparative example gathers.
Comparative example 1
Under rotating speed 2000r/min, add successively the poly ethyldiol modified dihydroxyphenyl propane aqueous epoxy resins of 150g, 1.5g Graphene, 15g TriMethylolPropane(TMP) epoxy, 15g Macrogol 200,30g fineness are that Siloxane-Oxyalkylene Copolymers, 0.3gBYK-381 flow agent, 60g graphite and the 120g deionized water of the large red water-based color paste of 5 μ m, alkoxyl group Styrene oxide 98min. polyethers phosphoric acid salt dispersion agent that 0.3g molecular weight is 6000,0.3g molecular weight 2000 stirs evenly and make A component.
By adding 50g deionized water high-speed stirring after 60gAradur435,1g propylene glycol monobutyl ether film coalescence aid, 4g Airex962 mixing to uniform solution, obtain B component.
The ratio that is 1:1 in amino reactive hydrogen and epoxy group(ing) mol ratio by B component and A component mixes rear curing of coating, obtain aqueous antistatic epoxy floor paint, it is carried out to Performance Detection, the results are shown in Table 1, table 1 is that the electrical property result of the coating prepared of the embodiment of the present invention and comparative example gathers.
The electrical property result of coating prepared by table 1 embodiment of the present invention and comparative example gathers
From above-described embodiment and comparative example, the straight chain compound that the present invention adopts two end groups to be respectively hydroxyl and epoxy group(ing) carries out modification to Graphene, then the Graphene after modification is applied in aqueous epoxy floor coating, has greatly improved the anti-static ability of coating.The Antistatic Paint of preparation is specially adapted to the production plant of electronic element and the applications of storage area such as the extremely sensitive electronic machine of static, unicircuit.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (18)
1. a preparation method for modified graphene, comprising:
By Graphene and straight chain compound, under the effect of quaternary ammonium salt, reaction obtains modified graphene;
Described straight chain compound is the straight chain compound that two end groups are respectively hydroxyl and epoxy group(ing).
2. preparation method according to claim 1, is characterized in that, the mass ratio of described Graphene and straight chain compound is 1:(0.1～10).
3. preparation method according to claim 1, is characterized in that, described straight chain compound is the C that two end groups are respectively hydroxyl and epoxy group(ing)
3～20straight chain compound.
4. preparation method according to claim 1, is characterized in that, described reaction is carried out in organic solvent.
5. preparation method according to claim 1, is characterized in that, described reaction is ultrasonic reaction, and the temperature of described reaction is 60 DEG C～80 DEG C, and the time of described reaction is 2h～8h.
6. preparation method according to claim 1, is characterized in that, described Graphene is porous graphene.
7. preparation method according to claim 6, is characterized in that, described Graphene is prepared in accordance with the following methods:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain porous graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
8. preparation method according to claim 7, is characterized in that, described biomass carbon source is one or both in Mierocrystalline cellulose and xylogen.
9. preparation method according to claim 8, is characterized in that, described biomass carbon source is porous cellulose.
10. preparation method according to claim 9, is characterized in that, the preparation method of described porous cellulose comprises the following steps:
A), biomass resource is hydrolyzed in acid, obtain lignocellulose, described biomass resource comprises one or more in plant and agriculture and forestry organic waste material;
B), described lignocellulose is processed, obtain porous cellulose, described processing comprises that acid treatment, salt processes or organic solvent processing.
11. preparation methods according to claim 10, is characterized in that, described step B) in the method for salt processing be that acid sulfite process is processed or alkali sulfite process processing.
12. 1 kinds of modified graphenes, are reacted and obtain under the effect of quaternary ammonium salt by Graphene and straight chain compound;
Described straight chain compound is the straight chain compound that two end groups are respectively hydroxyl and epoxy group(ing).
13. modified graphenes according to claim 12, is characterized in that, described Graphene is porous graphene.
14. modified graphenes according to claim 12, is characterized in that, the mass ratio of described Graphene and straight chain compound is 1:(0.1～10).
15. modified graphenes according to claim 12, is characterized in that, described straight chain compound is the C that two end groups are respectively hydroxyl and epoxy group(ing)
3～20straight chain compound.
16. 1 kinds of aqueous antistatic epoxy floor paints, comprising:
A component:
40wt%～60wt% aqueous epoxy resins,
0.1wt%～1wt% modified graphene,
20wt%～30wt% graphite,
The auxiliary agent of surplus,
Described modified graphene is modified graphene prepared by the preparation method described in claim 1～11, or modified graphene described in claim 12;
B component:
50wt%～70wt% amine waterborne curing agent,
1wt%～2wt% film coalescence aid,
10wt%～60wt% water,
5wt%～3wt% defoamer;
Described amine waterborne curing agent, film coalescence aid, water and defoamer total amount are 100%;
The amino reactive hydrogen of described B combination and the epoxy group(ing) mol ratio of A component are 1:1.
17. coating according to claim 16, is characterized in that, described auxiliary agent comprises:
2wt%～5wt% reactive thinner,
5wt%～10wt% toughner,
10wt%～15wt% mill base,
0.1wt%～0.3wt% dispersion agent,
0.1wt%～0.3wt% wetting agent,
0.1wt%～0.3wt% flow agent.
The preparation method of the aqueous antistatic epoxy floor paint described in 18. 1 kinds of claims 16, comprising:
A) modified graphene is mixed with graphite, aqueous epoxy resins and auxiliary agent, obtain A component;
B) amine waterborne curing agent, film coalescence aid, defoamer and water are mixed, obtain B component;
B component and A component are mixed with the ratio of epoxy group(ing) mol ratio 1:1 according to amino reactive hydrogen, obtain aqueous antistatic epoxy floor paint;
Described steps A), B) there is no a sequencing.
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