CN108707407A - A kind of graphene modified water-soluble composite material and preparation method - Google Patents
A kind of graphene modified water-soluble composite material and preparation method Download PDFInfo
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- CN108707407A CN108707407A CN201810635247.9A CN201810635247A CN108707407A CN 108707407 A CN108707407 A CN 108707407A CN 201810635247 A CN201810635247 A CN 201810635247A CN 108707407 A CN108707407 A CN 108707407A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
A kind of graphene/Zinc oxide/titanium dioxide compound be include that the groups of following weight percents is grouped as, graphene about 1.5wt% ~ 15wt%, nano zine oxide about 25wt% ~ 65wt%, titanium dioxide about 25wt% ~ 65wt%.Aqueous polyurethane coating produced by the present invention, combine the feature performance benefit of graphene, zinc oxide, titanium dioxide, aqueous polyurethane, with environmental-friendly, good product dispersibility, agglomeration will not occur, with superpower antiseptic property, water resistance and ageing-resistant performance, the performances such as paint machine intensity is high, hardness is high, adhesive force is good, chemical-resistant is strong.
Description
Technical field
The present invention relates to paint fields, and in particular to a kind of graphene/Zinc oxide/titanium dioxide compound, modified water-soluble
Polyurethane material and preparation method thereof.
Background technology
Coating has the performances such as excellent erosion resistant, flexibility, adhesive force and chemical-resistant, be widely used as woodcare paint,
Building coating, automobile coating and water-repellent paint etc., product increase year by year with kind, are the advanced macromolecules that there is major application to be worth
Material has become a kind of new material that kind is most, purposes is most wide, with fastest developing speed in contemporary high molecular material.But due to
Solvent based coating contains a large amount of organic solvents, seriously pollutes the residual isocyanide in environment, especially solvent-type double-component polyurethane
Acid ester monomer, toxicity is high, causes to seriously affect to human body and ecological environment.
Aqueous polyurethane is to replace organic solvent as the new polyurethane system of decentralized medium using water, is had elastic, resistance to
The advantages that mill property, toughness, adhesive force and low-temperature impact resistance are excellent, and VOC contents are low and energy conservation and environmental protection.Although aqueous polyurethane
With many excellent performances, but there is also many deficiencies, and the water resistance such as film is bad, stability of emulsion, from thickening property,
The performance of solid content etc. is not ideal enough, and mechanical strength is not high, and especially hardness is not high enough, and anti-corrosion ability is not strong, anti-ageing
Change poor performance etc., thus limits the further extensive use of aqueous polyurethane.
Graphene has high-specific surface area, high conductivity, mechanical property outstanding, zinc oxide and titanium dioxide nano-particle
The advantages that size that has is small, large specific surface area generates skin effect and quantum effect.
But since solvent based coating contains a large amount of organic solvents, the poly- ammonia of environment, especially solvent-type double-component is seriously polluted
Residual isocyanate monomer in ester, toxicity is high, causes to seriously affect to human body and ecological environment.
At present apparently, traditional solvent-borne coating contains a large amount of organic solvents, seriously pollutes environment；Each existing coating there is also
Product antiseptic property, water resistance, mechanical strength, hardness, adhesive force, chemical-resistant etc. are not ideal enough, and coating
Stability is poor, exposed for a long time in external environment to be easy to happen rotten, corrosion resistance in the natural environment and wearability
Can be also particularly poor, influence its application range.
Invention content
The present invention first is designed to provide a kind of graphene/Zinc oxide/titanium dioxide compound.
Second object of the present invention is to provide a kind of preparation method of graphene/Zinc oxide/titanium dioxide compound.
It is poly- that third object of the present invention is to provide a kind of graphene/Zinc oxide/titanium dioxide compound modified water-soluble
The preparation method of urethane material.
The object of the invention is achieved through the following technical solutions：
A kind of graphene/Zinc oxide/titanium dioxide compound, it is characterised in that：It is the component for including following weight percents
Composition, graphene 1.5wt% ~ 15wt%, nano zine oxide 25wt% ~ 65wt%, titanium dioxide 25wt% ~ 65wt%.
Further preferably, a kind of graphene/Zinc oxide/titanium dioxide compound, it is characterised in that：It is include following
The group of weight percent is grouped as, graphene 5wt% ~ 10wt%, nano zine oxide 48wt% ~ 60wt%, and titanium dioxide 48wt% ~
60wt%。
A kind of preparation method of graphene/Zinc oxide/titanium dioxide compound, it is characterised in that：It is with graphite oxide
Alkene, nano zine oxide, titanium dioxide are raw material, pass through preparation, the graphene/zinc oxide/titanium dioxide of graphene dispersing solution respectively
The preparation of titanium compound and it is final obtained.
Further, the preparation method of a kind of graphene/Zinc oxide/titanium dioxide compound, it is characterised in that：The graphite
The preparation of alkene dispersion liquid is first to obtain graphene oxide using improved Hummers legal systems, is then scattered in graphene oxide
Water and dimethylformamide（DMF）Mixed liquor in, be made into a concentration of 1mg/ml ~ 20mg/ml of graphene oxide solution, use
Ultrasonic cell disintegration instrument, graphene oxide dispersion is made in 1 ~ 2h of ultrasound at 15 ~ 25KHz；The wherein described Hummers methods be
The reaction bulb of appropriate volume is assembled in ice-water bath, the concentrated sulfuric acid is added, and is added with stirring the solid mixing of graphite powder and sodium nitrate
Object, then divide 3 ~ 5 addition potassium permanganate, controlling reaction temperature is no more than 20 DEG C, is stirred to react 1 ~ 2h, is then warming up to 34 ~ 36
DEG C, continue to stir 30 min, is slow added into deionized water, continues 20 ~ 25min of stirring, and appropriate hydrogen peroxide is added to make solution
Become glassy yellow, filter while hot, it is that 3 ~ 5%HCl solution and deionized water are washed until sulfate radical-free in filtrate that volume fraction, which is used in combination,
Until being detected, filter cake is finally placed in 60 DEG C of vacuum drying chamber to fully dry, obtained graphene oxide；Wherein graphite
Powder, sodium nitrate, potassium permanganate mass ratio be 2:1：6；The concentrated sulfuric acid, graphite powder, deionized water mass ratio be 55 ~ 65：
1：30~40.
Further, the preparation method of a kind of graphene/Zinc oxide/titanium dioxide compound, it is characterised in that：The water with
Dimethylformamide（DMF）Mixed solution in water and dimethylformamide（DMF）Volume ratio be 1：1~10.
Further, the preparation method of a kind of graphene/Zinc oxide/titanium dioxide compound, it is characterised in that：The graphite
The preparation of alkene/Zinc oxide/titanium dioxide compound is to take nano zine oxide/titanium dioxide compound, and graphene oxide point is added
Dispersion liquid makes graphene oxide account for the 0.5% ~ 5% of compound mass percentage, 30 ~ 35min of ultrasound at 15 ~ 25KHz, mixes
It closes uniformly, is warming up to 80 DEG C, hydrazine hydrate solution is then added, be uniformly mixed, filtered after reacting 24 h with this condition, will
To product rinsed respectively 5 ~ 10 times with methanol and water successively, then in 60 DEG C of vacuum drying chamber it is fully dry, turn after drying
It is finely ground in dislocation grinding, obtain graphene/Zinc oxide/titanium dioxide powder；Graphene oxide/the Zinc oxide/titanium dioxide
Compound dispersion liquid：The volume ratio of hydrazine hydrate solution is 40 ~ 60:1.
Further, the preparation method of a kind of graphene/Zinc oxide/titanium dioxide compound, it is characterised in that：The nanometer
The mass ratio of Zinc oxide/titanium dioxide compound is 1 ~ 3:1 ~ 3, the graphene oxide/Zinc oxide/titanium dioxide compound point
Dispersion liquid：Hydrazine hydrate solution volume is 50:1.
Further, the preparation method of a kind of graphene/Zinc oxide/titanium dioxide compound modified aqueous polyurethane material,
It is characterized in that：It is by graphene/Zinc oxide/titanium dioxide powder and aqueous polyurethane coating be mixed evenly to get；
The mass ratio of wherein described graphene/Zinc oxide/titanium dioxide powder and aqueous polyurethane coating is 1:2~5.
The present invention has following advantageous effect：
Graphene produced by the present invention/Zinc oxide/titanium dioxide compound modified aqueous polyurethane coating, combine graphene,
The feature performance benefit of zinc oxide, titanium dioxide, aqueous polyurethane has environmental-friendly, good product dispersibility, will not occur to reunite existing
As there is superpower antiseptic property, water resistance and ageing-resistant performance, paint machine intensity is high, hardness is high, adhesive force is good, resistance to
The performances such as chemicals are strong.More than, the composite modified coating of the present invention not only has the modified water-soluble of independent graphene-titanium dioxide
Polyurethane, and the individually effect of the modified aqueous polyurethane of zinc oxide, graphene-titanium dioxide-oxidation produced by the present invention
Zinc modification aqueous polyurethane also achieves synergy.
Specific implementation mode
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, person skilled in art can
To make some nonessential modifications and adaptations to the present invention according to aforementioned present invention content.
Embodiment 1：
1. the preparation of graphene dispersing solution：It is that graphene oxide is first obtained using improved Hummers legal systems, then will aoxidizes stone
It is 1 that black alkene, which is scattered in volume ratio,:5 water and dimethylformamide（DMF）Mixed liquor in, be made into the dense of graphene oxide solution
Degree is 12mg/ml, and using ultrasonic cell disintegration instrument, graphene oxide dispersion is made in ultrasound 1.5h at 20KHz；It is wherein described
Hummers methods are that the reaction bulb of appropriate volume is assembled in ice-water bath, and the 120g concentrated sulfuric acids are added, are added with stirring 2 g graphite
The solid mixture of powder and 1 g sodium nitrate, then divide 3 ~ 56 g potassium permanganate of addition, controlling reaction temperature is no more than 20 DEG C, stirs
Reaction 1.5h is mixed, is then warming up to 35 DEG C, continues to stir 30 min, is slow added into 70g deionized waters, continues to stir 23min,
And appropriate hydrogen peroxide, which is added, makes solution become glassy yellow, filters while hot, it is 4%HCl solution and deionization washing that volume fraction, which is used in combination,
It washs until sulfate radical-free is detected in filtrate, filter cake is finally placed in 60 DEG C of vacuum drying chamber to fully dry, system
Obtain graphene oxide；
2. the preparation of graphene/Zinc oxide/titanium dioxide compound：It is 1 to take mass ratio:2 nano zine oxide/titanium dioxide
Compound is added graphene oxide dispersion and graphene oxide is made to account for the 3% of compound mass percentage, at 20KHz
Ultrasonic 32min is uniformly mixed, is warming up to 80 DEG C, hydrazine hydrate solution is then added, and is uniformly mixed, reacts 24 h with this condition
After filter, obtained product is rinsed 8 times with methanol and water respectively successively, then in 60 DEG C of vacuum drying chamber it is fully dry,
Transfer is set finely ground in grinding after drying, obtains graphene/Zinc oxide/titanium dioxide powder；Graphene oxide/the zinc oxide/
Titanium dioxide compound dispersion liquid：The volume ratio of hydrazine hydrate solution is 50:1.
3. the preparation of graphene/Zinc oxide/titanium dioxide compound modified aqueous polyurethane material：
It is 1 to take graphene obtained above/Zinc oxide/titanium dioxide powder and aqueous polyurethane coating in mass ratio:3 mixing are stirred
Mix uniformly to get.
It is observed in preparation process, mixed process good product dispersibility has no generation agglomeration.
Experiment one：Waterproof, anticorrosion, ageing-resistant performance experiment
By graphene made from embodiment 1/Zinc oxide/titanium dioxide compound modified aqueous polyurethane, it is coated in 30*50mm processes
On the 45# steel plates of processing of rust removing, the steel plate after drying is placed on the NaCl that mass percent is 3.5% by the dry 12h at 70 DEG C
It is impregnated in saline solution, changes primary brine, the corrosion condition of each week observation steel plate every three days, while whether observe coating complete
It is whole.Steel plate does not get rusty phenomenon substantially after 30 days, and coating is also intact, the experimental results showed that coating have superpower waterproof and
Antiseptic property.The steel plate for being coated with coating is placed in ultraviolet ageing case and does ultraviolet ageing experiment, in each UV exposure 8h, condensation
Under 4h, 20 DEG C of condensation temperature, 30 DEG C of Exposure Temperature are done respectively；30 DEG C of condensation temperature, 40 DEG C of Exposure Temperature；40 DEG C of condensation temperature,
50 DEG C of Exposure Temperature；Condensation temperature 50 C, 60 DEG C of Exposure Temperature ultraviolet ageing 15 times, coating does not occur bright after ultraviolet ageing
Aobvious variation illustrates that coating has superpower ageing-resistant performance.
Embodiment 2：
1. the preparation of graphene dispersing solution：It is that graphene oxide is first obtained using improved Hummers legal systems, then will aoxidizes stone
It is 1 that black alkene, which is scattered in volume ratio,:1 water and dimethylformamide（DMF）Mixed liquor in, be made into the dense of graphene oxide solution
Degree is 1mg/ml, and using ultrasonic cell disintegration instrument, graphene oxide dispersion is made in ultrasound 1h at 15KHz；It is wherein described
Hummers methods are that the reaction bulb of appropriate volume is assembled in ice-water bath, and the 110g concentrated sulfuric acids are added, are added with stirring 2 g graphite
The solid mixture of powder and 1 g sodium nitrate, then divide 3 ~ 56 g potassium permanganate of addition, controlling reaction temperature is no more than 20 DEG C, stirs
Reaction 1h is mixed, is then warming up to 34 DEG C, continues to stir 30 min, is slow added into 60g deionized waters, continues to stir 20min, and
Appropriate hydrogen peroxide, which is added, makes solution become glassy yellow, filters while hot, and it is 3%HCl solution and deionized water washing that volume fraction, which is used in combination,
Until sulfate radical-free is detected in filtrate, finally filter cake is placed in 60 DEG C of vacuum drying chamber and is fully dried, is made
Graphene oxide；
2. the preparation of graphene/Zinc oxide/titanium dioxide compound：It is 1 to take mass ratio:1 nano zine oxide/titanium dioxide
Compound is added graphene oxide dispersion and graphene oxide is made to account for the 0.5% of compound mass percentage, in 15KHz
Lower ultrasound 35min is uniformly mixed, is warming up to 80 DEG C, hydrazine hydrate solution is then added, and is uniformly mixed, reacts 24 with this condition
It is filtered after h, obtained product is rinsed 5 times with methanol and water respectively successively, then fully dried in 60 DEG C of vacuum drying chamber,
Transfer is set finely ground in grinding after drying, obtains graphene/Zinc oxide/titanium dioxide powder；Graphene oxide/the zinc oxide/
Titanium dioxide compound dispersion liquid：The volume ratio of hydrazine hydrate solution is 40:1.
3. the preparation of graphene/Zinc oxide/titanium dioxide compound modified aqueous polyurethane material：
It is 1 to take graphene obtained above/Zinc oxide/titanium dioxide powder and aqueous polyurethane coating in mass ratio:2 mixing are stirred
Mix uniformly to get.
It is observed in preparation process, mixed process good product dispersibility has no generation agglomeration.
Experiment one：Waterproof, anticorrosion, ageing-resistant performance experiment
By graphene made from embodiment 2/Zinc oxide/titanium dioxide compound modified aqueous polyurethane, it is coated in 30*50mm processes
On the 45# steel plates of processing of rust removing, the steel plate after drying is placed on the NaCl that mass percent is 3.5% by the dry 12h at 70 DEG C
It is impregnated in saline solution, changes primary brine, the corrosion condition of each week observation steel plate every three days, while whether observe coating complete
It is whole.Steel plate does not get rusty phenomenon substantially after 30 days, and coating is also intact, the experimental results showed that coating have superpower waterproof and
Antiseptic property.The steel plate for being coated with coating is placed in ultraviolet ageing case and does ultraviolet ageing experiment, in each UV exposure 8h, condensation
Under 4h, 20 DEG C of condensation temperature, 30 DEG C of Exposure Temperature are done respectively；30 DEG C of condensation temperature, 40 DEG C of Exposure Temperature；40 DEG C of condensation temperature,
50 DEG C of Exposure Temperature；Condensation temperature 50 C, 60 DEG C of Exposure Temperature ultraviolet ageing 15 times, coating does not occur bright after ultraviolet ageing
Aobvious variation illustrates that coating has superpower ageing-resistant performance.
Embodiment 3
1. the preparation of graphene dispersing solution：It is that graphene oxide is first obtained using improved Hummers legal systems, then will aoxidizes stone
It is 1 that black alkene, which is scattered in volume ratio,:10 water and dimethylformamide（DMF）Mixed liquor in, be made into graphene oxide solution
A concentration of 20mg/ml, using ultrasonic cell disintegration instrument, graphene oxide dispersion is made in ultrasound 2h at 25KHz；It is wherein described
Hummers methods are that the reaction bulb of appropriate volume is assembled in ice-water bath, and the 130g concentrated sulfuric acids are added, are added with stirring 2 g graphite
The solid mixture of powder and 1 g sodium nitrate, then divide 3 ~ 56 g potassium permanganate of addition, controlling reaction temperature is no more than 20 DEG C, stirs
1 ~ 2h of reaction is mixed, is then warming up to 34 ~ 36 DEG C, continues to stir 30 min, is slow added into 80g deionized waters, continues to stir
25min, and appropriate hydrogen peroxide, which is added, makes solution become glassy yellow, filters while hot, be used in combination volume fraction be 5%HCl solution and go from
Filter cake is finally placed in fully dry in 60 DEG C of vacuum drying chamber by sub- water washing until sulfate radical-free is detected in filtrate
It is dry, graphene oxide is made；
2. the preparation of graphene/Zinc oxide/titanium dioxide compound：It is 3 to take mass ratio:1 nano zine oxide/titanium dioxide
Compound is added graphene oxide dispersion and graphene oxide is made to account for the 5% of compound mass percentage, at 25KHz
Ultrasonic 30min is uniformly mixed, is warming up to 80 DEG C, hydrazine hydrate solution is then added, and is uniformly mixed, reacts 24 h with this condition
After filter, obtained product is rinsed 10 times with methanol and water respectively successively, then in 60 DEG C of vacuum drying chamber it is fully dry,
Transfer is set finely ground in grinding after drying, obtains graphene/Zinc oxide/titanium dioxide powder；Graphene oxide/the zinc oxide/
Titanium dioxide compound dispersion liquid：The volume ratio of hydrazine hydrate solution is 60:1.
3. the preparation of graphene/Zinc oxide/titanium dioxide compound modified aqueous polyurethane material：
It is 1 to take graphene obtained above/Zinc oxide/titanium dioxide powder and aqueous polyurethane coating in mass ratio:5 mixing are stirred
Mix uniformly to get.
It is observed in preparation process, mixed process good product dispersibility has no generation agglomeration.
Experiment one：Waterproof, anticorrosion, ageing-resistant performance experiment
By graphene made from embodiment 1/Zinc oxide/titanium dioxide compound modified aqueous polyurethane, it is coated in 30*50mm processes
On the 45# steel plates of processing of rust removing, the steel plate after drying is placed on the NaCl that mass percent is 3.5% by the dry 12h at 70 DEG C
It is impregnated in saline solution, changes primary brine, the corrosion condition of each week observation steel plate every three days, while whether observe coating complete
It is whole.Steel plate does not get rusty phenomenon substantially after 30 days, and coating is also intact, the experimental results showed that coating have superpower waterproof and
Antiseptic property.The steel plate for being coated with coating is placed in ultraviolet ageing case and does ultraviolet ageing experiment, in each UV exposure 8h, condensation
Under 4h, 20 DEG C of condensation temperature, 30 DEG C of Exposure Temperature are done respectively；30 DEG C of condensation temperature, 40 DEG C of Exposure Temperature；40 DEG C of condensation temperature,
50 DEG C of Exposure Temperature；Condensation temperature 50 C, 60 DEG C of Exposure Temperature ultraviolet ageing 15 times, coating does not occur bright after ultraviolet ageing
Aobvious variation illustrates that coating has superpower ageing-resistant performance.
Claims (7)
1. a kind of graphene/Zinc oxide/titanium dioxide compound, it is characterised in that：It is the group for including following weight percents
It is grouped as, graphene about 1.5wt% ~ 15wt%, nano zine oxide about 25wt% ~ 65wt%, titanium dioxide about 25wt% ~ 65wt%.
2. a kind of graphene/Zinc oxide/titanium dioxide compound as described in claim 1, it is characterised in that：It is under including
The group of row weight percent is grouped as, graphene 5wt% ~ 10wt%, nano zine oxide 48wt% ~ 60wt%, and titanium dioxide 48wt% ~
60wt%。
3. a kind of preparation method of graphene/Zinc oxide/titanium dioxide compound as claimed in claim 2, it is characterised in that：
It is using graphene oxide, nano zine oxide, titanium dioxide as raw material, pass through respectively the preparation of graphene dispersing solution, graphene/
The preparation of Zinc oxide/titanium dioxide compound and be finally made.
4. a kind of preparation method of graphene/Zinc oxide/titanium dioxide compound as claimed in claim 3, it is characterised in that：
The preparation of the graphene dispersing solution is first to obtain graphene oxide using improved Hummers legal systems, then by graphite oxide
Alkene is scattered in water and dimethylformamide（DMF）Mixed liquor in, be made into a concentration of 1mg/ml of graphene oxide solution ~
20mg/ml, using ultrasonic cell disintegration instrument, graphene oxide dispersion is made in 1 ~ 2h of ultrasound at 15 ~ 25KHz；It is wherein described
Hummers methods are that the reaction bulb of appropriate volume is assembled in ice-water bath, and the concentrated sulfuric acid is added, is added with stirring graphite powder and nitric acid
The solid mixture of sodium, then divide 3 ~ 5 addition potassium permanganate, controlling reaction temperature is no more than 20 DEG C, is stirred to react 1 ~ 2h, then
34 ~ 36 DEG C are warming up to, continues to stir 30 min, is slow added into deionized water, continues 20 ~ 25min of stirring, and is added appropriate double
Oxygen water makes solution become glassy yellow, filters while hot, and it is that 3 ~ 5%HCl solution and deionized water are washed until filtrate that volume fraction, which is used in combination,
Until middle sulfate radical-free is detected, filter cake is finally placed in 60 DEG C of vacuum drying chamber to fully dry, obtained graphite oxide
Alkene；Wherein graphite powder, sodium nitrate, potassium permanganate mass ratio be 2:1:6；The quality of the concentrated sulfuric acid, graphite powder, deionized water
Than being 55 ~ 65：1：30~40.
5. a kind of preparation method of graphene/Zinc oxide/titanium dioxide compound as claimed in claim 4, it is characterised in that：
The water and dimethylformamide（DMF）Mixed solution in water and dimethylformamide（DMF）Volume ratio be 1：1~10.
6. a kind of preparation method of graphene/Zinc oxide/titanium dioxide compound as claimed in claim 5, it is characterised in that：
The preparation of the graphene/Zinc oxide/titanium dioxide compound is to take nano zine oxide/titanium dioxide compound, and oxidation is added
Graphene dispersing solution makes graphene oxide account for the 0.5% ~ 5% of compound mass percentage, ultrasonic 30 at 15 ~ 25KHz ~
35min is uniformly mixed, is warming up to 80 DEG C, hydrazine hydrate solution is then added, and is uniformly mixed, reacts mistake after 24 h with this condition
Filter, obtained product is rinsed 5 ~ 10 times with methanol and water respectively successively, then fully dry, the baking in 60 DEG C of vacuum drying chamber
Transfer is set finely ground in grinding after dry, obtains graphene/Zinc oxide/titanium dioxide powder；Graphene oxide/zinc oxide/bis-
Titanium oxide compound dispersion liquid：The volume ratio of hydrazine hydrate solution is 40 ~ 60:1.
7. a kind of preparation method of graphene/Zinc oxide/titanium dioxide compound as claimed in claim 6, it is characterised in that：
The mass ratio of the nano zine oxide/titanium dioxide compound is 1 ~ 3:1 ~ 3, the graphene oxide/Zinc oxide/titanium dioxide
Compound dispersion liquid：Hydrazine hydrate solution volume is 50:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113289453A (en) * | 2021-04-24 | 2021-08-24 | 深圳市华净科技有限公司 | Integrative purifier of gaseous pollutant |
| CN113999605A (en) * | 2021-12-17 | 2022-02-01 | 青岛墨金烯碳新材料科技有限公司 | Antibacterial air-purifying graphene water-based paint and preparation method thereof |
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Application publication date: 20181026 |