CN109337505A - A kind of corrosion-resistant graphene oxide/aqueous epoxide resin paint and preparation method - Google Patents
A kind of corrosion-resistant graphene oxide/aqueous epoxide resin paint and preparation method Download PDFInfo
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- CN109337505A CN109337505A CN201811082021.7A CN201811082021A CN109337505A CN 109337505 A CN109337505 A CN 109337505A CN 201811082021 A CN201811082021 A CN 201811082021A CN 109337505 A CN109337505 A CN 109337505A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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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Abstract
The invention belongs to the technical fields of coating preparation, and in particular to graphene oxide is prepared into functional graphene oxide by a kind of corrosion-resistant graphene oxide/aqueous epoxide resin paint and preparation method；Polyflon Mechanical Crushing is ground, swelling is added in hexichol ether solvents and forms suspension, then plus functional graphene oxide ultrasonic disperse, it is cooled into gel, the diphenyl ether in gel is extracted, washing, it is dry, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon is obtained, is added in aqueous epoxy resin emulsion, ultrasonic disperse, add aqueous epoxy curing agent, defoaming agent, stirring, it adjusts to viscosity appropriate, obtains graphene oxide/aqueous epoxide resin paint.The present invention makes an addition in aqueous epoxide resin paint the antiseptic property for improving the coating using graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon, which has excellent corrosion resistance, can be used for the fields such as painting dressing automobiles.
Description
Technical field
The invention belongs to the technical fields of coating preparation, and in particular to a kind of corrosion-resistant graphene oxide/water-base epoxy tree
Grease coating material and preparation method.
Background technique
Aqueous epoxy resins refer to that epoxy resin is dispersed in the form of particle or drop and are situated between by the dispersion of continuous phase of water
In matter and with stable dispersion system, aqueous epoxy resins to be mainly characterized by antiseptic property excellent, except being used for painting dressing automobiles
Outside, the fields such as medical instrument, electric appliance and light industrial products are also used to.
Epoxy resin has excellent adhesive force, excellent mechanical property, good resistance to corrosive chemicals can and it is excellent
Good thermal stability is widely used in machine-building and daily life production；But traditional epoxy resin is insoluble in water, only
It can be dissolved in the organic solvent of aromatic hydrocarbons, ketone and alcohols, so organic solvent must be used as decentralized medium, by epoxy resin
The cold coating for being made into a certain concentration and viscosity could use.Organic solvent diluting epoxy resin is not only at high cost, but also organic
Solvent is inflammable and explosive, brings great security risk, while the poisonous and hazardous volatile ingredient of organic solvent is to the strong of operator
Health brings high risks, also results in serious pollution to environment.Requirement with people to environment is higher and higher, and country has put into effect one
The laws and regulations of serial strict control Volatile organic emissions.Therefore, environmental-friendly environmentally protective chemical material is more next
More concerned, development is of great significance to the research of aqueous epoxide resin paint.
The special application number 201610520073.2 of Chinese invention discloses a kind of graphene modified epoxy anticorrosive paint, should
Coating include following parts by weight of component: 70-80 parts of aqueous epoxy resins, 4-7 parts of isopropyl benzene hydroperoxide, 10-18 parts of graphene,
2.5-4.5 parts of hexamethylene diisocyanate biruet, 2.4-3.6 parts of disodium ethylene diamine tetraacetate, methyl benzotriazazole 5-9
Part, 7-10 parts of nonylphenol polyoxyethylene ether, 5-8 parts of phytase, 4-6 parts of wax powder, 4-13 parts of polysulfone resin, copper sulphate 4-
6 parts.Graphene modified epoxy anticorrosive paint of the present invention has good wearability and high temperature resistance, improves coating and base
Bond strength between face improves curing rate at various temperatures, and also has good water resistance and resist chemical
Property.
Chinese invention patent application number 201610566088.2 discloses a kind of graphene oxide based high-temp-resistant two-component ring
Oxygen cold coating, is made of component A and B component, and the mass ratio of component A and B component is 3:1；The component A includes: poly- ammonia
Ester modified 100 parts by weight of epoxy resin, hydrogenated bisphenol A epoxy resin 30-60 parts by weight, modified graphene oxide 1-6 parts by weight,
Aluminum oxide 10-20 parts by weight, antioxidant 1-3 parts by weight, solvent 20-30 parts by weight；The component B includes: phenolic cure
Agent 6-10 parts by weight, organosilicon curing agent 3-5 parts by weight, solvent 10-30 parts by weight.Product has excellent resistance to after paint solidification
High temperature and water resistance, meanwhile, flexibility, thermal conductivity, inoxidizability of epoxy coating etc. are also improved, is met existing
The demand of technology.
Chinese invention patent application number 201610540900.4 discloses a kind of graphene modified epoxy antistatic painting
Material, the coating include following parts by weight of component: 90-99 parts of aqueous epoxy resins, 15-20 parts of Lauxite, two silicon oxygen of hexamethyl
5-9 parts of alkane, 5-9 parts of dipropylene, 4-6 parts of nonylphenol polyoxyethylene ether, 5-12 parts of graphene, 7-10 parts of polysulfone resin,
5-8 parts of glacial acetic acid, 3-5 parts of p-methyl benzenesulfonic acid, 10-15 parts of alkyl glycosides, 4-9 parts of isopropyl benzene hydroperoxide.Graphene of the present invention
Modified epoxy anti-static coatings can effectively prevent electrostatic, and environmental protection, green, weatherability are strong, and surface of the paint film it is smooth,
Hard wear resistant, pressure-resistant impact resistance, good corrosion resistance can play effect and protect, long service life, and easy for construction.
Chinese invention patent application number 201710894372.7 discloses a kind of aqueous epoxy resin emulsion of containing graphene
And preparation method thereof, the specific preparation step of the aqueous epoxy resin emulsion includes: polyethylene glycol/graphene composite material system
Standby, aqueous epoxy resins emulsifier preparation, the preparation of aqueous epoxy resin emulsion.Wherein polyethylene glycol/graphene composite wood
Material is prepared by situ aggregation method, is can be uniformly dispersed graphene and is anchored in polyethylene glycol matrix, is preparing emulsifier
When, the hydroxyl on polyethylene glycol surface reacts with epoxy resin under the action of catalyst, realize polyethylene glycol, graphene,
The triangular connection of epoxy resin, during preparing lotion, graphene enters in lotion with emulsifier, solves graphene
The difficult dispersion and the problems such as poor compatibility in lotion, obtains the evenly dispersed aqueous epoxy resin emulsion containing graphene.This hair
The aqueous epoxy resin emulsion of the bright containing graphene being prepared has centrifugation, dilution and storage stability good, relative to tradition
Epoxy resin, cost is relatively low, safety and environmental protection and nontoxic；Applied in anticorrosive paint, anticorrosive property and adhesive force are stronger, resist
Impact is good, is easy to construct.
Currently, aqueous epoxy resins, which are prepared into coating, is widely used in painting dressing automobiles field, but since automobile is long-term
In a natural environment, due to ultraviolet irradiation in sunlight, rainwater, it is poor that high/low temperature etc. influences its anti-corrosion ability, therefore improves for exposure
The anti-corrosive properties of aqueous epoxide resin paint are very crucial.Graphene and its derivative can improve in the case where few additive amount
Performances such as the corrosion-resistant of coating, high temperature resistant, but graphene and graphene oxide are not easy to disperse, thus after adding coating anti-corrosion
Performance is still relatively low.
Summary of the invention
For the defect of anti-corrosive properties difference in existing aqueous epoxide resin paint, the present invention proposes a kind of corrosion-resistant graphite oxide
Alkene/aqueous epoxide resin paint and preparation method.
To solve the above problems, the invention adopts the following technical scheme:
A kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint, comprising the following steps:
S1, graphene oxide and amphiphilic surfactant are added to the water, at 35~50 DEG C, disperse, filters, freeze-drying
Obtain functional graphene oxide；
S2, by after polyflon Mechanical Crushing, be put into ball mill, grind into powder, which be added to hexichol
In ether solvents, when temperature is 20~50 DEG C, stirring is swollen it sufficiently and forms suspension, adds the function that step S1 is obtained
Graphene oxide can be changed, dispersed, mixed liquor is formed；
S3, the obtained mixed liquor of step S2 is poured into cooling device, be put into cold-trap, quenched, formed gel, gel will be filled
Device quickly removes and immerses 0.5~2h in ethanol solution, extracts to the diphenyl ether in gel, washs, dry, obtains oxidation stone
Black alkene/polytetrafluoroethylstephanoporate stephanoporate microballoon；
S4, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon that step S3 is obtained is added in aqueous epoxy resin emulsion, is surpassed
Sound dispersion, adds aqueous epoxy curing agent, defoaming agent, and stirring adjusts viscosity with deionized water, obtains graphene oxide/water
Property epoxy coating.
Further, a kind of preparation method of above-mentioned corrosion-resistant graphene oxide/aqueous epoxide resin paint, wherein S1
Ultrasonic disperse is separated into described in step, jitter time is 1.5~4 h；The graphene oxide and amphiphilic surfactant
Mass ratio be 10~30:5~10.
Amphiphilic surfactant is called amphiphilic polymer, refers in same macromolecule while having to two kinds of properties not
Same phase (such as water phase and oily phase, two kinds of oily phases, two kinds of incompatible solid phases etc.) all has the polymer of compatibility.Further,
The preparation method of above-mentioned a kind of corrosion-resistant graphene oxide/aqueous epoxide resin paint, wherein amphiphilic surfactant is alkane
Base phenol polyethenoxy ether, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, number-average molecular weight are 2000~50000
Amphiphilic diblock copolymer, fatty acid methyl ester ethoxylate, the ethylene oxide adduct of polypropylene glycol, alkylolamides,
At least one of sucrose ester, non-ion fluorin carbon surface active agent.
Further, a kind of preparation method of above-mentioned corrosion-resistant graphene oxide/aqueous epoxide resin paint, wherein S2
Polyflon described in step and the mass ratio of functional graphene oxide are 10~30:10~15；The powder
Partial size is less than 50nm.
Further, a kind of preparation method of above-mentioned corrosion-resistant graphene oxide/aqueous epoxide resin paint, wherein S2
The mixing time of stirring described in step be 10~for 24 hours.
Further, a kind of preparation method of above-mentioned corrosion-resistant graphene oxide/aqueous epoxide resin paint, wherein S2
Ultrasonic disperse is separated into described in step, jitter time is 0.5~2h.
Further, a kind of preparation method of above-mentioned corrosion-resistant graphene oxide/aqueous epoxide resin paint, wherein S3
The temperature of cold-trap described in step is -10~0 DEG C；The cool time of the quenching is 1~3h.
Further, a kind of preparation method of above-mentioned corrosion-resistant graphene oxide/aqueous epoxide resin paint, wherein S3
Dry mode described in step is vacuum drying；Drying temperature is 45~70 DEG C；Drying time is 12~36h.
Further, a kind of preparation method of above-mentioned corrosion-resistant graphene oxide/aqueous epoxide resin paint, wherein S4
The time of ultrasonic disperse described in step is 30~60min；The graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon, aqueous ring
The mass ratio of oxygen resin emulsion, aqueous epoxy curing agent and defoaming agent is 10~15:50~80:1~7:1~10；The stirring
For magnetic agitation, mixing time is 0.5~3h.
Each raw material is all made of existing and conventional raw material in the present invention, including but not limited to following model and producer, such as water
Property epoxy resin latex can choose 3520 aqueous epoxy resin emulsion of model that the U.S. steps figure, defoaming agent can choose Bath
The defoaming agent of the model 2550 of husband, aqueous epoxy curing agent can choose the water-base epoxy that the U.S. steps the model 8538 of figure
Curing agent.
The present invention also provides above-mentioned a kind of corrosion-resistant graphene oxide/aqueous rings that a kind of above-mentioned preparation method is prepared
Oxygen cold coating.
The features such as epoxy resin (EP) has excellent adhesion energy, mechanical strength, heat resistance and dielectricity, but it solidifies
Contain a large amount of epoxy groups afterwards；And graphene is substance most hard in the world, and has excellent electric conductivity and thermal conductivity.Cause
This has good application value the advantages of both having both manufactured composite material after graphene and EP compounding.In addition, stone
Black alkene has very big table specific area, in addition the dispersion of the molecular level of graphene, can form very strong interface between polymer
Effect, the functional groups such as hydroxyl and manufacturing process can make graphene become the state of fold, these nanoscale out-of-flatnesses can increase
Interaction between strong graphene and polymer chain.Hydroxyl is contained on functional group's graphite alkene surface, and the chemical groups such as carboxyl can
Stronger hydrogen bond is formed with polarity macromolecule such as polyflon.
A kind of corrosion-resistant graphene oxide/aqueous epoxide resin paint of the present invention, using graphene oxide/polytetrafluoroethylene (PTFE)
Porous microsphere makes an addition in aqueous epoxide resin paint the antiseptic property for improving the coating.The graphene oxide of preparation/poly- four
In vinyl fluoride porous microsphere, the mutual of graphene oxide and polytetrafluoroethylene (PTFE) interspersed can improve the evenly dispersed of graphene oxide
Property, and the porous microsphere has bigger reference area, so that graphene oxide layer and the contact area of coating matrix are bigger,
The coating can be improved and absorb ultraviolet light, protective coating is degraded itself survivable ability, while its repellency can reduce water and
Infiltration of the oxygen to coating, to reduce water and oxygen accelerating the failure to reach excellent corrosion resistance, polytetrafluoroethylene (PTFE) to coating
Introducing, corrosion-resistant with graphene oxide have synergistic effect.The coating has excellent corrosion resistance, can be used for painting dressing automobiles
Equal fields.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint, comprising the following steps:
S1, graphene oxide and amphiphilic surfactant are added to the water, when temperature is 40 DEG C, ultrasonic disperse, when dispersion
Between be 2 h, filtering, freeze-drying obtain functional graphene oxide；The graphene oxide and amphiphilic surfactant
Mass ratio is 20:8；The amphiphilic surfactant is alkyl phenol polyoxyethylene ether；
S2, by after polyflon Mechanical Crushing, be put into ball mill, be ground into partial size be 30nm powder, by the powder
End is added in hexichol ether solvents, when temperature is 30 DEG C, is stirred 12h, is swollen it sufficiently and forms suspension, add step
The functional graphene oxide that S1 is obtained, ultrasonic disperse, time 1h form mixed liquor；Polyflon and functionalization
The mass ratio of graphene oxide is 20:12；
S3, the obtained mixed liquor of step S2 is poured into cooling device, being put into temperature is quenching in -5 DEG C of cold-traps, and the cool time is
2h forms gel, the device for filling gel is quickly removed to and immersed 1h in ethanol solution, extracts to the diphenyl ether in gel,
Washing, vacuum drying, drying temperature are 50 DEG C, and the time is for 24 hours, to obtain graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon；
S4, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon that step S3 is obtained is added to aqueous epoxy resin emulsion and is stepped and is schemed
In 3520, ultrasonic disperse, time 40min；Add aqueous epoxy curing agent step Figure 85 38, defoaming agent 2550, magnetic agitation,
Mixing time is 1h, adjusts viscosity with deionized water, obtains graphene oxide/aqueous epoxide resin paint；The graphite oxide
Alkene/polytetrafluoroethylstephanoporate stephanoporate microballoon, step figure 3520 aqueous epoxy resin emulsion of model, step figure model 8538 it is aqueous
Epoxy hardener, BASF model 2550 defoaming agent mass ratio be 10:50:3:2.
Embodiment 2
A kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint, comprising the following steps:
S1, graphene oxide and amphiphilic surfactant are added to the water, when temperature is 35 DEG C, ultrasonic disperse, when dispersion
Between be 1.5 h, filtering, freeze-drying obtain functional graphene oxide；The graphene oxide and amphiphilic surfactant
Mass ratio be 10:5；The amphiphilic surfactant is high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate；
S2, by after polyflon Mechanical Crushing, be put into ball mill, be ground into the powder of partial size 20nm, by the powder
It is added in hexichol ether solvents, when temperature is 25 DEG C, stirs 10h, be swollen it sufficiently and form suspension, add step S1
Obtained functional graphene oxide, ultrasonic disperse, time 0.6h form mixed liquor；Polyflon and functionalization
The mass ratio of graphene oxide is 12:15；
S3, the obtained mixed liquor of step S2 is poured into cooling device, being put into temperature is quenching in -10 DEG C of cold-traps, and the cool time is
1h forms gel, the device for filling gel is quickly removed to and immersed 0.5h in ethanol solution, extracts to the diphenyl ether in gel
It takes, washs, vacuum drying, drying temperature is 50 DEG C, time 12h, obtains graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon；
S4, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon that step S3 is obtained is added to aqueous epoxy resin emulsion and is stepped and is schemed
In 3520, ultrasonic disperse, time 30min；Add aqueous epoxy curing agent step Figure 85 38, defoaming agent 2550, magnetic agitation,
Mixing time is 2h, adjusts viscosity with deionized water, obtains graphene oxide/aqueous epoxide resin paint；The graphite oxide
Alkene/polytetrafluoroethylstephanoporate stephanoporate microballoon, step figure 3520 aqueous epoxy resin emulsion of model, step figure model 8538 it is aqueous
Epoxy hardener, BASF model 2550 defoaming agent mass ratio be 15:60:4:3.
Embodiment 3
A kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint, comprising the following steps:
S1, graphene oxide and amphiphilic surfactant are added to the water, when temperature is 50 DEG C, ultrasonic disperse, when dispersion
Between be 4 h, filtering, freeze-drying obtain functional graphene oxide；The graphene oxide and amphiphilic surfactant
Mass ratio is 30:10；The amphiphilic surfactant is polyoxyethylene carboxylate；
S2, by after polyflon Mechanical Crushing, be put into ball mill, be ground into the powder of partial size 30nm, by the powder
It is added in hexichol ether solvents, when temperature is 45 DEG C, stirs 20h, be swollen it sufficiently and form suspension, add step S1
Obtained functional graphene oxide, ultrasonic disperse, time 2h form mixed liquor；Polyflon and functionalization oxygen
The mass ratio of graphite alkene is 18:10；
S3, the obtained mixed liquor of step S2 is poured into cooling device, being put into temperature is quenching in 0 DEG C of cold-trap, and the cool time is
3h forms gel, the device for filling gel is quickly removed to and immersed 2h in ethanol solution, extracts to the diphenyl ether in gel,
Washing, vacuum drying, drying temperature are 60 DEG C, time 30h, obtain graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon；
S4, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon that step S3 is obtained is added to aqueous epoxy resin emulsion and is stepped and is schemed
In 3520, ultrasonic disperse, time 40min；Add aqueous epoxy curing agent step Figure 85 38, defoaming agent 2550, magnetic agitation,
Mixing time is 2h, adjusts viscosity with deionized water, obtains graphene oxide/aqueous epoxide resin paint；The graphite oxide
Alkene/polytetrafluoroethylstephanoporate stephanoporate microballoon, step figure 3520 aqueous epoxy resin emulsion of model, step figure model 8538 it is aqueous
Epoxy hardener, BASF model 2550 defoaming agent mass ratio be 12:70:7:5.
Embodiment 4
A kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint, comprising the following steps:
S1, graphene oxide and amphiphilic surfactant are added to the water, when temperature is 40 DEG C, ultrasonic disperse, when dispersion
Between be 2 h, filtering, freeze-drying obtain functional graphene oxide；The graphene oxide and amphiphilic surfactant
Mass ratio is 25:7；The amphiphilic surfactant is the amphiphilic diblock copolymer that number-average molecular weight is 2000~50000；
S2, by after polyflon Mechanical Crushing, be put into ball mill, be ground into the powder of partial size 35nm, by the powder
It is added in hexichol ether solvents, when temperature is 40 DEG C, stirs 16h, be swollen it sufficiently and form suspension, add step S1
Obtained functional graphene oxide, ultrasonic disperse, time 1.5h form mixed liquor；Polyflon and functionalization
The mass ratio of graphene oxide is 15:14；
S3, the obtained mixed liquor of step S2 is poured into cooling device, being put into temperature is quenching in -5 DEG C of cold-traps, and the cool time is
3h forms gel, the device for filling gel is quickly removed to and immersed 1.5h in ethanol solution, extracts to the diphenyl ether in gel
It takes, washs, vacuum drying, drying temperature is 60 DEG C, and the time is for 24 hours, to obtain graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon；
S4, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon that step S3 is obtained is added to aqueous epoxy resin emulsion and is stepped and is schemed
In 3520, ultrasonic disperse, time 60min；Add aqueous epoxy curing agent step Figure 85 38, defoaming agent 2550, magnetic agitation,
Mixing time is 0.5h, adjusts viscosity with deionized water, obtains graphene oxide/aqueous epoxide resin paint；The oxidation stone
The water of the model 8538 of black alkene/polytetrafluoroethylstephanoporate stephanoporate microballoon, 3520 aqueous epoxy resin emulsion of model for stepping figure, figure advanced in years
Property epoxy hardener, BASF model 2550 defoaming agent mass ratio be 10:80:5:3.
Embodiment 5
A kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint, comprising the following steps:
S1, graphene oxide and amphiphilic surfactant are added to the water, when temperature is 45 DEG C, ultrasonic disperse, when dispersion
Between be 3 h, filtering, freeze-drying obtain functional graphene oxide；The graphene oxide and amphiphilic surfactant
Mass ratio is 28:8；The amphiphilic surfactant is ethylene oxide adduct, the alkylolamides of polypropylene glycol；
S2, by after polyflon Mechanical Crushing, be put into ball mill, be ground into the powder of partial size 25nm, by the powder
It is added in hexichol ether solvents, when temperature is 40 DEG C, stirs 20h, be swollen it sufficiently and form suspension, add step S1
Obtained functional graphene oxide, ultrasonic disperse, time 1h form mixed liquor；Polyflon and functionalization oxygen
The mass ratio of graphite alkene is 12:15；
S3, the obtained mixed liquor of step S2 is poured into cooling device, being put into temperature is quenching in 0 DEG C of cold-trap, and the cool time is
2h forms gel, the device for filling gel is quickly removed to and immersed 1.5h in ethanol solution, extracts to the diphenyl ether in gel
It takes, washs, vacuum drying, drying temperature is 50 DEG C, and the time is for 24 hours, to obtain graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon；
S4, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon that step S3 is obtained is added to aqueous epoxy resin emulsion and is stepped and is schemed
In 3520, ultrasonic disperse, time 40min；Add aqueous epoxy curing agent step Figure 85 38, defoaming agent 2550, magnetic agitation,
Mixing time is 1.5h, adjusts viscosity with deionized water, obtains graphene oxide/aqueous epoxide resin paint；The oxidation stone
The water of the model 8538 of black alkene/polytetrafluoroethylstephanoporate stephanoporate microballoon, 3520 aqueous epoxy resin emulsion of model for stepping figure, figure advanced in years
Property epoxy hardener, BASF model 2550 defoaming agent mass ratio be 12:75:4:6.
Embodiment 6
A kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint, comprising the following steps:
S1, graphene oxide and amphiphilic surfactant are added to the water, when temperature is 45 DEG C, ultrasonic disperse, when dispersion
Between be 3 h, filtering, freeze-drying obtain functional graphene oxide；The graphene oxide and amphiphilic surfactant
Mass ratio is 14:5；The amphiphilic surfactant is non-ion fluorin carbon surface active agent；
S2, by after polyflon Mechanical Crushing, be put into ball mill, be ground into the powder of partial size 35nm, by the powder
It is added in hexichol ether solvents, when temperature is 45 DEG C, stirs 15h, be swollen it sufficiently and form suspension, add step S1
Obtained functional graphene oxide, ultrasonic disperse, time 1.5h form mixed liquor；Polyflon and functionalization
The mass ratio of graphene oxide is 28:15；
S3, the obtained mixed liquor of step S2 is poured into cooling device, being put into temperature is quenching in -2 DEG C of cold-traps, and the cool time is
1.5h forms gel, the device for filling gel is quickly removed to and immersed 1h in ethanol solution, extracts to the diphenyl ether in gel
It takes, washs, vacuum drying, drying temperature is 55 DEG C, time 25h, obtains graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon；
S4, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon that step S3 is obtained is added to aqueous epoxy resin emulsion and is stepped and is schemed
In 3520, ultrasonic disperse, time 30min；Add aqueous epoxy curing agent step Figure 85 38, defoaming agent 2550, magnetic agitation,
Mixing time is 1h, adjusts viscosity with deionized water, obtains graphene oxide/aqueous epoxide resin paint；The graphite oxide
Alkene/polytetrafluoroethylstephanoporate stephanoporate microballoon, step figure 3520 aqueous epoxy resin emulsion of model, step figure model 8538 it is aqueous
Epoxy hardener, BASF model 2550 defoaming agent mass ratio be 15:80:7:5.
Comparative example 1
A kind of preparation method of aqueous epoxide resin paint, comprising the following steps:
In hydrotropism's epoxy resin latex, aqueous epoxy curing agent is added, defoaming agent, magnetic agitation, mixing time 1h spends
Ionized water adjusts viscosity, obtains aqueous epoxide resin paint；Its raw material and proportion are the same as embodiment 1；
Corrosion-resistant graphene oxide/the aqueous epoxide resin paint and comparative example 1 that embodiment 1 to embodiment 6 is prepared
To aqueous epoxide resin paint be tested for the property, be sprayed on sheet iron surface, coating thickness is 200 μm, and test result is such as
Shown in the following table 1:
Table 1
| Test item | Testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Resistance to 3%NaCl(d) | GB/T9274-1998 | 110 | 120 | 100 | 95 | 105 | 115 | 70 |
| Resistance to 10%H2SO4(d) | GB/T9274-1998 | 135 | 120 | 110 | 130 | 120 | 125 | 80 |
| Resistance to 10%NaOH(d) | GB/T9274-1998 | 105 | 100 | 95 | 90 | 110 | 102 | 65 |
| Salt fog resistance (h) | GB/T1771-2007 | 7000 | 7500 | 6500 | 7000 | 7000 | 7500 | 5500 |
Claims (10)
1. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint, which is characterized in that including following step
It is rapid:
S1, graphene oxide and amphiphilic surfactant are added to the water, at 35~50 DEG C, disperse, filters, freeze-drying
Obtain functional graphene oxide；
S2, by after polyflon Mechanical Crushing, be put into ball mill, grind into powder, which be added to hexichol
In ether solvents, when temperature is 20~50 DEG C, stirring is swollen it sufficiently and forms suspension, adds the function that step S1 is obtained
Graphene oxide can be changed, dispersed, mixed liquor is formed；
S3, the obtained mixed liquor of step S2 is poured into cooling device, be put into cold-trap, quenched, formed gel, gel will be filled
Device quickly removes and immerses 0.5~2h in ethanol solution, extracts to the diphenyl ether in gel, washs, dry, obtains oxidation stone
Black alkene/polytetrafluoroethylstephanoporate stephanoporate microballoon；
S4, graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon that step S3 is obtained is added in aqueous epoxy resin emulsion, is surpassed
Sound dispersion, adds aqueous epoxy curing agent, defoaming agent, and stirring adjusts viscosity with deionized water, obtains graphene oxide/water
Property epoxy coating.
2. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint according to claim 1, feature
It is, ultrasonic disperse is separated into described in S1 step, and jitter time is 1.5~4 h；The graphene oxide and amphiphilic surface
The mass ratio of activating agent is 10~30:5~10.
3. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint according to claim 1, feature
It is, amphiphilic surfactant described in S1 step is alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, rouge
Fat acid polyoxyethylene ester, the amphiphilic diblock copolymer that number-average molecular weight is 2000~50000, fatty acid methyl ester ethoxylation
Object, the ethylene oxide adduct of polypropylene glycol, alkylolamides, sucrose ester, at least one in non-ion fluorin carbon surface active agent
Kind.
4. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint according to claim 1, feature
It is, the mass ratio of polyflon described in S2 step and functional graphene oxide is 10~30:10~15；It is described
The partial size of powder is less than 50nm.
5. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint according to claim 1, feature
It is, the mixing time of stirring described in S2 step is 10~for 24 hours.
6. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint according to claim 1, feature
It is, ultrasonic disperse is separated into described in S2 step, and jitter time is 0.5~2h.
7. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint according to claim 1, feature
It is, the temperature of cold-trap described in S3 step is -10~0 DEG C；The cool time of the quenching is 1~3h.
8. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint according to claim 1, feature
It is, dry mode described in S3 step is vacuum drying；Drying temperature is 45~70 DEG C；Drying time is 12~36h.
9. a kind of preparation method of corrosion-resistant graphene oxide/aqueous epoxide resin paint according to claim 1, feature
It is, the time of ultrasonic disperse described in S4 step is 30~60min；The graphene oxide/polytetrafluoroethylstephanoporate stephanoporate microballoon,
The mass ratio of aqueous epoxy resin emulsion, aqueous epoxy curing agent and defoaming agent is 10~15:50~80:1~7:1~10；Institute
Stating stirring is magnetic agitation, and mixing time is 0.5~3h.
10. a kind of corrosion-resistant graphene oxide/aqueous epoxide resin paint is characterized in by any one of claim 1~9 system
Preparation Method is prepared.
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| CN110128916A (en) * | 2019-05-31 | 2019-08-16 | 四川轻化工大学 | A kind of preparation method of graphene/epoxy flake anticorrosive paint |
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2018
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Cited By (1)
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| CN110128916A (en) * | 2019-05-31 | 2019-08-16 | 四川轻化工大学 | A kind of preparation method of graphene/epoxy flake anticorrosive paint |
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Application publication date: 20190215 |