CN107033732B - A kind of graphene coating and preparation method thereof - Google Patents
A kind of graphene coating and preparation method thereof Download PDFInfo
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- CN107033732B CN107033732B CN201611116065.8A CN201611116065A CN107033732B CN 107033732 B CN107033732 B CN 107033732B CN 201611116065 A CN201611116065 A CN 201611116065A CN 107033732 B CN107033732 B CN 107033732B
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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
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- 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
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Abstract
The invention discloses a kind of graphene coating and preparation method thereof, the preparation method of graphene coating is the following steps are included: be made mixed liquor for water and resin, by mass parts, 0.2~5 part of expanded graphite is added in every 100 portions of mixed liquors, by being crushed after stirring, grind uniformly with supersonic cell disintegrating apparatus, again by vacuum distillation and freeze-drying, it is prepared into graphene coating.This method also simplifies the production technology of graphite alkenes coating, reduces production cost；And the various performances of the graphite alkenes coating of production are improved.
Description
Technical field
The present invention relates to a kind of graphene coating and preparation method thereof.
Background technique
With the fast development of all trades and professions, the requirement to industry is higher and higher.Water conservancy and hydropower, space flight and aviation, ship code
The first-class equal appearance waterproof and anticorrosion anti scuffing protection to building and equipment has new requirement, the work of the various protection encountered
Condition all becomes extremely complex.In addition, high-tech develop also proposed new requirement, such as space flight and aviation to surface protecting material
, naval vessels ship, deep sea submarine, deep-sea drilling and exploitation etc. rapid development, also to the technology of surface protection coating material
Performance requirement is higher and higher, and some requirements are heat-resisting, some requirement resistance to erosion, wear-resisting, and requirement also is at low or elevated temperatures just
Often operation.Therefore, existing coating material much can not meet present coating process requirement.Operating environment is also sent out constantly
Changing, the engineering-environments such as high temperature high fever, deep-etching are seen everywhere.Therefore, it is necessary to a kind of safe and efficient and adapt to various works
The coating for the various complex environments that condition requires, to prevent the corrosion of all kinds of water environments, acid or alkali environment to structure, also wanting can be in height
It is used under temperature or low temperature condition.The resin base graphene that we develop now utilizes the distinctive various superior functions of graphene, solution
It has determined the coating problem of appeal, can use the technical performance of various resins itself, produced and various be adapted to various operating conditions
Resin base graphene corrosion protection abrasion resistant loses coating, improves and improve the performance of resin, and has the skill of good wear-resisting antiscour
Art performance, waterproof and anticorrosion effect are very good.
Graphene be it is found that the first by the material of single layer atomic building, be interconnected to hexagonal between carbon atom
Grid, electric conductivity, mechanical performance are all very excellent, usually have the graphene of the title of " dark fund " to be applied to mobile device, boat at first
Empty space flight, new energy field of batteries, due to characteristics such as high conductivity, high intensity, ultra-thins, graphene is in space flight military industry field
Application advantage is also extremely prominent.Graphene is transparent under visible light, but airtight, and electric conductivity is strong, bent, mechanical strength
Good, these features can play very big advantage in terms of protective coating.As the graphite of graphene raw materials for production, in China's energy storage
Abundant, the newest research achievement in China has successfully breached mass production and large scale produces this two hang-up.
In addition, high performance resin is also quickly grown, fire resistant resin, low temperature resistant resin, wear resistant resin, uvioresistant tree
The performance indexes of the resin of rouge and resistance to various corrosive mediums suffers from great raising, this utilizes this high-performance for us
Resin and graphene provide more choices range with the use of producing various high performance coating materials.
Currently, the graphite alkenes corrosion protection abrasion resistant corrosion material of domestic development, mainly using the graphene produced with
Resin mixing, produces graphite alkenes coating material.It includes following 3 kinds of preparation methods: (1) melt blending.It will gather under high temperature
Object and graphene melting mixing are closed, can avoid using organic solvent；(2) solution blending.Suitable solvent is selected first to dissolve polymerization
Object, then uniformly mixed with graphene dispersing solution, finally remove solvent；(3) in-situ polymerization.By graphene dispersion to polymer monomer
In, it polymerize between generation monomer-monomer, between monomer-graphene-monomer, raw material is usually modified graphene, to improve the two
Compatibility.First two method is to enter polymer to form intercalated compound inside graphene, and the 3rd kind of method is that polymer is made to exist
It is grown on graphene.There is the problem for effectively making graphene uniform dispersion, uniting in three, affect graphite alkenes coating
Various performances, and complex process, high production cost limit the development of graphite alkenes coating.
Summary of the invention
It is an object of the invention to study the method for the corrosion protection abrasion resistant erosion coating of the manufacture graphite alkenes of a kind of " one-step method ",
It solves the problems, such as that graphene is difficult to substantially uniformity distribution in resin, reduces manufacturing cost, manufacture is inexpensively and various high performance
Graphite alkenes corrosion protection abrasion resistant loses coating, is protected with being suitable for the external coating of all trades and professions, makes this high performance material of graphene
Material is fully utilized in paint industry, reduces energy consumption, contributes for the development of national economy.
The technical scheme is that a kind of preparation method of graphene coating " one-step method " is provided, by water and resin system
At mixed liquor, by mass parts, 0.2~5 part of expanded graphite is added in every 100 portions of mixed liquors, by using after stirring, grind uniformly
Supersonic cell disintegrating apparatus is crushed, then by vacuum distillation and freeze-drying, is prepared into graphene coating.
Preferably, the mixed liquor is the aqueous solution and/or emulsifying resins of water-soluble resin.
Preferably, when mixed liquor is the aqueous solution of water-soluble resin, by mass parts, every 100 portions of mixed liquors are by 20~80
The water-soluble resin of part and 80~20 parts of water composition.
Preferably, when resin is water-soluble resin, by mass parts, every 100 portions of mixed liquors are by 20~80 parts of water solubility
Resin and 80~20 parts of water composition.
Preferably, the emulsifying resins the preparation method is as follows: press mass parts: by 20~60 parts of non-water-soluble resin, water
It is stirred after 30~10 parts of soluble resin, 50~30 parts of water and 0.1~1 part of emulsifier mixing, obtains emulsifying resins.
Preferably, the mixing speed is 1800 turns/min or more, and mixing time is 1~2 hour.
Preferably, freeze-drying is first at temperature -5~-8 DEG C, and 1~2h of pre-freeze makes free water cure, then in temperature -5
~-8 DEG C, it is dry under the conditions of vacuum degree≤20Pa, until moisture≤0.5% in resin base graphene；It is prepared into resin base graphene.
Preferably, the temperature of material is controlled at 35 DEG C hereinafter, grinding time is 1~8 hour in crushing process.
Preferably, the viscosity of water and resin mixture liquor is controlled in 100mPas or less.
Expanded graphite preferably can effectively disperse in low viscosity mixed liquor.Water can be such that ultrasonic wavelength increases, and expand broken
Broken range.Resin is with certain viscosity, the active force collective effect with ultrasonic wave, expanded graphite is preferably sheared,
Removing is crushed.In addition, because the minute bubbles that the cavitation of ultrasonic wave is formed also have put into big gun as explosive by resin film package
It in cylinder, forms many small " bombs ", these " bombs " can constantly move with the vibration of surrounding medium, grow up or quick-fried suddenly
It is fried.Explosion time surrounding liquid pours bubble suddenly and generates high temperature, high pressure, while generating shock wave, effectively improves ultrasonic wave
Mechanical effect, improve the efficiency that expanded graphite is prepared into graphene in mixing liquid.
Preferably, by above-mentioned process for producing, corresponding various kinds of resin can be selected to carry out reasonable according to working condition requirement
The resin base corrosion protection abrasion resistant erosion coating of various performance requirements is produced in collocation mixing.
Graphene coating is obtained by above-mentioned preparation method the present invention further provides a kind of.
Preferably, toughener, defoaming agent and levelling agent are also added in the graphene coating.
Graphene cold coating of the invention, is not added to finished product graphene in resin and is stirred,
It is added in resin by expanded graphite, carries out broken dispersion, make expanded graphite with resin in the case where mixing, makes to expand stone
Ink is converted to graphene.
The present invention is the expanded graphite and resin mixture liquor of preparation, by thin with ultrasonic wave after high-speed stirred, grinding uniformly
Born of the same parents' disintegrating apparatus is crushed again through vacuum distillation and freeze-drying, and graphene cold coating is prepared into.Because containing in resin
A certain proportion of water, various research achievements show that ultrasonic wave can generate bigger big gun when there is water and break power.In addition, resin
It is both the dispersion liquid of graphene and the remover of expanded graphite.Expanded graphite breaks power in ultrasonic wave big gun and resin viscosity generates
Shearing force collective effect under, expanded graphite is slowly crushed, tear, is removed and become 10 layers of graphene below, and
Even is distributed in the mixing liquid of resin and water, is prepared as the mixing liquid of resin, water, graphene.
The present invention mixes micro material by the dosage of the standard empirical formula of cold coating in the graphene cold coating of preparation
After expecting that (such as toughener, defoaming agent, levelling agent) carries out high-speed stirred, that is, it can be prepared into the component A in coating system.Again and admittedly
Agent --- i.e. B component is used cooperatively.Curing agent can be selected according to corresponding resin and working condition requirement, curing agent as
B component in coating system, volume are calculated according to the epoxide number of resin.
The invention has the advantages that expanded graphite breaks the common of the shearing force of power and resin viscosity generation in ultrasonic wave big gun
Under effect, expanded graphite is slowly crushed, tear, is removed and becomes 10 layers of graphene below, and is evenly distributed in resin
In the mixing liquid of water, this method also simplifies the production technology of graphite alkenes coating, reduces production cost；And it is raw
The various performances of the graphite alkenes coating of production are improved.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
The present embodiments relate to a kind of graphene cold coating and its preparation methods of one-step method, and available with the technology
Various water-soluble resins and non-water-soluble resin are prepared into various graphene coating component As, then prepare with curing agent component
At various anti scuffing anticorrosive paint series of products.Water-soluble resin is to implement with glycolylurea epoxide resin and water soluble phenol resin
Example is prepared into hydantoin epoxy base graphene anti scuffing coating using the technology and water soluble phenol resin base graphene anti scuffing applies
Material, non-water-soluble resin is by taking high viscosity E44 epoxy resin and the low viscosity epoxy resin trade mark are 6002 epoxy resin as an example, application
The technology is prepared into E44 epoxy resin-matrix graphene anti scuffing coating and 6002 epoxy group graphene corrosion protection abrasion resistants erosion coating.Respectively
Material in embodiment is with mass parts or mass percentage.Glycolylurea resin, that is, glycolylurea epoxide resin abbreviation.
Embodiment (one)
With glycolylurea epoxide resin be prepared into glycolylurea resin base graphene corrosion protection abrasion resistant erosion Paint Examples the following steps are included:
1, glycolylurea resin is dissolved in water, optimal proportion is 60 parts of glycolylurea resin, 40 parts of water, is then added and accounts for resin and water
0.5% expanded graphite of gross mass.The viscosity of water and resin mixture liquor is controlled in 100mPas hereinafter, expanded graphite is low viscous
Preferably can effectively it disperse in degree mixed liquor.Water can be such that ultrasonic wavelength increases, and expand broken range.Resin has certain glue
Property, the active force collective effect with ultrasonic wave is preferably sheared expanded graphite, is removed, is crushed.In addition, because of ultrasonic wave
The minute bubbles that are formed of cavitation also put into gun barrel as explosive by resin film package, form many small " fried
Bullet ", these " bombs " can constantly move with the vibration of surrounding medium, grow up or big gun is fried suddenly.Surrounding liquid is unexpected when big gun is fried
It pours bubble and generates high temperature, high pressure, while generating shock wave, effectively improve the mechanical effect of ultrasonic wave.
2, glycolylurea epoxide resin, water, expanded graphite stir evenly mixture by high-speed mixer, mixing time
It most preferably 60 minutes, is then ground with grinder, grinding Best Times are 120 minutes.
3, the mixture stirred evenly is put into ultrasonic cell-break equipment and is crushed, in shattering process, broken
Broken drum is peripherally equipped with cooling system, carries out overcurrent cooling with normal-temperature water, controls the temperature for the material being crushed at 35 DEG C
Hereinafter, the broken time is -8 hours 1 hour, mixed liquor is made to be prepared into the mixed liquor of glycolylurea resin, water, graphene.
4, the mixed liquor of glycolylurea epoxide resin, water, graphene is sampled, whether detection expanded graphite conversion graphene is complete
And graphene number of plies detects and be evenly distributed state of the graphene in resin:
1. whether complete and graphene number of plies detects expanded graphite conversion graphene: the mixing for taking 500 grams of steps 3 to prepare
Liquid is added 50% water and stirs evenly, then the mixed liquor of water mixing is poured into filter-press (pressure 0.20MPa, filter membrane
Aperture is 20 μm) after filtering, it is the mixed liquor of water and graphene that resin, which stays the liquid in the filter, being obtained by filtration, then is led to
It crosses and is dried to obtain graphene, obtained graphene is detected by SPM-9700 Japan Shimadzu scanning probe microscopy, lead to
It is completely broken to cross detection expanded graphite, the graphene number of plies being obtained by filtration is 10 layers or less.
2. graphene in resin uniformity detection: take 100 Kehaiyin medicine resins, water, graphene mixed liquor sample into
Row drying makes moisture content less than 1%, and the glycolylurea resin that is dried to obtain, graphene mixed liquor are then applied to the silicon throwing film and crossing
On piece 20 microns of coating layer thickness, is detected with metallographic microscope LV100D, detects that graphene is evenly distributed in resin.
5, the mixed liquor being crushed is carried out vacuum decompression distillation, carries out preliminary hydro-extraction, is down to water content in mixture
6%。
6, the mixture after vacuum decompression distillation, carries out vacuum freeze drying followed by vacuum freeze drier, specifically
Step are as follows: first at temperature -5~-8 DEG C, 1~2h of pre-freeze makes its free water cure, prevents blistering, shrinks, then in temperature -5
~-8 DEG C, it is dry under the conditions of vacuum degree≤20Pa, until moisture≤0.5% in resin base graphene；It is prepared into glycolylurea resin foundation stone
Black alkene.
7, the glycolylurea resin base graphene of preparation add 1% polysulfide rubber, 0.1% levelling agent, 0.2% defoaming agent
It after carrying out high-speed stirred, is packed, is prepared into the component A of glycolylurea resin base graphene corrosion protection abrasion resistant erosion coating.
8, curing agent selects 650 polyurethane curing agents, is prepared into the B group of glycolylurea resin base graphene corrosion protection abrasion resistant erosion coating
Point.
9, glycolylurea resin base graphene corrosion protection abrasion resistant erosion coating is made of component A and B component, by component A and B group when use
The ratio divided is 100 to 35, can be brushed to body surface after mixing, and corrosion protection abrasion resistant erosion protective effect is played after solidification.
10, the application and technical performance of glycolylurea resin base graphene corrosion protection abrasion resistant erosion coating
1. viscosity is low, good manufacturability.Coating made from its viscosity ratio bisphenol A type epoxy resin is much lower, agent without dilution
Just there is good processing performance, can be used as solventless coatings, solvent-free adhesive, photoelectric cell packaging material etc..
2. thermal stability is good, heat resistance is high.5000h or more can be used in its insulation filling material at 180 DEG C;At 130 DEG C
Service life is 40 years.
3. good weatherability.Its coating is not easy jaundice and dusting under daylight or UV exposure.Performance is better than bisphenol A-type
Epoxy resin and acrylic resin paint.Its salt spray resistance, corrosion resistance are also very prominent, can be used as the anti-of marine structure and ship
Dirt covering coating, adhesive for building etc..
4. electrical property is prominent under high voltage and super-pressure, especially there is excellent arc resistance and tracking-resistant trace
Property, it can be used as high voltage withstanding insulating device.
5. polarity is very strong, viscosity is low, thus to glass fibre, carbon fiber and a variety of fillers have good wetting power and
Cementability can add mass filler under the premise of not reducing craftsmanship, so that linear expansion coefficient and cost be made to reduce.
6. small toxicity.Belong to the coating of environment-friendly type, Non-toxic adhesive can be made into.
7. the glycolylurea resin base graphene anti scuffing coating prepared by embodiment (one), in addition to excellent with above-mentioned items
Outside performance, following performance indexes is better than the performance indicator of glycolylurea epoxide resin solidfied material itself, as adhesion strength is big
In 24MPa, compression strength is greater than 100MPa, and wear-resisting property is through HKCM-120 high speed concrete anti-abrasion tester sample punching mill 7
It, waste zero, acidproof, alkaline-resisting, salt resistant character all increases substantially.
Embodiment (two)
Being prepared into water soluble phenol resin base graphene corrosion protection abrasion resistant erosion Paint Examples with water soluble phenol resin includes
Following steps:
1, water soluble phenol resin is dissolved in water, optimal proportion is 60 parts of water soluble phenol resin, 40 parts of water, then plus
Enter to account for 0.5% expanded graphite of resin and water gross mass.
2, water soluble phenol resin, water, expanded graphite stir evenly mixture by high-speed mixer, mixing time
It most preferably 60 minutes, is then ground with grinder, grinding Best Times are 120 minutes.
3, the mixture stirred evenly is put into ultrasonic cell-break equipment and is crushed, in shattering process, broken
Broken drum is peripherally equipped with cooling system, carries out overcurrent cooling with normal-temperature water, controls the temperature for the material being crushed 350C
Hereinafter, the broken time is -8 hours 1 hour, preferably 1.5 hours, mixed liquor is made to be prepared into the mixing of glycolylurea resin, water, graphene
Liquid.
4, the mixed liquor of water soluble phenol resin, water, graphene is sampled, whether detection expanded graphite conversion graphene is complete
The detection of complete and graphene number of plies and be evenly distributed state of the graphene in resin:
1. whether complete and graphene number of plies detects expanded graphite conversion graphene: the mixing for taking 500 grams of steps 3 to prepare
Liquid is added 50% water and stirs evenly, then the mixed liquor of water mixing is poured into homemade filter-press (pressure 0.20MPa,
Filtering membrane aperture is 20 μm) after filtering, it is the mixing of water and graphene that resin, which stays the liquid in the filter, being obtained by filtration,
Liquid, then by being dried to obtain graphene, obtained graphene is carried out by SPM-9700 Japan Shimadzu scanning probe microscopy
Detection, completely broken by detection expanded graphite, the graphene number of plies being obtained by filtration is 10 layers or less.
2. graphene in resin uniformity detection: take 100 grams of phenolic resin, water, graphene mixed liquor sample into
Row drying makes moisture content less than 1%, and the phenolic resin that is dried to obtain, graphene mixed liquor are then applied to the silicon throwing film and crossing
On piece 20 microns of coating layer thickness, is detected with metallographic microscope LV100D, detects that graphene is evenly distributed in resin.
5, the mixed liquor being crushed is carried out vacuum decompression distillation, carries out preliminary hydro-extraction, is down to water content in mixture
6%。
6, the mixture after vacuum decompression distillation, carries out vacuum freeze drying followed by vacuum freeze drier, specifically
Step are as follows: first at temperature -5~-8 DEG C, 1~2h of pre-freeze makes its free water cure, then temperature -5~-8 DEG C, vacuum degree≤
It is dry under the conditions of 20Pa, until moisture≤0.5% in resin base graphene；It is prepared into water soluble phenol resin base graphene.
7, the water soluble phenol resin base graphene of preparation is added 1% polysulfide rubber, 0.1% levelling agent, 0.2%
It after defoaming agent etc. carries out high-speed stirred, is packed, is prepared into the A of water soluble phenol resin base graphene corrosion protection abrasion resistant erosion coating
Component.
8, curing agent selects hexamethylenetetramine.As the B of water soluble phenol resin base graphene corrosion protection abrasion resistant erosion coating
Component.
9, water soluble phenol resin base graphene corrosion protection abrasion resistant erosion coating is made of component A and B component, by A group when use
Divide and the ratio of B component is 100 to 8, body surface can be brushed to after mixing, corrosion protection abrasion resistant erosion protection is played after solidification and is made
With.
10, the application and technical performance of water soluble phenol resin base graphene corrosion protection abrasion resistant erosion coating
1. its characteristic of water soluble phenol resin is a large amount of organic molten to be replaced with water, pollution is eliminated, cost is reduced.As layer
The binder of pressing plate and various coating compositions.
2. the water soluble phenol resin base graphene anti scuffing coating prepared by embodiment (two), in addition to above-mentioned each
Outside item excellent performance, following performance indexes is better than the performance indicator of water soluble phenol resin solidfied material itself, such as viscous
Knotting strength is greater than 24MPa, and compression strength is greater than 100MPa, and wear-resisting property is tried through HKCM-120 high speed concrete anti-abrasion tester
Sample punching mill 7 days, waste zero, resistance to saltfog can be increased to 5000h.
Embodiment (three)
It is that 6002 epoxy resin are prepared into the erosion painting of 6002 resin base graphene corrosion protection abrasion resistants with the low viscosity epoxy resin trade mark
Expect embodiment the following steps are included:
1,6002 epoxy resin are prepared into 6002 epoxy emulsifying resins.The technology path of the emulsifying resins of preparation is as follows:
20-60 parts of 6002 epoxy resin of its quality proportioning, preferably 40 parts: 30-10 parts of water-solubility hydantoin epoxy resins, preferably 20 parts:
50-30 parts of water, preferably 40 parts.Dow DOWFAX 2A1 emulsifier volume is the 0.1%-1% of resin water inventory, preferably
0.5%.Being stirred after resin, water, emulsifier mixing through high-speed mixer (speed of agitator be 2000 turns/min), when stirring
Between be 1-2 hours, preferably 1.5 hours.Obtain 6002 emulsifying resins.
2, divide in mass ratio, 100 parts of 6002 emulsifying resins are made, add the expanded graphite for accounting for emulsifying resins 0.5%.
3,6002 emulsion epoxy resins, expanded graphite stir evenly mixture by high-speed mixer, mixing time
It most preferably 60 minutes, is then ground with grinder, grinding Best Times are 120 minutes.
4, the mixture stirred evenly is put into ultrasonic cell-break equipment and is crushed, in shattering process, broken
Broken drum is peripherally equipped with cooling system, carries out overcurrent cooling with normal-temperature water, controls the temperature for the material being crushed at 35 DEG C
Hereinafter, the broken time is -8 hours 1 hour, preferably 1.5 hours, mixed liquor is made to be prepared into the mixing of 6002 resins, water, graphene
Liquid.
5, the mixed liquor of 6002 resins, water, graphene is sampled, completely and stone whether detection expanded graphite conversion graphene
Black alkene number of plies detection and be evenly distributed state of the graphene in resin:
1. expanded graphite converts graphene, whether complete and graphene number of plies is detected: 6002 resins, the stone for taking 500 restraints standby
The mixing liquid of black alkene, water is added 50% water and stirs evenly, then the mixed liquor of water mixing is poured into homemade filter-press
(pressure 0.20MPa, filtering membrane aperture are 20 μm) after filtering, it is water that resin, which stays the liquid in the filter, being obtained by filtration,
Obtained graphene is passed through SPM-9700 Japan Shimadzu with the mixed liquor of graphene and is scanned then by being dried to obtain graphene
Probe microscope is detected, completely broken by detection expanded graphite, and the graphene number of plies being obtained by filtration is 10 layers or less.
2. graphene in resin uniformity detection: take 100 gram of 6002 resin, water, graphene mixed liquor sample into
Row drying makes moisture content less than 1%, and 6002 resins that are dried to obtain, graphene mixed liquor are then applied to the silicon throwing film and crossing
On piece 20 microns of coating layer thickness, is detected with metallographic microscope LV100D, detects that graphene is evenly distributed in resin.
6, the mixed liquor being crushed is carried out vacuum decompression distillation, carries out preliminary hydro-extraction, is down to water content in mixture
6%。
7, the mixture after vacuum decompression distillation, carries out vacuum freeze drying followed by vacuum freeze drier, specifically
Step are as follows: first at temperature -5~-8 DEG C, 1~2h of pre-freeze makes its free water cure, prevents blistering, shrinks, then in temperature -5
~-8 DEG C, it is dry under the conditions of vacuum degree≤20Pa, until moisture≤0.5% in resin base graphene；It is prepared into 6002 resin foundation stones
Black alkene.
8,6002 resin base graphenes of preparation add 1% polysulfide rubber, 0.1% levelling agent, 0.2% defoaming agent
It after carrying out high-speed stirred, is packed, is prepared into the component A of 6002 resin base graphene corrosion protection abrasion resistants erosion coating.
9, it is 593 curing agent that curing agent, which selects the trade mark, and the erosion of 6002 resin base graphene corrosion protection abrasion resistants is prepared into after packaging
The B component of coating.
10,6002 resin base graphene corrosion protection abrasion resistants erosion coating is made of component A and B component, when in use by component A and
The ratio of B component is 100 to 12, can be brushed to body surface solidification after mixing and play corrosion protection abrasion resistant erosion protective effect.
11, the application and technical performance of 6002 resin base graphene corrosion protection abrasion resistants erosion coating
1. 6002 epoxy resin, its viscosity is very low, only 1/10th of E-51 epoxy resin, good fluidity, is easy
Construction, solidfied material still keep a series of excellent performances of ordinary epoxy resin.It is usually used in coating, casting, composite material and glues
It closes.
2. 6002 epoxy resin can be made solvent-free type environment-friendly coating because viscosity is low.
3. the 6002 resin base graphene anti scuffing coating prepared by embodiment (three), in addition to excellent with above-mentioned items
Outside performance, following performance indexes is better than the performance indicator of 6002 resin cured matters itself, as adhesion strength is greater than
24MPa, compression strength are greater than 80MPa, and wear-resisting property is ground 7 days through the punching of HKCM-120 high speed concrete anti-abrasion tester sample,
Waste is zero, and resistant abrasion ability is stronger than the resistant abrasion ability of tungsten carbide spray coating and titanium alloy surface, acidproof, alkaline-resisting, salt tolerant
Performance all increases substantially.
Embodiment (four)
Using high-viscosity epoxy resin, the trade mark is that E44 epoxy resin is prepared into the erosion painting of E44 resin base graphene corrosion protection abrasion resistant
Expect embodiment the following steps are included:
1, E44 epoxy resin is prepared into E44 epoxy emulsifying resins.The technology path of the emulsifying resins of preparation is as follows: its
Quality proportioning 20-60 parts of E44 epoxy resin, preferably 35 parts: 30-10 parts of water-solubility hydantoin epoxy resins, preferably 25 parts: water
50-30 parts, preferably 40 parts.Dow DOWFAX 2A1 emulsifier volume be resin water inventory 0.1%-1%, preferably 0.5%.
Through high-speed mixer, (speed of agitator is stirred, mixing time 1- for 2000 turns/min) after resin, water, emulsifier mixing
2 hours, preferably 1.5 hours.Obtain E44 epoxy emulsifying resins.
2, divide in mass ratio, 100 parts of E44 epoxy emulsifying resins are made, add the expanded graphite for accounting for emulsifying resins quality 0.5%.
3, E44 emulsion epoxy resin, expanded graphite are mixed, mixture is stirred evenly by high-speed mixer, stirred
Time optimal is 60 minutes, is then ground with grinder, and grinding Best Times are 120 minutes.
4, the mixture stirred evenly is put into ultrasonic cell-break equipment and is crushed, in shattering process, broken
Broken drum is peripherally equipped with cooling system, carries out overcurrent cooling with normal-temperature water, controls the temperature for the material being crushed at 35 DEG C
Hereinafter, the broken time is -8 hours 1 hour, preferably 1.5 hours, mixed liquor is made to be prepared into E44 epoxy resin, water, graphene
Mixed liquor.
5, the mixed liquor of the E44 epoxy resin of preparation, water, graphene is sampled, detection expanded graphite conversion graphene is
No complete and graphene number of plies detection and be evenly distributed state of the graphene in resin:
1. whether complete and graphene number of plies detects expanded graphite conversion graphene: taking the E44 asphalt mixtures modified by epoxy resin that 500 restraints are standby
The mixing liquid of rouge, graphene, water is added 50% water and stirs evenly, then the mixed liquor of water mixing is poured into filter-press
(pressure 0.20MPa, filtering membrane aperture are 20 μm) after filtering, it is water that resin, which stays the liquid in the filter, being obtained by filtration,
Obtained graphene is passed through SPM-9700 Japan Shimadzu with the mixed liquor of graphene and is scanned then by being dried to obtain graphene
Probe microscope is detected, completely broken by detection expanded graphite, and the graphene number of plies being obtained by filtration is 10 layers or less.
2. uniformity detection of the graphene in resin: taking the mixed liquor sample of 100 grams of E44 epoxy resin, water, graphene
It is dried, makes moisture content less than 1%, the E44 epoxy resin that is dried to obtain, graphene mixed liquor are then applied to throwing film
On the silicon wafer crossed, 20 microns of coating layer thickness, is detected with metallographic microscope LV100D, detect that graphene is distributed in resin
Uniformly.
6, the mixed liquor being crushed is carried out vacuum decompression distillation, carries out preliminary hydro-extraction, is down to water content in mixture
6%.Then the mixture after vacuum decompression being distilled carries out vacuum freeze drying, specific steps using vacuum freeze drier
Are as follows: first at temperature -5~-8 DEG C, 1~2h of pre-freeze makes its free water cure, prevents blistering, shrinks, then in temperature -5~-8
DEG C, it is dry under the conditions of vacuum degree≤20Pa, until moisture≤0.5% in resin base graphene；It is prepared into E44 epoxy resin foundation stone
Black alkene.
7, the E44 epoxy resin base graphene of preparation is added 1% polysulfide rubber, 0.1% levelling agent, 0.2%
It after defoaming agent etc. carries out high-speed stirred, is packed, is prepared into the A group of E44 epoxy resin-matrix graphene corrosion protection abrasion resistant erosion coating
Point.
8, it is 593 curing agent that curing agent, which selects the trade mark, is prepared into E44 epoxy resin-matrix graphene corrosion protection abrasion resistant after packaging
Lose the B component of coating.
9, E44 epoxy resin-matrix Anti-corrosion graphite anti scuffing coating is made of component A and B component, when in use by component A with
The ratio of B component be 100 to 12, after mixing can brushing alkene to body surface solidify play corrosion protection abrasion resistant lose protective effect.
10, the application and technical performance of E44 resin base graphene corrosion protection abrasion resistant erosion coating
1. epoxy resin E44 is a kind of important thermosetting resin kind.Especially because it is with excellent physical mechanical
Performance, electrical insulation capability, resistance to chemical corrosion, heat-resisting and adhesive property.The epoxy resin gluing prepared with epoxy resin E44
Agent is known as the title of " all-purpose adhesive ", can be widely applied to chemical industry, light industry, water conservancy, traffic, machinery, electronics.Its modest viscosity, dosage
Maximum is widely used in coating, adhesive etc..
2. the E44 resin base graphene anti scuffing coating prepared by embodiment (four), in addition to excellent with above-mentioned items
Outside performance, following performance indexes is better than the performance indicator of E44 resin cured matter itself, as adhesion strength is greater than
24MPa, compression strength are greater than 90MPa, and wear-resisting property is ground 7 days through the punching of HKCM-120 high speed concrete anti-abrasion tester sample,
Waste is zero, and acidproof, alkaline-resisting, salt resistant character all increases substantially.
Conclusion: special performance possessed by graphene makes it before every field all presents huge potentiality and application
Scape has become the hot spot of domestic and international scientific research at present.However, the application of graphene and its composite material in paint field, also
Key technology problems need to solve, and how to realize extensive, the inexpensive graphene coating for preparing high quality, and realize
The Modulatory character of its quality.The innovation of graphene coating functional modification method, study graphene and polymer compatibility and
Its mechanism of action in coating system provides fundamental basis for its application in paint field, realizes graphene-polymer
The industrially scalable of nanocomposite is combined to and its becomes in the industrial application of paint field study in coating industry
Main flow direction.Currently, there are three types of the preparation methods of graphene coating: (1) melt blending.By polymer and graphene under high temperature
Melting mixing can avoid using organic solvent；(2) solution blending.Select suitable solvent first to dissolve polymer, then with graphene
Homogeneous dispersion mixing, finally removes solvent；(3) in-situ polymerization.By graphene dispersion into polymer monomer, monomer-occurs
It polymerize between monomer, between monomer-graphene-monomer, raw material is usually modified graphene, to improve the two compatibility.First two
Method is to enter polymer to form intercalated compound inside graphene, and the 3rd kind of method is to grow polymer on graphene,
There is the problem for effectively making graphene uniform dispersion, uniting in three, and complex process, high production cost are difficult to realize
Industrial scale production.And the present invention we be defined as " one-step method ", exactly expanded graphite is directly mixed with resin, by stirring
It mixes, grind, ultrasonic grind removing, making to polymerize between monomer-monomer, between monomer-graphene-monomer, direct One-step production
Graphene coating out thoroughly solves the problems, such as the phenomenon that graphene is united in coating and cannot be mass produced, and produces work
Skill is simple, easy to operate, and production capacity is big, and quality is stablized, and reduces production cost, and complete solvent free produces Environmental Safety, can be with
Realize industrial scale production.
The resin base graphene anti scuffing coating prepared by above-mentioned four kinds of embodiments, it is characterised in that remain resin
Every excellent performance.And adhesive property, compression strength and wearability are improved, as adhesion strength is both greater than 24MPa, compression strength
Greater than 80MPa, wear-resisting property is ground 7 days through the punching of HKCM-120 high speed concrete anti-abrasion tester sample, waste zero.It is resistance to
Acid, alkali, salt function admirable more demonstrate the feasibility of One-step production resin base graphene.
Claims (8)
1. a kind of preparation method of graphene coating, which is characterized in that mixed liquor is made in water and resin, by mass parts, every
0.2~5 part of expanded graphite is added in 100 portions of mixed liquors, by being carried out after stirring, grind uniformly with supersonic cell disintegrating apparatus
It crushes, then by vacuum distillation and freeze-drying, is prepared into graphene coating；
The freeze-drying is first at temperature -5~-8 DEG C, and 1~2h of pre-freeze makes free water cure, then temperature -5~-8 DEG C,
It is dry under the conditions of vacuum degree≤20Pa, until moisture≤0.5% in resin base graphene；It is prepared into resin base graphene；
The temperature of material is controlled at 35 DEG C hereinafter, grinding time is 1~8 hour in the crushing process.
2. preparation method as described in claim 1, which is characterized in that the mixed liquor be water-soluble resin aqueous solution and/
Or emulsifying resins.
3. preparation method as claimed in claim 2, which is characterized in that when mixed liquor is the aqueous solution of water-soluble resin, press
Mass parts, every 100 portions of mixed liquors are made of 20~80 parts of water-soluble resin and 80~20 parts of water.
4. preparation method as claimed in claim 2, which is characterized in that the emulsifying resins the preparation method is as follows: press quality
Part, after 20~60 parts of non-water-soluble resin, 30~10 parts of water-soluble resin, 50~30 parts of water and 0.1~1 part of emulsifier mixing
It is stirred, obtains emulsifying resins.
5. preparation method as claimed in claim 4, which is characterized in that the mixing speed is 1800 turns/min or more, stirring
Time is 1~2 hour.
6. preparation method as described in claim 1, which is characterized in that the viscosity of the mixed liquor of control water and resin exists
100mPas or less.
7. a kind of graphene coating, which is characterized in that obtained by the described in any item preparation methods of claim 1~6.
8. graphene coating as claimed in claim 7, which is characterized in that also add toughener in the graphene coating, disappear
Infusion and levelling agent.
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| CN109666370B (en) * | 2017-10-16 | 2021-08-24 | 山东欧铂新材料有限公司 | Conductive anticorrosive paint containing graphene and preparation method thereof |
| CN108630338B (en) * | 2018-03-08 | 2019-03-22 | 北京地泽科技有限公司 | A kind of method, apparatus for producing graphene conductive slurry in batches and graphene conductive slurry prepared therefrom |
| CN110003760A (en) * | 2018-12-21 | 2019-07-12 | 常熟市方塔涂料化工有限公司 | A kind of epoxy conductive paint |
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