CN107033732A - 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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- CN107033732A CN107033732A CN201611116065.8A CN201611116065A CN107033732A CN 107033732 A CN107033732 A CN 107033732A CN 201611116065 A CN201611116065 A CN 201611116065A CN 107033732 A CN107033732 A CN 107033732A
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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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- 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
- 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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- 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
- 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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- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
The invention discloses a kind of graphene coating and preparation method thereof, the preparation method of graphene coating comprises the following steps：Mixed liquor is made in 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, grinding uniformly with supersonic cell disintegrating apparatus, then by vacuum distillation and freeze-drying, graphene coating is prepared into.This method also simplify the production technology of graphite alkenes coating, reduce 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 technology
With the fast development of all trades and professions, the requirement more and more higher to industry.Water conservancy and hydropower, space flight and aviation, ship code
First-class grade has new requirement to building and the protection of the appearance water-tight corrosion-proof anti scuffing of equipment, the work of the various protection run into
It is extremely complex that condition all becomes.In addition, high-tech develop it is also proposed new requirement, such as space flight and aviation to surface protecting material
, naval vessels ship, deep sea submarine, deep-sea drilling with exploitation etc. develop rapidly, also to the technology of surface protection coating material
Performance requirement more and more higher, some requirements are heat-resisting, some requirement resistance to erosion, wear-resisting, and the requirement also having 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-environment such as high temperature hyperpyrexia, deep-etching is seen everywhere.Accordingly, it would be desirable to which one kind is safe efficient and adapts to various works
The coating of the various complex environments of condition requirement, to prevent the corrosion of all kinds of water environments, acid or alkali environment to structure, also wanting can be in height
Used under temperature or low temperature condition.The resin base graphene that we develop now, utilizes the distinctive various superior functions of graphene, solution
Determine the application problem of appeal, it is possible to use the technical performance of various resins in itself, produced and various be adapted to various operating modes
Resin base graphene corrosion protection abrasion resistant loses coating, improves and improve the performance of resin, and with the skill of good wear-resisting antiscour
Art performance, water-tight corrosion-proof effect is very good.
Graphene be it is found that the first by the material of individual layer atomic building, be interconnected to hexagonal between carbon atom
Grid, electric conductivity, mechanical performance are all very excellent, and the graphene for usually having the title of " dark fund " is 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 achievement in research of 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 property indices of the resin of fat and resistance to various corrosive mediums suffer from great raising, and this utilizes this high-performance for us
Resin and graphene provide more choices scope with the use of producing various high performance coating materials.
At present, the domestic graphite alkenes corrosion protection abrasion resistant corrosion material developed, mainly use the graphene that has produced and
Mixed with resin, produces graphite alkenes coating material.It includes following 3 kinds of preparation methods：(1) melt blending.Will be poly- under high temperature
Compound and graphene melting mixing, can avoid using organic solvent；(2) solution blending.Suitable solvent is selected first to dissolve polymerization
Thing, 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 both
Compatibility.First two method is polymer is internally formed intercalated compound into graphene, and the 3rd kind of method is polymer is existed
Grown on graphene.There is the problem for effectively disperseing graphene uniform, uniting in three, have impact on graphite alkenes coating
Various performances, and complex process, production cost are high, limit the development of graphite alkenes coating.
The content of the invention
It is an object of the invention to the method that the corrosion protection abrasion resistant for the manufacture graphite alkenes for studying a kind of " one-step method " loses coating,
The problem that graphene is difficult to substantially uniformity distribution in resin is solved, manufacturing cost is reduced, manufacture is cheap and various high performance
Graphite alkenes corrosion protection abrasion resistant loses coating, to be protected 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 resource consumption, is that the development of national economy contributes.
The technical scheme is that there is provided a kind of preparation method of graphene coating " one-step method ", by water and resin-made
Into mixed liquor, by mass parts, 0.2~5 part of expanded graphite is added in every 100 portions of mixed liquors, by being used after stirring, grinding 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 preparation method of the emulsifying resins is as follows：By mass parts：By 20~60 parts of non-water-soluble resin, water
It is stirred after 30~10 parts of soluble resin, 0.1~1 part of mixing of 50~30 parts of water and emulsifying agent, that is, emulsifying resins is made.
Preferably, the mixing speed is 1800 turns/more than min, and mixing time is 1~2 hour.
Preferably, freeze-drying is that 1~2h of pre-freeze makes free water cure first at temperature -5~-8 DEG C, then in temperature -5
~-8 DEG C, dry under the conditions of vacuum≤20Pa, moisture≤0.5% into resin base graphene；Prepare resin base graphite alkene.
Preferably, the temperature control of material is below 35 DEG C in crushing process, and grinding time is 1~8 hour.
Preferably, the viscosity of control water and resin mixture liquor is in below 100mPas.
Expanded graphite preferably can effectively disperse in low viscosity mixed liquor.Water can increase ultrasonic wavelength, expand broken
Broken scope.Resin has certain viscosity, the active force collective effect with ultrasonic wave, it is more preferable to expanded graphite sheared,
Peel off, crush.In addition, also having put into big gun as explosive because the minute bubbles of the cavitation formation of ultrasonic wave are wrapped up by resin film
In cylinder, form 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 produces high temperature, high pressure, while producing shock wave, is effectively improved ultrasonic wave
Mechanical effect, improve the efficiency that expanded graphite is prepared into graphene in mixing liquid.
Preferably, can be according to working condition requirement by above-mentioned process for producing, it is reasonable to be carried out from corresponding various kinds of resin
Collocation mixing, produces the resin base corrosion protection abrasion resistant erosion coating of various performance requirements.
The present invention further provides a kind of by above-mentioned preparation method acquisition graphene coating.
Preferably, toughener, defoamer and levelling agent are also added in the graphene coating.
The graphene cold coating of the present invention, is not that finished product graphene is added to be stirred in resin to form, but
It is added to by expanded graphite in resin, crush and disperse, make expanded graphite with resin in the case where mixing, make expansion stone
Ink changes into graphene.
Expanded graphite and resin mixture liquor of the invention preparation, by thin with ultrasonic wave after high-speed stirred, grinding uniformly
Born of the same parents' disintegrating apparatus is crushed again by vacuum distillation and freeze-drying, is prepared into graphene cold coating.Because containing in resin
A certain proportion of water, various achievements in research show that ultrasonic wave can produce bigger big gun in the case of having water and break power.In addition, resin
It is both the dispersion liquid of graphene, is the remover of expanded graphite again.Expanded graphite breaks power in ultrasonic wave big gun and resin viscosity is produced
Shearing force collective effect under, expanded graphite is slowly crushed, tear, peeled off and as less than 10 layers of graphene, 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 in the consumption that the graphene cold coating of preparation is formulated by the standard empirical of cold coating
Expect that (such as toughener, defoamer, levelling agent) is carried out after high-speed stirred, you can be prepared into the component A in coating system.Again with consolidating
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, its volume is calculated according to the epoxide number of resin.
The beneficial effects of the invention are as follows expanded graphite breaks the common of the shearing force that power and resin viscosity are produced in ultrasonic wave big gun
Under effect, expanded graphite is slowly crushed, tear, peeled off and turns into less than 10 layers of graphene, and is evenly distributed in resin
With in the mixing liquid of water, this method also simplify the production technology of graphite alkenes coating, reduce production cost；And it is raw
The various performances of the graphite alkenes coating of production are improved.
Embodiment
With reference to embodiment, the invention will be further described.
The present embodiments relate to a kind of graphene cold coating and its preparation method of one-step method, and it is available with the technology
Various water-soluble resins and non-water-soluble resin are prepared into various graphene coating component As, then are prepared with curing agent component
Into various anti scuffing anticorrosive paint series of products.Water-soluble resin is using glycolylurea epoxide resin and water soluble phenol resin as implementation
Example, is prepared into hydantoin epoxy base graphene anti scuffing coating using the technology and water soluble phenol resin base graphene anti scuffing is applied
Material, non-water-soluble resin is so that 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-matrixes graphene anti scuffing coating and 6002 epoxy radicals graphene corrosion protection abrasion resistants erosion coating.Respectively
Material in embodiment is with mass parts or mass percentage.Glycolylurea resin is the abbreviation of glycolylurea epoxide resin.
Embodiment (one)
Glycolylurea resin base graphene corrosion protection abrasion resistant erosion Paint Examples are prepared into glycolylurea epoxide resin to comprise the following steps：
1st, glycolylurea resin is dissolved in water, optimal proportion is 60 parts of glycolylurea resin, and then 40 parts of water add and account for resin and water
0.5% expanded graphite of gross mass.Control the viscosity of water and resin mixture liquor in below 100mPas, expanded graphite is low
Preferably can effectively it disperse in viscosity mixed liquor.Water can increase ultrasonic wavelength, expand broken scope.Resin has certain
Viscosity, the active force collective effect with ultrasonic wave is more preferable to expanded graphite to be sheared, peeled off, and crushes.In addition, because of ultrasound
The minute bubbles of the cavitation formation of ripple have also been put into gun barrel by resin film parcel as explosive, are formd many small " fried
Bullet ", these " bombs " can constantly be moved with the vibration of surrounding medium, grow up or suddenly big gun fry.Surrounding liquid is unexpected when big gun is fried
Pour bubble and produce high temperature, high pressure, while producing shock wave, be effectively improved the mechanical effect of ultrasonic wave.
2nd, glycolylurea epoxide resin, water, expanded graphite stir compound by homogenizer, mixing time is most
Good is 60 minutes, is then ground with grinder, and grinding Best Times are 120 minutes.
3rd, the compound stirred is put into ultrasonic cell-break equipment and crushed, in shattering process, broken
Broken drum is peripherally equipped with cooling system, and excessively stream cooling is carried out with normal-temperature water, makes the temperature control of the material crushed at 35 DEG C
Hereinafter, it is -8 hours 1 hour to crush the time, mixed liquor is prepared into the mixed liquor of glycolylurea resin, water, graphene.
4th, the mixed liquor of glycolylurea epoxide resin, water, graphene is sampled, whether detection expanded graphite conversion graphene is complete
And the detection of the graphene number of plies and be evenly distributed state of the graphene in resin：
1. whether the complete and graphene number of plies is detected expanded graphite conversion graphene：The mixing for taking 500 grams of steps 3 to prepare
Liquid, the water for adding 50% stirs, then the mixed liquor of water mixing is poured into filter-press (pressure is 0.20MPa, filter membrane
Aperture is 20 μm) after filtering, resin stays the liquid in the filter, being filtrated to get to be water and the mixed liquor of graphene, then leads to
Cross and be dried to obtain graphene, obtained graphene is detected by the Japanese Shimadzu scanning probe microscopies of SPM-9700, led to
Cross detection expanded graphite to crush completely, the graphene number of plies being filtrated to get is less than 10 layers.
2. uniformity detection of the graphene in resin：The mixed liquor sample of 100 Kehaiyin medicine resins, water, graphene is taken to enter
Row drying, makes moisture be less than 1%, and then the glycolylurea resin, graphene mixed liquor that are dried to obtain are applied to and throw what film was crossed
On silicon chip, 20 microns of coating layer thickness is detected with metallographic microscope LV100D, is detected graphene and is distributed in resin
It is even.
5th, the mixed liquor crushed is carried out vacuum decompression distillation, carries out preliminary hydro-extraction, be down to water content in compound
6%.
6th, the compound after vacuum decompression distillation, carries out vacuum freeze drying, specifically followed by vacuum freeze drier
Step is：First at temperature -5~-8 DEG C, 1~2h of pre-freeze makes its free water cure, prevents from bubbling, shrinks, then in temperature -5
~-8 DEG C, dry under the conditions of vacuum≤20Pa, moisture≤0.5% into resin base graphene；It is prepared into glycolylurea resin base
Graphene.
7th, the glycolylurea resin base graphene of preparation is added 1% polysulfide rubber, 0.1% levelling agent, 0.2% froth breaking
Agent etc. is carried out after high-speed stirred, is packed, and is prepared into the component A that glycolylurea resin base graphene corrosion protection abrasion resistant loses coating.
8th, curing agent selects 650 polyurethane curing agents, is prepared into the B groups that glycolylurea resin base graphene corrosion protection abrasion resistant loses coating
Point.
9th, glycolylurea resin base graphene corrosion protection abrasion resistant erosion coating is made up of component A and B component, by component A and B groups when using
The ratio divided is 100 to 35, just can be brushed to after body surface, solidification after being well mixed and play corrosion protection abrasion resistant erosion protective effect.
10th, the application of glycolylurea resin base graphene corrosion protection abrasion resistant erosion coating and technical performance
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. heat endurance is good, and heat resistance is high.More than 5000h 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 difficult jaundice and efflorescence 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 protruded under high voltage and super-pressure, especially with excellent arc resistance and tracking-resistant vestige
Property, it can be used as high voltage withstanding insulating device.
5. polarity is very strong, viscosity is low, thus have to glass fibre, carbon fiber and a variety of fillers good wetting power and
Cementability, can add mass filler on the premise of manufacturability is not reduced, so that linear expansion coefficient and cost reduction.
6. small toxicity.Belong to the coating of environment-friendly type, Non-toxic adhesive can be made.
7. the glycolylurea resin base graphene anti scuffing coating prepared by embodiment (one), except excellent with above-mentioned items
Outside performance, following property indices are better than the performance indications of glycolylurea epoxide resin solidfied material in itself, and such as adhesion strength is big
In 24MPa, compression strength is more than 100MPa, and anti-wear performance is through HKCM-120 high speed concrete anti-abrasion testers sample punching mill 7
My god, waste is zero, and acidproof, alkaline-resisting, salt resistant character is all increased substantially.
Embodiment (two)
Water soluble phenol resin base graphene corrosion protection abrasion resistant erosion Paint Examples are prepared into water soluble phenol resin to be included
Following steps：
1st, water soluble phenol resin is dissolved in water, optimal proportion is 60 parts of water soluble phenol resin, 40 parts of water, Ran Houjia
Enter to account for resin and 0.5% expanded graphite of water gross mass.
2nd, water soluble phenol resin, water, expanded graphite stir compound by homogenizer, mixing time
Most preferably 60 minutes, then it is ground with grinder, grinding Best Times are 120 minutes.
3rd, the compound stirred is put into ultrasonic cell-break equipment and crushed, in shattering process, broken
Broken drum is peripherally equipped with cooling system, and excessively stream cooling is carried out with normal-temperature water, makes the temperature control of the material crushed at 35 DEG C
Hereinafter, it is -8 hours 1 hour to crush the time, preferably 1.5 hours, mixed liquor is prepared into the mixing of glycolylurea resin, water, graphene
Liquid.
4th, the mixed liquor of water soluble phenol resin, water, graphene is sampled, whether detection expanded graphite conversion graphene is complete
The detection of the complete and graphene number of plies and be evenly distributed state of the graphene in resin：
1. whether the complete and graphene number of plies is detected expanded graphite conversion graphene：The mixing for taking 500 grams of steps 3 to prepare
Liquid, the water for adding 50% stirs, then the mixed liquor of water mixing is poured into homemade filter-press (pressure is 0.20MPa,
It is 20 μm to filter membrane aperture) after filtering, resin stays the mixing that the liquid in the filter, being filtrated to get is water and graphene
Liquid, then by being dried to obtain graphene, obtained graphene is carried out by the Japanese Shimadzu scanning probe microscopies of SPM-9700
Detection, by detecting that expanded graphite is crushed completely, the graphene number of plies being filtrated to get is less than 10 layers.
2. uniformity detection of the graphene in resin：The mixed liquor sample of 100 grams of phenolic resin, water, graphene is taken to enter
Row drying, makes moisture be less than 1%, and then the phenolic resin, graphene mixed liquor that are dried to obtain are applied to and throw what film was crossed
On silicon chip, 20 microns of coating layer thickness is detected with metallographic microscope LV100D, is detected graphene and is distributed in resin
It is even.
5th, the mixed liquor crushed is carried out vacuum decompression distillation, carries out preliminary hydro-extraction, be down to water content in compound
6%.
6th, the compound after vacuum decompression distillation, carries out vacuum freeze drying, specifically followed by vacuum freeze drier
Step is：First at temperature -5~-8 DEG C, 1~2h of pre-freeze makes its free water cure, then temperature -5~-8 DEG C, vacuum≤
Dried under the conditions of 20Pa, moisture≤0.5% into resin base graphene；It is prepared into water soluble phenol resin base graphene.
7th, the water soluble phenol resin base graphene of preparation add 1% polysulfide rubber, 0.1% levelling agent, 0.2%
Defoamer etc. carry out after high-speed stirred, packed, be prepared into water soluble phenol resin base graphene corrosion protection abrasion resistant erosion coating
Component A.
8th, curing agent selects hexamethylenetetramine.The B of coating is lost as water soluble phenol resin base graphene corrosion protection abrasion resistant
Component.
9th, water soluble phenol resin base graphene corrosion protection abrasion resistant erosion coating is made up of component A and B component, by A groups when using
The ratio divided with B component is 100 to 8, just can be brushed to after body surface, solidification after being well mixed and play corrosion protection abrasion resistant erosion protection work
With.
10th, the application of water soluble phenol resin base graphene corrosion protection abrasion resistant erosion coating and technical performance
1. its characteristic of water soluble phenol resin is a large amount of organic molten to be replaced with water, eliminates pollution, reduces cost.As lamination
The binding agent of plate and various coating compositions.
2. the water soluble phenol resin base graphene anti scuffing coating prepared by embodiment (two), except with above-mentioned each
Outside item premium properties, following property indices are better than the performance indications of water soluble phenol resin solidfied material in itself, such as viscous
Knotting strength is more than 24MPa, and compression strength is more than 100MPa, and anti-wear performance is tried through HKCM-120 high speeds concrete anti-abrasion tester
Sample punching mill 7 days, waste is zero, and resistance to saltfog can bring up 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
Material embodiment comprises the following steps：
1st, 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, preferably 40 parts of 6002 epoxy resin of its quality proportioning：30-10 parts of water-solubility hydantoin epoxy resins, preferably 20 parts：
50-30 parts of water, preferably 40 parts.LG-DOW DOWFAX 2A1 emulsifying agents volume is the 0.1%-1% of resin water inventory, preferably
0.5%.It is stirred after resin, water, emulsifying agent are mixed through homogenizer (speed of agitator is 2000 turns/min), during stirring
Between be 1-2 hours, preferably 1.5 hours.6002 emulsifying resins are made.
2nd, divide in mass ratio, 100 parts of 6002 emulsifying resins are made, plus account for the expanded graphite of emulsifying resins 0.5%.
3rd, 6002 emulsion epoxy resins, expanded graphite stir compound by homogenizer, mixing time
Most preferably 60 minutes, then it is ground with grinder, grinding Best Times are 120 minutes.
4th, the compound stirred is put into ultrasonic cell-break equipment and crushed, in shattering process, broken
Broken drum is peripherally equipped with cooling system, and excessively stream cooling is carried out with normal-temperature water, makes the temperature control of the material crushed in 350C
Hereinafter, it is -8 hours 1 hour to crush the time, preferably 1.5 hours, mixed liquor is prepared into the mixing of 6002 resins, water, graphene
Liquid.
5th, 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. whether the complete and graphene number of plies is detected expanded graphite conversion graphene：Take 6002 standby resins of 500 restraints, stone
The mixing liquid of black alkene, water, the water for adding 50% is stirred, then the mixed liquor of water mixing is poured into homemade filter-press
(pressure is 0.20MPa, and filtering membrane aperture is 20 μm) after filtering, resin stays the liquid in the filter, being filtrated to get to be water
With the mixed liquor of graphene, then by being dried to obtain graphene, obtained graphene is passed through the Japanese Shimadzus of SPM-9700 and scanned
Probe microscope is detected that, by detecting that expanded graphite is crushed completely, the graphene number of plies being filtrated to get is less than 10 layers.
2. uniformity detection of the graphene in resin：100 gram of 6002 resin, water, the mixed liquor sample of graphene is taken to enter
Row drying, makes moisture be less than 1%, and then 6002 resins, graphene mixed liquor that are dried to obtain are applied to and throw what film was crossed
On silicon chip, 20 microns of coating layer thickness is detected with metallographic microscope LV100D, is detected graphene and is distributed in resin
It is even.
6th, the mixed liquor crushed is carried out vacuum decompression distillation, carries out preliminary hydro-extraction, be down to water content in compound
6%.
7th, the compound after vacuum decompression distillation, carries out vacuum freeze drying, specifically followed by vacuum freeze drier
Step is：First at temperature -5~-8 DEG C, 1~2h of pre-freeze makes its free water cure, prevents from bubbling, shrinks, then in temperature -5
~-8 DEG C, dry under the conditions of vacuum≤20Pa, moisture≤0.5% into resin base graphene；It is prepared into 6002 resin bases
Graphene.
8th, 6002 resin base graphenes of preparation are added 1% polysulfide rubber, 0.1% levelling agent, 0.2% froth breaking
Agent etc. is carried out after high-speed stirred, is packed, and is prepared into the component A that 6002 resin base graphene corrosion protection abrasion resistants lose coating.
9th, curing agent, which is selected, is prepared into the erosion of 6002 resin base graphene corrosion protection abrasion resistants after the curing agent that the trade mark is 593, packaging
The B component of coating.
10th, 6002 resin base graphene corrosion protection abrasion resistants erosion coating is made up of component A and B component, when in use by component A and
The ratio of B component is 100 to 12, and body surface solidification just can be brushed to after being well mixed and plays corrosion protection abrasion resistant erosion protective effect.
11st, the application of 6002 resin base graphene corrosion protection abrasion resistants erosion coating and technical performance
1. 6002 epoxy resin, its viscosity is very low, only 1/10th of E-51 epoxy resin, good fluidity, easily
Construction, solidfied material still keeps a series of excellent performances of ordinary epoxy resin.It is usually used in coating, cast, composite and glues
Close.
2. 6002 epoxy resin because viscosity it is low, solvent-free type environment-friendly coating can be made.
3. the 6002 resin base graphene anti scuffing coating prepared by embodiment (three), except excellent with above-mentioned items
Outside performance, following property indices are better than the performance indications of 6002 resin cured matters in itself, and such as adhesion strength is more than
24MPa, compression strength is more than 80MPa, and anti-wear performance is ground 7 days through the punching of HKCM-120 high speed concrete anti-abrasion testers sample,
Waste is zero, and resistant abrasion ability is stronger than the resistant abrasion ability of tungsten carbide sprayed coating and titanium alloy surface, acidproof, alkaline-resisting, salt tolerant
Performance is all increased 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 graphenes corrosion protection abrasion resistant
Material embodiment comprises the following steps：
1st, E44 epoxy resin is prepared into E44 epoxy emulsifying resins.The technology path of the emulsifying resins of preparation is as follows：Its
20-60 parts, preferably 35 parts of E44 epoxy resin of quality proportioning：30-10 parts of water-solubility hydantoin epoxy resins, preferably 25 parts：Water
50-30 parts, preferably 40 parts.LG-DOW DOWFAX 2A1 emulsifying agents volume is the 0.1%-1% of resin water inventory, preferably
0.5%.It is stirred after resin, water, emulsifying agent are mixed through homogenizer (speed of agitator is 2000 turns/min), during stirring
Between be 1-2 hours, preferably 1.5 hours.E44 epoxy emulsifying resins are made.
2nd, divide in mass ratio, 100 parts of E44 epoxies emulsifying resins are made, plus account for the expansion stone of emulsifying resins quality 0.5%
Ink.
3rd, E44 emulsion epoxy resins, expanded graphite are mixed, compound stirred by homogenizer, stirred
Time optimal is 60 minutes, is then ground with grinder, and grinding Best Times are 120 minutes.
4th, the compound stirred is put into ultrasonic cell-break equipment and crushed, in shattering process, broken
Broken drum is peripherally equipped with cooling system, and excessively stream cooling is carried out with normal-temperature water, makes the temperature control of the material crushed in 350C
Hereinafter, it is -8 hours 1 hour to crush the time, preferably 1.5 hours, mixed liquor is prepared into E44 epoxy resin, water, graphene
Mixed liquor.
5th, the mixed liquor of the E44 epoxy resin, water, graphene of preparation 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 the complete and graphene number of plies is detected expanded graphite conversion graphene：Take the E44 asphalt mixtures modified by epoxy resin that 500 restraints are standby
Fat, graphene, the mixing liquid of water, the water for adding 50% are stirred, then the mixed liquor of water mixing is poured into filter-press
(pressure is 0.20MPa, and filtering membrane aperture is 20 μm) after filtering, resin stays the liquid in the filter, being filtrated to get to be water
With the mixed liquor of graphene, then by being dried to obtain graphene, obtained graphene is passed through the Japanese Shimadzus of SPM-9700 and scanned
Probe microscope is detected that, by detecting that expanded graphite is crushed completely, the graphene number of plies being filtrated to get is less than 10 layers.
2. uniformity detection of the graphene in resin：Take the mixed liquor sample of 100 grams of E44 epoxy resin, water, graphene
It is dried, moisture is less than 1%, the E44 epoxy resin, graphene mixed liquor that are dried to obtain then are applied to throwing film
On the silicon chip crossed, 20 microns of coating layer thickness is detected with metallographic microscope LV100D, is detected graphene and is distributed in resin
Uniformly.
6th, the mixed liquor crushed is carried out vacuum decompression distillation, carries out preliminary hydro-extraction, be down to water content in compound
6%.Then the compound after vacuum decompression being distilled, vacuum freeze drying, specific steps are carried out using vacuum freeze drier
For：First at temperature -5~-8 DEG C, 1~2h of pre-freeze makes its free water cure, prevents from bubbling, shrinks, then in temperature -5~-8
DEG C, dry under the conditions of vacuum≤20Pa, moisture≤0.5% into resin base graphene；It is prepared into E44 epoxy resin foundation stones
Black alkene.
7th, the E44 epoxy resin bases graphene of preparation add 1% polysulfide rubber, 0.1% levelling agent,
0.2% defoamer etc. is carried out after high-speed stirred, is packed, and is prepared into the erosion painting of E44 epoxy resin-matrix graphenes corrosion protection abrasion resistant
The component A of material.
8th, curing agent is prepared into E44 epoxy resin-matrix graphene corrosion protection abrasion resistants after selecting the curing agent that the trade mark is 593, packaging
Lose the B component of coating.
9th, E44 epoxy resin-matrixes Anti-corrosion graphite anti scuffing coating is made up of component A and B component, when in use by component A with
The ratio of B component is 100 to 12, it is well mixed after just can brushing alkene play corrosion protection abrasion resistant to body surface solidification and lose protective effect.
10th, the application of E44 resins base graphene corrosion protection abrasion resistant erosion coating and technical performance
1. epoxy resin E44 is a kind of important thermosetting resin kind.Especially because it has excellent physical mechanical
Performance, electrical insulation capability, resistance to chemical corrosion, heat-resisting and adhesive property.The epoxy resin prepared with epoxy resin E44 is gluing
Agent have the title of " all-purpose adhesive ", can be widely applied to chemical industry, light industry, water conservancy, traffic, machinery, electronics.Its modest viscosity, consumption
Maximum, is widely used in coating, adhesive etc..
2. the E44 resin base graphene anti scuffing coating prepared by embodiment (four), except excellent with above-mentioned items
Outside performance, following property indices are better than the performance indications of E44 resin cured matters in itself, and such as adhesion strength is more than
24MPa, compression strength is more than 90MPa, and anti-wear performance is ground 7 days through the punching of HKCM-120 high speed concrete anti-abrasion testers sample,
Waste is zero, and acidproof, alkaline-resisting, salt resistant character is all increased substantially.
Conclusion：The special performance that graphene has makes it before every field all presents huge potentiality and application
Scape, turns into the focus of domestic and international scientific research at present.However, the application of graphene and its composite in paint field, also has
Key technology problems need to solve, how to realize it is extensive, inexpensive prepare high-quality graphene coating, and realize
The Modulatory character of its quality.The innovation of graphene coating functional modification method, research graphene and polymer compatibility and
Its mechanism of action in coating system, is that it provides fundamental basis in the application of paint field, realizes graphene-polymer
The industrially scalable of nano composite material is combined to and its turns into the research in coating industry in the commercial application of paint field
Main flow direction.At present, the preparation method of graphene coating has three kinds：(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 is mixed, and finally removes solvent；(3) in-situ polymerization.By graphene dispersion into polymer monomer, generation monomer-
It polymerize between monomer, between monomer-graphene-monomer, raw material is usually modified graphene, to improve both compatibilities.First two
Method is polymer is internally formed intercalated compound into graphene, and the 3rd kind of method is polymer is grown on graphene,
There is the problem for effectively disperseing graphene uniform, uniting, and complex process in three, production cost is high, is difficult to realize
Industrial scale is produced.And the present invention we be defined as " one-step method ", directly mixed with resin exactly by expanded graphite, by stirring
Mix, grind, ultrasonic grind is peeled off, making between monomer-monomer, polymerize between monomer-graphene-monomer, direct One-step production
Go out graphene coating, thoroughly solve the phenomenon that graphene is united in coating and the problem that can not be mass produced, produce work
Skill is simple, easy to operate, and production capacity is big, steady quality, reduces production cost, and complete solvent free produces Environmental Safety, can be with
Realize that industrial scale is produced.
The resin base graphene anti scuffing coating prepared by above-mentioned four kinds of embodiments, it is characterised in that remain resin
Every premium properties.And adhesive property, compression strength and wearability are improved, such as adhesion strength is both greater than 24MPa, compression strength
More than 80MPa, anti-wear performance is ground 7 days through the punching of HKCM-120 high speed concrete anti-abrasion testers sample, and waste is zero.It is resistance to
Acid, alkali, salt function admirable, more demonstrate the feasibility of One-step production resin base graphene.
Claims (10)
1. a kind of preparation method of graphene coating, it is characterised 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, grinding uniformly with supersonic cell disintegrating apparatus
Crush, then by vacuum distillation and freeze-drying, be prepared into graphene coating.
2. preparation method as claimed in claim 1, it is characterised in that the mixed liquor for water-soluble resin the aqueous solution and/
Or emulsifying resins.
3. preparation method as claimed in claim 2, it is characterised in that when mixed liquor is the aqueous solution of water-soluble resin, press
Mass parts, every 100 portions of mixed liquors are made up of 20~80 parts of water-soluble resin and 80~20 parts of water.
4. preparation method as claimed in claim 2, it is characterised in that the preparation method of the emulsifying resins is as follows：By quality
Part, after 20~60 parts of non-water-soluble resin, 30~10 parts of water-soluble resin, 0.1~1 part of mixing of 50~30 parts of water and emulsifying agent
It is stirred, that is, emulsifying resins is made.
5. preparation method as claimed in claim 4, it is characterised in that the mixing speed is 1800 turns/more than min, stirring
Time is 1~2 hour.
6. preparation method as claimed in claim 1, it is characterised in that freeze-drying is the pre-freeze 1 first at temperature -5~-8 DEG C
~2h, makes free water cure, then is dried under the conditions of temperature -5~-8 DEG C, vacuum≤20Pa, to resin base graphene reclaimed water
Divide≤0.5%；Prepare resin base graphite alkene.
7. preparation method as claimed in claim 1, it is characterised in that in crushing process the temperature control of material 35 DEG C with
Under, grinding time is 1~8 hour.
8. preparation method as claimed in claim 1, it is characterised in that the viscosity of the mixed liquor of control water and resin exists
Below 100mPas.
9. a kind of graphene coating, it is characterised in that obtained as the preparation method described in any one of claim 1~8.
10. graphene coating as claimed in claim 9, it is characterised in that toughener is also added in the graphene coating, is disappeared
Infusion and levelling agent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108630338A (en) * | 2018-03-08 | 2018-10-09 | 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 |
| CN109666370A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of conductive anti-corrosion coating and preparation method thereof containing graphene |
| 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 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015529A (en) * | 2008-02-28 | 2011-04-13 | 巴斯夫欧洲公司 | Graphite nanoplatelets and compositions |
| CN103642361A (en) * | 2013-12-10 | 2014-03-19 | 北京新立机械有限责任公司 | Water-soluble nano camouflage paint and preparation method thereof |
| CN104293195A (en) * | 2014-09-22 | 2015-01-21 | 铜陵市新泰电容电器有限责任公司 | Electrolytic capacitor shell cooling coating containing rare-earth elements |
| CN104640808A (en) * | 2011-11-14 | 2015-05-20 | 沃尔贝克材料有限公司 | Graphene containing compositions |
| CN105001597A (en) * | 2015-08-12 | 2015-10-28 | 哈尔滨理工大学 | Needle-shaped nanometer aluminium oxide/graphene oxide/epoxy resin composite and preparation method |
| CN105017831A (en) * | 2014-04-18 | 2015-11-04 | 新材料与产业技术北京研究院 | Composition for water-based electric heating nano paint, water-based electric heating nano paint as well as preparation method and application of water-based electric heating nano paint |
| JP2016029004A (en) * | 2014-07-18 | 2016-03-03 | 積水化学工業株式会社 | Method for manufacturing flaky graphite, flaky graphite, flaky graphite dispersion, and flaky graphite-resin composite material |
| WO2016045035A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene |
| CN105505108A (en) * | 2015-11-27 | 2016-04-20 | 沈阳顺风新城建筑材料有限公司 | Waterborne fireproof coating and preparation method thereof |
| CN105694370A (en) * | 2016-04-08 | 2016-06-22 | 西南石油大学 | Toughened-flame-retardant epoxy resin material and preparation method thereof |
| CN105925168A (en) * | 2016-05-20 | 2016-09-07 | 武汉工程大学 | Microencapsulated water-based fire retardant coating and preparation method thereof |
-
2016
- 2016-12-07 CN CN201611116065.8A patent/CN107033732B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015529A (en) * | 2008-02-28 | 2011-04-13 | 巴斯夫欧洲公司 | Graphite nanoplatelets and compositions |
| CN104640808A (en) * | 2011-11-14 | 2015-05-20 | 沃尔贝克材料有限公司 | Graphene containing compositions |
| CN103642361A (en) * | 2013-12-10 | 2014-03-19 | 北京新立机械有限责任公司 | Water-soluble nano camouflage paint and preparation method thereof |
| CN105017831A (en) * | 2014-04-18 | 2015-11-04 | 新材料与产业技术北京研究院 | Composition for water-based electric heating nano paint, water-based electric heating nano paint as well as preparation method and application of water-based electric heating nano paint |
| JP2016029004A (en) * | 2014-07-18 | 2016-03-03 | 積水化学工業株式会社 | Method for manufacturing flaky graphite, flaky graphite, flaky graphite dispersion, and flaky graphite-resin composite material |
| CN104293195A (en) * | 2014-09-22 | 2015-01-21 | 铜陵市新泰电容电器有限责任公司 | Electrolytic capacitor shell cooling coating containing rare-earth elements |
| WO2016045035A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene |
| CN105001597A (en) * | 2015-08-12 | 2015-10-28 | 哈尔滨理工大学 | Needle-shaped nanometer aluminium oxide/graphene oxide/epoxy resin composite and preparation method |
| CN105505108A (en) * | 2015-11-27 | 2016-04-20 | 沈阳顺风新城建筑材料有限公司 | Waterborne fireproof coating and preparation method thereof |
| CN105694370A (en) * | 2016-04-08 | 2016-06-22 | 西南石油大学 | Toughened-flame-retardant epoxy resin material and preparation method thereof |
| CN105925168A (en) * | 2016-05-20 | 2016-09-07 | 武汉工程大学 | Microencapsulated water-based fire retardant coating and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109666370A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of conductive anti-corrosion coating and preparation method thereof containing graphene |
| 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 |
| CN108630338A (en) * | 2018-03-08 | 2018-10-09 | 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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