CN108707355A - A kind of anticorrosive paint - Google Patents
A kind of anticorrosive paint Download PDFInfo
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- CN108707355A CN108707355A CN201810654298.6A CN201810654298A CN108707355A CN 108707355 A CN108707355 A CN 108707355A CN 201810654298 A CN201810654298 A CN 201810654298A CN 108707355 A CN108707355 A CN 108707355A
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- ethylene
- alcohol copolymer
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- vinyl alcohol
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0853—Vinylacetate
- C09D123/0861—Saponified vinylacetate
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
The present invention relates to the preparing technical fields of anticorrosive paint, provide a kind of anticorrosive paint, it includes preparing ethylene-vinyl alcohol copolymer presoma first, and with coupling agent modified graphene oxide further in high pressure, the association reaction of silane and ethylene-vinyl alcohol copolymer presoma is completed in heating under conditions of at the uniform velocity stirring, it is incorporated in graphene oxide surface layer with ethylene-vinyl alcohol copolymer presoma and coupling agent and forms dense film, greatly improve the dispersibility of graphene oxide, keep it uniform, stable being scattered in resin forms efficient graphene hot melt anticorrosive paint.
Description
Technical field
The present invention relates to the preparing technical fields of anticorrosive paint, and in particular to a kind of anticorrosive paint.
Background technology
For anticorrosive paint, traditional defense coating is limited to own material property and technique, the corruption to metallic matrix
Erosion protective action is often not satisfactory, and the exsertile cost of individual is again very high, reduces the cost performance of coating, and suitable one
Divide coating because of the heavy metals such as leaded zinc or chromate or noxious material, there are certain risk of environmental pollution, also consumes a large amount of
Non-renewable resources, be unfavorable for the sustainable development of social economy.Therefore, the anticorrosion for developing all kinds of New-type long-acting environmental protection applies
Material becomes new hot spot.
Graphene is extensively and unique performance presents its great potential in metal material corrosion-resistant field.First, graphite
The sp2 hybrid structures that alkene is stablized can form Physical barriers between metal and active medium, prevent the progress of scattering and permeating；
Secondly, graphene has good thermal stability and chemical stability, whether under the high temperature conditions（Up to 1500 DEG C）, also
It is that can keep stabilization in corrosion or the gas of oxidisability, liquid environment.In addition, the good conductive, heat conduction of graphene
The environment that performance is on active service to metal provides advantage.Graphene still most thin so far material, to base metal
Influence can be ignored.High intensity and good tribological property are also had both simultaneously, electric conductivity or resistance to can not only be improved
Salt fog performance, moreover it is possible to further decrease coating layer thickness, increase the adhesive force to base material, promote the wearability of coating.
Not only there is epoxy by adding new coating prepared by graphene on the basis of common corrosion-resistant epoxy paint
Cathodic protection effect, the screen effect of glass-flake coating of zinc-rich paint, with more good toughness, strong adhesive force, water-tolerant,
The features such as hardness is high not only has on the basis of common corrosion-resistant epoxy paint by adding new coating prepared by graphene
Cathodic protection effect, the screen effect of glass-flake coating of epoxy zinc-enriched paint, with more good toughness, strong adhesive force, water-fast
Property it is good, hardness is high the features such as, antiseptic property be more than existing anticorrosive paint, can be widely applied to ocean engineering, traffic fortune
The coating protection in the fields such as defeated, large industry equipment and municipal facilities.Coating is prepared with graphene to improve metal corrosion resistant
Potential in terms of corrosion, on the surface of copper and mickel, the graphite experiment of alkene proves, when being cultivated with chemical vapor deposition, the corruption of copper
Erosion speed slows down 7 times, slow 4 times of the corrosion rate of nickel.These discoveries illustrate that graphene is known most thin erosion shield.Therefore,
Graphene will become optimal corrosion-inhibiting coating.
The conjugated structure of graphene causes it poor with the compatibility of water, organic solvent and polymer, thus increases
Its application difficulty in paint field.Reunite since graphene will produce itself, destroy uniformity, the compactness of its dispersion,
It is applied to reunite when coating, and stress concentration is generated inside film, mechanical performance is caused to decline, and then leads to that coating is made
Anti-corrosion effect is poor, and barrier property is undesirable.
Invention content
Compatibility for graphene for anticorrosive paint and polymer is poor, itself reunites, and destroys the uniform of its dispersion
Property, the defect of compactness, the present invention proposes a kind of preparation method of efficient graphene heat molten type anticorrosive paint, by using second
Alkene-ethenol copolymer predecessor, graphene uniform is dispersed to inside coating, final to assign the good anti-corrosion effect of coating.
Can solve presently, there are due to graphene be produced from reunion caused by anticorrosion with coat effect it is poor, barrier property is poor not
Foot.
To achieve the above object, it adopts the following technical scheme that：
A kind of preparation method of efficient graphene hot melt anticorrosive paint, it is characterised in that before preparing ethylene-vinyl alcohol copolymer
Body is driven, and is granulated through reactive extrursion after being mixed with coupling agent modified graphene oxide, finally adds particulate abrasive to dry powder-shaped
It is added in resin and efficient graphene heat molten type anticorrosive paint is made；Specific preparation process is as follows：
（1）After Vinyl Acetate Monomer and solvent are mixed, initiator is added, is uniformly mixed, is added in reaction kettle, is passed through lazy
Property gas and raw material deoxygenation is carried out with certain speed stirring simultaneously, vinyl monomer is passed through after deoxygenation and heats polymerization, is obtained
To ethylene-vinyl alcohol copolymer presoma；The solvent is made of methanol, ethyl alcohol, the tert-butyl alcohol with arbitrary proportion；Described
Vinyl Acetate Monomer, solvent mass ratio be 1:1.5~3；The initiator is azodiisobutyronitrile or the peroxidating new last of the ten Heavenly stems
Any one in sour spy's pentyl ester, additive amount is the 0.2 ~ 1% of Vinyl Acetate Monomer and solvent gross mass；
（2）It is 10 by graphene oxide and silane coupling agent example in mass ratio:After 1 ~ 3 is uniformly mixed simultaneously ultrasonic disperse processing, water
Bath is heated and is stirred to react and rinses, dries up after a certain period of time, and it is for use to obtain coupling agent modified graphene oxide；
（3）By step（2）Obtained silane coupler modified graphene oxide and step（1）Ethylene-vinyl alcohol copolymer before
It is 1 that body, which is driven, by charged material weight ratio:5 ~ 8, in high pressure, is heated under conditions of at the uniform velocity stirring and complete silane and ethylene vinyl alcohol copolymer
The association reaction of object presoma cuts after extrusion and is granulated, obtains the compound of graphene oxide and ethylene-vinyl alcohol copolymer
Grain；
（4）By step（3）Obtained particle is refined into dry powder in micronizer, and sieving sub-elects the particle of suitable particle diameter,
Particle is mixed with resin in proportion, obtains graphene heat molten type anticorrosive paint.
Preferably, step（2）The silane coupling agent is 3- aminopropyl trimethoxysilanes, 3- aminopropyl-triethoxies
Silane, N-（2- aminoethyls）- 3- aminopropyls-trimethoxy silane, N-（2- aminoethyls）In -3- aminopropyls-triethoxysilane
It is one or more.
Preferably, step（1）The deoxygenation mixing speed is 100 ~ 120rpm, continues 10 ~ 15min.
Preferably, step（1）The intake of the vinyl monomer is to make the pressure of reaction kettle in 30 ~ 50bar.
Preferably, step（1）The described heating polymerization temperature being passed through after vinyl monomer is 65 ~ 75 DEG C.
Preferably, step（1）The heating polymerization time is 4 ~ 6 hours.
Preferably, step（3）The high pressure is 2-3MPa, and heating temperature is 75 ~ 85 DEG C, and the association reaction time is 4 ~ 5
Hour.
Preferably, step（4）The particle diameter sub-elected after the crushing is at 10 ~ 30 microns.
Preferably, step（4）The resin is at least one of epoxy resin, polyurethane resin, alkyd resin.
Preferably, step（4）The ratio of the particle and resin is mass ratio 1:2~5.
The oleophylic performance of graphene oxide can be improved in the modification technologies such as generally use surface decarboxylate, de-hydroxylated, increases
Its strong dispersibility in oil paint system, but effect is limited, the graphene oxide after surface treatment in a short time can be compared with
Good dispersion, but when left between extend after often there is the phenomenon that coating layering, uneven color, lead to coating and substrate
Binding force declines, weatherability, the service life reduction of coating.The present invention utilizes aminosilane coupling agent modifying graphene oxide, then
It is incorporated in graphene oxide surface layer with ethylene-vinyl alcohol copolymer presoma and coupling agent and forms dense film, greatly improves
The dispersibility of graphene oxide, make its can uniformly, being scattered in resin of stablizing.By controlling amino silicane coupling agent and oxygen
The ratio of graphite alkene can get the best film forming efficiency of ethylene-propylene alcohol copolymer, make the dispersibility of graphene oxide most
Bigization can get outstanding adhesiveness of the coating to substrate.Since the crosslinked action of graphene oxide makes itself and ethylene-vinyl alcohol
Copolymer closely connects, and crosslinked action is while solving the technical problem of graphene dispersion difference, when being scattered in coating,
This desmachyme being cross-linked to form keeps the dispersion of graphene oxide more stable, finally imparts the good anti-corrosion effect of coating
Fruit.
The present invention provides a kind of efficient graphene hot melt anticorrosive paint and preparation methods, compared with prior art,
Prominent feature and excellent effect are：
1, the graphene oxide surface layer in anticorrosive paint of the present invention is ethylene-propylene alcohol copolymer film so that in its coating
Dispersibility the phenomenon that greatly improving, being not in layering, the uneven color of coating.
2, the present invention is innovatively combined ethylene-propylene alcohol copolymer presoma with graphene oxide, is greatly improved
The crosslinked action of the dispersibility of graphene oxide, simultaneous oxidation graphene makes it closely connect shape with ethylene-vinyl alcohol copolymer
Tissue is reticulated, coating dispersibility is more stable.
3, raw material sources of the present invention are abundant, inexpensive, and preparation process is easy to operate, can carry out continuous high-efficient
Production, the product cost provided is low, and therefore, the technical program has broad application prospects.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of the step of preparation method of efficient graphene hot melt anticorrosive paint, preparation, is as follows：
It takes Vinyl Acetate Monomer 1kg to be uniformly mixed with 2kg methanol, 5g azodiisobutyronitriles is added as initiator, mixing is equal
It is even, it is added in reaction kettle, is passed through nitrogen and raw material deoxygenation is carried out with the stirring of the speed of 100rpm simultaneously, after continuing 12min,
Deoxygenation terminates, and being passed through vinyl monomer makes reactor pressure stablize in 35bar, and heating carries out polymerisation, and temperature rises to 70 DEG C of guarantors
During which warm 4h is continually fed into vinyl monomer and maintains pressure, cools down after reaction, obtain ethylene-vinyl alcohol copolymer presoma.
The uniformly mixed simultaneously ultrasonic disperse processing of 3- aminopropyl trimethoxysilanes of 100g graphene oxides, 20g are weighed, heating water bath is extremely
After 80 DEG C are stirred to react 5h simultaneously, filtering is rinsed, drying, and coupling agent modified graphene oxide is obtained.It is silane coupler modified
It is complete to be heated to 80 DEG C of heat preservation 2h in 2MPa, under conditions of at the uniform velocity stirring for graphene oxide and ethylene-vinyl alcohol copolymer presoma
At the association reaction of silane and ethylene-vinyl alcohol copolymer presoma, cuts and be granulated after hot extrusion before product cools down, obtain oxygen
The composite particles of graphite alkene and ethylene-vinyl alcohol copolymer.Particle is refined into dry powder by micronizer, is sieved,
Sub-elect particle of the grain size at 10-30 μm；Dry powder after taking 1kg to be sieved, mixes with 4kg epoxy resin, obtains graphene hot melt
Type anticorrosive paint.
To the graphene heat molten type anticorrosive paint that embodiment 1 obtains, surveyed according to coating standard JISK5664-2002
Examination, obtains that the results are shown in Table 1, it is seen then that utilizes ethylene-vinyl alcohol copolymer dispersed graphite alkene, the graphene anti-corrosion of acquisition
Coating, impact resistance, acid resistance, alkali resistance and resistance to salt water have reached standard requirement, meanwhile, than traditional graphite olefine resin
Coating has superior corrosion resistance.
Embodiment 2
A kind of the step of preparation method of efficient graphene hot melt anticorrosive paint, preparation, is as follows：
It takes Vinyl Acetate Monomer 1kg to be uniformly mixed with 1.5kg methanol, 0.8g ethyl alcohol, 8g azodiisobutyronitriles is added and are used as and draw
Agent is sent out, is uniformly mixed, is added in reaction kettle, be passed through nitrogen and raw material deoxygenation is carried out with the stirring of the speed of 120rpm simultaneously,
After continuing 10min, deoxygenation terminates, and being passed through vinyl monomer makes reactor pressure stablize in 50bar, and heating carries out polymerisation, temperature
Degree rises to 65 DEG C of heat preservation polymerisation 6h, is during which continually fed into vinyl monomer and maintains pressure, cools down after reaction, slightly produced
Object obtains ethylene-vinyl alcohol copolymer presoma after removing residual monomer.Weigh the 3- ammonia third of 150g graphene oxides, 30g
Ethyl triethoxy silicane alkane is uniformly mixed and ultrasonic disperse processing, after heating water bath is stirred to react 4h simultaneously to 85 DEG C, filtering, punching
It washes, dry up, obtain coupling agent modified graphene oxide.Silane coupler modified graphene oxide is total to ethylene-vinyl alcohol
Polymers presoma is heated to 85 DEG C of heat preservation 2h in 2.5MPa, under conditions of at the uniform velocity stirring and completes silane and ethylene vinyl alcohol copolymer
The association reaction of object presoma cuts after hot extrusion before product cools down and is granulated, it is total with ethylene-vinyl alcohol to obtain graphene oxide
The composite particles of polymers.Particle is refined into dry powder by micronizer, is sieved, it is micro- at 10-20 μm to sub-elect grain size
Grain；Dry powder after taking 1kg to be sieved, mixes with 2kg epoxy resin, obtains graphene heat molten type anticorrosive paint.
To the graphene heat molten type anticorrosive paint that embodiment 2 obtains, surveyed according to coating standard JISK5664-2002
Examination, obtains that the results are shown in Table 1, it is seen then that utilizes ethylene-vinyl alcohol copolymer dispersed graphite alkene, the graphene anti-corrosion of acquisition
Coating, impact resistance, acid resistance, alkali resistance and resistance to salt water have reached standard requirement, meanwhile, than traditional graphite olefine resin
Coating has superior corrosion resistance.
Embodiment 3
A kind of the step of preparation method of efficient graphene hot melt anticorrosive paint, preparation, is as follows：
It takes Vinyl Acetate Monomer 1kg to be uniformly mixed with the 2.5kg tert-butyl alcohols, 7g peroxidating neodecanoic acid spy's pentyl esters is added as initiation
Agent is uniformly mixed, is added in reaction kettle, is passed through nitrogen and carries out raw material deoxygenation simultaneously with the stirring of the speed of 110rpm, holds
After continuous 10min, deoxygenation terminates, and being passed through vinyl monomer makes reactor pressure stablize in 30bar, and heating carries out polymerisation, temperature
75 DEG C of heat preservation 4h are risen to, vinyl monomer is during which continually fed into and maintains pressure, cool down after reaction, obtain crude product, through removing
Ethylene-vinyl alcohol copolymer presoma is obtained after residual monomer.Weigh the 3- aminopropyl trimethoxies of 180g graphene oxides, 20g
The N- of base silane, 30g（2- aminoethyls）- 3- aminopropyls-trimethoxy silane is uniformly mixed and ultrasonic disperse processing, heating water bath
After being stirred to react 4.5h simultaneously to 85 DEG C, filtering is rinsed, drying, and coupling agent modified graphene oxide is obtained.The silicon that will be obtained
The coupling agent modified graphene oxide of alkane is with ethylene-vinyl alcohol copolymer presoma with mass ratio 1:5 feed intake, and in 3MPa, at the uniform velocity stir
The association reaction that 90 DEG C of heat preservation 2h complete silane and ethylene-vinyl alcohol copolymer presoma is heated under conditions of mixing, in product
It cuts and is granulated after hot extrusion before cooling, obtain the composite particles of graphene oxide and ethylene-vinyl alcohol.Pass through micronizer
Particle is refined into dry powder, is sieved, sub-elects particle of the grain size at 20-30 μm；Dry powder after taking 1kg to be sieved, with 4kg polyurethane
Resin mixes, and obtains graphene heat molten type anticorrosive paint.
To the graphene heat molten type anticorrosive paint that embodiment 3 obtains, surveyed according to coating standard JISK5664-2002
Examination, obtains that the results are shown in Table 1, it is seen then that utilizes ethylene-vinyl alcohol copolymer dispersed graphite alkene, the graphene anti-corrosion of acquisition
Coating, impact resistance, acid resistance, alkali resistance and resistance to salt water have reached standard requirement, meanwhile, than traditional graphite olefine resin
Coating has superior corrosion resistance.
Embodiment 4
A kind of the step of preparation method of efficient graphene hot melt anticorrosive paint, preparation, is as follows：
It takes Vinyl Acetate Monomer 1kg to be uniformly mixed with 1kg methanol, 1kg ethyl alcohol, the 1kg tert-butyl alcohols, two isobutyl of 10g azos is added
Nitrile is uniformly mixed, is added in reaction kettle as initiator, is passed through nitrogen and while being carried out with the stirring of the speed of 100rpm former
Expect deoxygenation, after continuing 12min, deoxygenation terminates, and being passed through vinyl monomer makes reactor pressure stablize in 45bar, and heating is polymerize
Reaction, temperature rise to 72 DEG C of heat preservation 4h, are during which continually fed into vinyl monomer and maintain pressure, cool down after reaction, slightly produced
Object obtains ethylene-vinyl alcohol copolymer presoma after removing residual monomer.Weigh the 3- ammonia third of 150g graphene oxides, 10g
Base trimethoxy silane, is uniformly mixed and ultrasonic disperse processing, heating water bath filter, punching to 75 DEG C while after being stirred to react 5h
It washes, dry up, obtain coupling agent modified graphene oxide.By obtained silane coupler modified graphene oxide and ethylene-second
Enol copolymer presoma is with mass ratio 1:7 feed intake, and in 2MPa, 80 DEG C of heat preservation 2h are heated under conditions of at the uniform velocity stirring and complete silicon
The association reaction of alkane and ethylene-vinyl alcohol copolymer presoma cuts after hot extrusion before product cools down and is granulated, obtains oxidation stone
The composite particles of black alkene and ethylene-vinyl alcohol copolymer.Particle is refined into dry powder by micronizer, is sieved, sorting
Go out particle of the grain size at 10-30 μm；Dry powder after taking 1kg to be sieved, mixes with 3.2kg alkyd resins, obtains graphene heat molten type
Anticorrosive paint.
To the graphene heat molten type anticorrosive paint that embodiment 4 obtains, surveyed according to coating standard JISK5664-2002
Examination, obtains that the results are shown in Table 1, it is seen then that utilizes ethylene-vinyl alcohol copolymer dispersed graphite alkene, the graphene anti-corrosion of acquisition
Coating, impact resistance, acid resistance, alkali resistance and resistance to salt water have reached standard requirement, meanwhile, than traditional graphite olefine resin
Coating has superior corrosion resistance.
Embodiment 5
A kind of the step of preparation method of efficient graphene hot melt anticorrosive paint, preparation, is as follows：
It takes Vinyl Acetate Monomer 1kg to be uniformly mixed with 1.8kg ethyl alcohol, 2g azodiisobutyronitriles is added as initiator, mixing
Uniformly, it is added in reaction kettle, is passed through nitrogen and raw material deoxygenation is carried out with the stirring of the speed of 120rpm simultaneously, continue 15min
Afterwards, deoxygenation terminates, and being passed through vinyl monomer makes reactor pressure stablize in 30bar, and heating carries out polymerisation, and temperature rises to 75 DEG C
6h is kept the temperature, vinyl monomer is during which continually fed into and maintains pressure, cool down after reaction, obtain crude product, through removing residual monomer
After obtain ethylene-vinyl alcohol copolymer presoma.Weigh the N- of 120g graphene oxides, 28g（2- aminoethyls）- 3- aminopropyls-
Triethoxysilane is uniformly mixed and ultrasonic disperse processing, after heating water bath is stirred to react 4h simultaneously to 80 DEG C, filter, rinse,
Drying, obtains coupling agent modified graphene oxide.The silane coupler modified graphene oxide and ethylene-vinyl alcohol that will be obtained
Copolymer presoma is by weight 1:8 feed intake, in 3MPa, at the uniform velocity stir under conditions of be heated to 90 DEG C heat preservation 2h complete silane with
The association reaction of ethylene-vinyl alcohol copolymer presoma cuts after hot extrusion before product cools down and is granulated, obtains graphene oxide
With the composite particles of ethylene-vinyl alcohol copolymer.Particle is refined into dry powder by micronizer, is sieved, sub-elects grain
Particle of the diameter at 15-25 μm；Dry powder after taking 1kg to be sieved, mixes with 2.2kg alkyd resins, obtains graphene heat molten type anti-corrosion
Coating.
To the graphene heat molten type anticorrosive paint that embodiment 5 obtains, surveyed according to coating standard JISK5664-2002
Examination, obtains that the results are shown in Table 1, it is seen then that utilizes ethylene-vinyl alcohol copolymer dispersed graphite alkene, the graphene anti-corrosion of acquisition
Coating, impact resistance, acid resistance, alkali resistance and resistance to salt water have reached standard requirement, meanwhile, than traditional graphite olefine resin
Coating has superior corrosion resistance.
Comparative example 1
Weigh the N- of 120g graphene oxides, 28g（2- aminoethyls）- 3- aminopropyls-triethoxysilane is uniformly mixed and ultrasound
Decentralized processing, after heating water bath is stirred to react 4h simultaneously to 80 DEG C, filtering is rinsed, drying, and coupling agent modified oxidation stone is obtained
Black alkene.By obtained silane coupler modified graphene oxide and commercially available ethylene-vinyl alcohol copolymer by weight 1:8 feed intake,
The association reaction that 90 DEG C of heat preservation 2h complete silane and ethylene-vinyl alcohol copolymer is heated in 3MPa, under conditions of at the uniform velocity stirring,
It cuts and is granulated after hot extrusion before product cools down, obtain the composite particles of graphene oxide and ethylene-vinyl alcohol copolymer.It is logical
It crosses micronizer and particle is refined into dry powder, be sieved, sub-elect particle of the grain size at 15-25 μm；It is dry after taking 1kg to be sieved
Powder is mixed with 2.2kg alkyd resins, obtains graphene heat molten type anticorrosive paint.
The graphene coating that comparative example 1 obtains, is tested also according to coating standard JISK5664-2002, is obtained
Arrive that the results are shown in Table 1.
Table 1：
。
Claims (1)
1. a kind of graphene heats anticorrosive paint, which is characterized in that prepare ethylene-vinyl alcohol copolymer presoma, and with coupling
It is granulated through reactive extrursion after the graphene oxide mixing that agent is modified, finally particulate abrasive to dry powder-shaped is added in resin and is made
Efficient graphene heat molten type anticorrosive paint；Specific preparation process is as follows：
（1）After Vinyl Acetate Monomer and solvent are mixed, initiator is added, is uniformly mixed, is added in reaction kettle, is passed through lazy
Property gas and raw material deoxygenation is carried out with certain speed stirring simultaneously, vinyl monomer is passed through after deoxygenation and heats polymerization, is obtained
To ethylene-vinyl alcohol copolymer presoma；The solvent is made of methanol, ethyl alcohol, the tert-butyl alcohol with arbitrary proportion；Described
Vinyl Acetate Monomer, solvent mass ratio be 1:1.5~3；The initiator is azodiisobutyronitrile or the peroxidating new last of the ten Heavenly stems
Any one in sour spy's pentyl ester, additive amount is the 0.2 ~ 1% of Vinyl Acetate Monomer and solvent gross mass；
（2）It is 10 by graphene oxide and silane coupling agent example in mass ratio:After 1 ~ 3 is uniformly mixed simultaneously ultrasonic disperse processing, water
Bath is heated and is stirred to react and rinses, dries up after a certain period of time, and it is for use to obtain coupling agent modified graphene oxide；
（3）By step（2）Obtained silane coupler modified graphene oxide and step（1）Ethylene-vinyl alcohol copolymer before
It is 1 that body, which is driven, by charged material weight ratio:5 ~ 8, in high pressure, is heated under conditions of at the uniform velocity stirring and complete silane and ethylene vinyl alcohol copolymer
The association reaction of object presoma cuts after extrusion and is granulated, obtains the compound of graphene oxide and ethylene-vinyl alcohol copolymer
Grain；
（4）By step（3）Obtained particle is refined into dry powder in micronizer, and sieving sub-elects the particle of suitable particle diameter,
Particle is mixed with resin in proportion, obtains graphene heat molten type anticorrosive paint；
Step（1）The deoxygenation mixing speed is 100 ~ 120rpm, continues 10 ~ 15min；
Step（1）The intake of the vinyl monomer is to make the pressure of reaction kettle in 30 ~ 50bar；
Step（1）The described heating polymerization temperature being passed through after vinyl monomer is 65 ~ 75 DEG C；
Step（1）The heating polymerization time is 4 ~ 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810654298.6A CN108707355B (en) | 2017-10-17 | 2017-10-17 | Anticorrosive paint |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810654298.6A CN108707355B (en) | 2017-10-17 | 2017-10-17 | Anticorrosive paint |
| CN201710963356.9A CN107641422B (en) | 2017-10-17 | 2017-10-17 | A kind of preparation method of efficient graphene hot melt anticorrosive paint |
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| CN108707355B CN108707355B (en) | 2020-09-01 |
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| CN201710963356.9A Expired - Fee Related CN107641422B (en) | 2017-10-17 | 2017-10-17 | A kind of preparation method of efficient graphene hot melt anticorrosive paint |
| CN201810654298.6A Active CN108707355B (en) | 2017-10-17 | 2017-10-17 | Anticorrosive paint |
| CN201810654297.1A Withdrawn CN108948954A (en) | 2017-10-17 | 2017-10-17 | A kind of anticorrosive paint that dispersibility is more stable |
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| CN110527405A (en) * | 2019-09-27 | 2019-12-03 | 安徽省聚科石墨烯科技股份公司 | A kind of Graphene glass fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861715A (en) * | 2006-06-13 | 2006-11-15 | 马锡华 | Environment protection type colour thermosol |
| CN101358097A (en) * | 2008-09-19 | 2009-02-04 | 河北科技大学 | Nano composite powder coatings and dispersion polymerization preparation method thereof |
| WO2009123771A2 (en) * | 2008-02-05 | 2009-10-08 | Crain John M | Coatings containing functionalized graphene sheets and articles coated therewith |
| CN105085835A (en) * | 2014-05-14 | 2015-11-25 | 泰山玻璃纤维有限公司 | Graphene modified polyvinyl acetate film forming agent preparation method |
| CN105985711A (en) * | 2015-03-18 | 2016-10-05 | 关西涂料株式会社 | Powder coating composition and coated film forming method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012068182A1 (en) * | 2010-11-15 | 2012-05-24 | Vorbeck Materials Corp. | Method of printing a conductive article and articles made thereby |
| CN105504125B (en) * | 2016-01-26 | 2017-10-17 | 厦门凯纳石墨烯技术股份有限公司 | A kind of method that in-situ polymerization prepares EVA/ graphene composite materials |
| CN105505212A (en) * | 2016-01-28 | 2016-04-20 | 赵栋 | Cold zinc-sprayed anticorrosion coating doped with modified graphene |
| CN105838183B (en) * | 2016-04-01 | 2019-01-29 | 常州华科聚合物股份有限公司 | Aqueous corrosion-resistant finishes material of modified graphene and its preparation method and application |
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- 2017-10-17 CN CN201810654296.7A patent/CN108929615A/en not_active Withdrawn
- 2017-10-17 CN CN201710963356.9A patent/CN107641422B/en not_active Expired - Fee Related
- 2017-10-17 CN CN201810654298.6A patent/CN108707355B/en active Active
- 2017-10-17 CN CN201810654297.1A patent/CN108948954A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861715A (en) * | 2006-06-13 | 2006-11-15 | 马锡华 | Environment protection type colour thermosol |
| WO2009123771A2 (en) * | 2008-02-05 | 2009-10-08 | Crain John M | Coatings containing functionalized graphene sheets and articles coated therewith |
| CN101358097A (en) * | 2008-09-19 | 2009-02-04 | 河北科技大学 | Nano composite powder coatings and dispersion polymerization preparation method thereof |
| CN105085835A (en) * | 2014-05-14 | 2015-11-25 | 泰山玻璃纤维有限公司 | Graphene modified polyvinyl acetate film forming agent preparation method |
| CN105985711A (en) * | 2015-03-18 | 2016-10-05 | 关西涂料株式会社 | Powder coating composition and coated film forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108929615A (en) | 2018-12-04 |
| CN107641422B (en) | 2018-08-07 |
| CN108948954A (en) | 2018-12-07 |
| CN107641422A (en) | 2018-01-30 |
| CN108707355B (en) | 2020-09-01 |
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