CN109880488A - A kind of Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal anti-corrosive paint - Google Patents
A kind of Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal anti-corrosive paint Download PDFInfo
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Abstract
The present invention provides that a kind of Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal anti-corrosive paint, belong to technical field of coatings, the present invention includes following components by weight: 16-20 parts of epoxy resin, 1-2 parts of dispersing agent, 1-3 parts of levelling agent, 13-23 parts of zinc powder, Diamines salicylide Schiff 's base modification graphene or graphene oxide it is slurry 1-9 parts pre-dispersed, 3-20 parts of curing agent.The present invention makes it form effective interface cohesion between polymeric matrix, achievees the effect that in the base evenly dispersed using the interaction between the graphene or surface of graphene oxide functional group and polymeric matrix molecule after modification；Simultaneously it is modified be easier to zinc powder by coordinate bond in conjunction with, more stable is attached in graphene network structure, reduces the usage amount of zinc powder；Graphene oxide, graphene after modification are easier to be adsorbed in metal surface, increase the adhesion of coating, and zinc powder usage amount is few.
Description
Technical field
The present invention relates to technical field of coatings, and in particular to a kind of Diamines salicylide Schiff 's base is grapheme modified or aoxidizes
Graphene metal anti-corrosive paint.
Background technique
As China's power grid is built on a large scale, substation continues to bring out like the mushrooms after rain, however, the corruption of grid equipment
Erosion problem is the one of the major reasons for influencing its service life and leading to equipment and structural failure.Electricity power engineering overlay area is wide
Wealthy, the complicated multiplicity of locating natural environment, wherein coastal area primary equipment anticorrosive metal problem also emerges therewith.It is complete
Equipment at power generation, transmission and disttrbution function is called primary equipment, such as generator, transformer, motor, fuse and keeps apart
Close etc., current most effective most direct anti-corrosion method is exactly in metal surface brushing anticorrosive paint, to prevent or slow down metal
Corrosion.
Common anticorrosive paint mainly have red lead anti-corrosive paint, phthalic resin coating, epoxy coating, polyurethane coating,
Acrylic resin paint and zinc-rich paint.Epoxy zinc rich primer is ship, marine facility, bridge, large scale equipment and all kinds of big
It is most important in terms of the steel structure of type building, using one of most common heavy-duty anticorrosive coating kind, anticorrosion mechanism is based on gold
Belong to zinc powder to act on the cathodic protection of steel, zinc content and its anti-corrosion effect are closely related, but high-content zinc powder (60%~
85%) also for zinc rich primer bring not environmentally, many drawbacks such as quality is big, affect it in the popularization and use of special dimension.For
The long-effective corrosion for guaranteeing coating generallys use and increases the method for common anticorrosive paint coating thickness to extend anticorrosion time limit, such as
The thickness of dry film of ship priming paint is typically designed as 300 μm or more, thereby increases material consumption, increases the invalid load of ship
Weight.
Graphene (Graphene, G) is a kind of very important low-dimensional carbon member, is by carbon atom with sp2Hybrid form
It is formed by honeycomb flat film, is current most thin two-dimensional material known in the world.Research finds it in mechanics, electricity
, calorifics and magnetics etc. all have peculiar and excellent performance, and unique nanostructure is expected to it in high-performance electric
The fields such as sub- device, composite material, biomaterial and gas sensor are widely applied.Meanwhile in the anti-of metal material
Rotten field also has very big potentiality: firstly, the sp that graphene is stable2Hybrid structure can be between metal and active medium
Physical barriers are formed, the progress of scattering and permeating is prevented；Secondly, graphene has good thermal stability and chemical stability,
In addition, the environment that the good conductive, heating conduction of graphene is on active service to metal provides advantage；It also has both simultaneously high strong
Degree and good tribological property.Electric conductivity or salt spray resistance can not only be improved, moreover it is possible to further decrease coating layer thickness, increase
To the adhesive force of substrate, the wearability of coating is promoted.
But the graphene annular-oxygen and rich zinc antiseptic dope prepared in the prior art, since graphene surface lacks active function
Group, and specific surface area is huge, so that the interface bond strength of they and polymeric matrix (such as epoxy resin, alkyd resin)
It is low, easily reunite, uniformity of the graphene particles in coating can reduce after reuniting, and be coated in metal surface in coating
It is uneven to will lead to conduction later, weak to the protective capacities of metal, the place for causing local graphite alkene less can not form barrier
Effect.In addition weaker with the binding ability of zinc powder because graphene surface lacks functional group, it is unfavorable for the attachment of zinc powder,
More zinc powders can be added under conditions of identical conductive capability, protection effect, the additive amount of zinc powder is very big, not only increases warp
Ji cost also will increase the weight of protection metal, and the wearability of coating is not high.
Summary of the invention
In view of this, the present invention provides, a kind of Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal is anti-
Rotten coating, can reduce that zinc powder usage amount, adhesive force are strong, water-tolerant, hardness are high.
The present invention is that a kind of Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal anti-corrosive paint, by weight
Measuring part includes following components: 16-20 parts of epoxy resin, 1-2 parts of dispersing agent, 1-3 parts of levelling agent, 13-29 parts of zinc powder, Diamines water
The graphene of poplar aldehyde Schiff 's base modification or graphene oxide is slurry 1-9 parts pre-dispersed, 3-20 parts of curing agent, 8-10 parts of iron oxide red, cloud
10-15 parts of female powder, 5-23 parts of diluent, 1-10 parts of functional filler, 17-25 parts of mixed solvent.
The mass concentration of the graphene or the pre-dispersed slurry of graphene oxide is 5-36%.
Silane coupling agent KH550, dispersing agent KH570 etc. can be used in dispersing agent；Isophorone, two can be used in levelling agent
Pyruvic alcohol etc..
The method of modifying of graphene or graphene oxide the following steps are included:
(1) graphene or graphene oxide are dispersed in a solvent, Diamines salicylide Schiff 's base, graphene or oxidation stone is added
The molar ratio of black alkene and Diamines salicylide Schiff 's base is 1:3-6, ultrasonic, isolated Diamines salicylide Schiff 's base modification
Graphene or graphene oxide crude product；
0.5~2h of each ultrasonic time；, the general structure such as following formula of Diamines salicylide Schiff 's base:
In formula, in the alkyl of open chain or cyclic structure of the R1 selected from straight or branched structure, alkenyl, aryl or alkylaryl group
Any one；The Diamines salicylide Schiff 's base includes the compound of at least one logical formula (I) structure.
(2) diamines will be obtained after the graphene of modification described in step (1) or the purification of graphene oxide crude product
The graphene or graphene oxide of class salicylide Schiff 's base modification.
The pre-dispersed method used be common dispersing method, by Diamines salicylide Schiff 's base it is grapheme modified or oxidation
Graphene ultrasonic disperse in a solvent, the pre-dispersed solvent used can for one of toluene, cyclohexanol, ethyl alcohol, methanol or
It is a variety of.
Wherein, functional filler is one of bentonite, silica, titanium dioxide, barium sulfate or a variety of mixtures；Institute
The mixed solvent stated can be two or more in toluene, dimethylbenzene, alcohols (ethyl alcohol), ketone (ketone), esters
Mixture.The partial size of the zinc powder can be 900-1100 mesh.The epoxy average value of the epoxy resin be 0.12,0.20,
One of 0.44 or a variety of, E-12 epoxy resin, E-20 epoxy resin, E-44 epoxy resin can be expressed as.
Specifically the preparation method comprises the following steps: 16-20 parts and mixed solvent 17-25 parts of epoxy resin are uniformly mixed with high-speed mixer
It is added in paint mixing tank afterwards, opens high-speed mixer, sequentially add 1-2 parts of dispersing agent, 1-3 parts of levelling agent, 8-10 parts of iron oxide red, mica
10-15 parts of powder, 1-10 parts of functional filler, after mixing evenly with three-roll grinder by the fineness of mill base be ground to 30 μm hereinafter,
It is subsequently placed in paint mixing tank；High-speed mixer is opened, the graphene of zinc powder 13-23 parts and the modification of Diamines salicylide Schiff 's base is added
Or pre-dispersed slurry 1-9 parts of graphene oxide, high speed (3000 r/min) stirs 10 min and is filtered with 90-110 mesh filter screen, then to
Curing agent 3-20 parts, 5-23 parts of diluent are added in solution, after mixing, obtains Diamines salicylide Schiff 's base modification graphite
Alkene or graphene oxide metal anti-corrosive paint.
Since graphene surface lacks active function groups, and specific surface area is huge, so that them and polymeric matrix (such as ring
Oxygen resin, alkyd resin etc.) interface bond strength it is low, easily reunite.Graphene is surface modified, its table is utilized
Interaction between face functional group and polymeric matrix molecule makes it form effective interface knot between polymeric matrix
It closes, achievees the effect that in the base evenly dispersed；In conjunction with other materials and can also react, by graphene or its spread out
Biology is carried on other materials by distinct methods, will lead to the physics of material, chemical property changes.Certainly, graphite
Alkene is nano material, and additive amount properly can just work, and dosage is very few, and graphene can not form blocking effect in coating；
Dosage is excessive, will lead to graphene and reunites, and generates defect, reduces the corrosion resistance of coating.
Graphene oxide (graphene oxide, GO) is the oxide of graphene, generally by graphite through strong acid aoxidize and
, if Hummers method is a kind of most common method for preparing GO, the timeliness of preparation process preferably and is made relatively
It is also relatively safer during standby.It using in the concentrated sulfuric acid potassium permanganate and powdered graphite after oxidation reaction, obtain brown
Edge have derivative carboxylic acid group and in the plane be mainly phenolic hydroxyl group and epoxy group graphite flake, this graphene layers can
To be vigorously stirred removing through ultrasound or high shear as graphene oxide, and formed in water stable, sundown mono-layer oxidized
Graphene suspension.Graphite oxide still keeps the layer structure of graphite, but introduces many on each layer of graphene monolithic
Oxy functional groups (such as-COOH ,-OH, epoxy group), these active oxygen functional groups can increase itself and epoxy resin or polyurethane
Compatibility and dispersibility.
Graphene or graphene oxide be it is a kind of by carbon atom with sp2 hybridized orbit form hexangle type be in honeycomb lattice two
Tie up carbon nanomaterial.Carbon atom in each hexatomic ring is with the sp of the carbon atom on sp2 hybridized orbit and adjacent hexatomic ring2It is miscellaneous
Change track and forms carbon carbon σ key along Maximum overlap direction.3 sp of each carbon atom2The symmetry axis of hybridized orbit is all distributed in together
In one plane, angle is 120 degree, forms the carbon skeleton of regular hexagon；In addition, there are one perpendicular to this for each carbon atom
The non-hydridization P track of plane, they are parallel to each other, side overlaps to form the delocalized big pi bond of height.And phenyl ring also has positive six
Side shape is conjugated the structure of the big pi bond of delocalization, these pi-electrons can pass through π-π non-covalent bond effect with other compounds containing pi-electron
It combines, so the surface of carbon nanotube has strong suction-operated to the aromatic compound containing phenyl ring.
Therefore Diamines salicylide Schiff phenyl ring with have strong pi bond phase interaction between graphene or graphene oxide
With promotion salicylaldehyde diamine Schiff is combined with it, and especially R1 is aromatic compound.Schiff is that one kind contains
The organic compound of imines or azomethine characteristic group (- RC=N -), easily with metal ion formed complex, because its own
The effect of group functionality and central ion and at the factors such as bonding effect and electronic effect, Schiff and its complex permitted
Various aspects have important application.By preliminary tribology experiments the result shows that, salicylaldehyde diamine Schiff copper complex
Presence the coefficient of friction of material can not only reduced, and can reduce material abrasion.
Graphene or graphene oxide are easier to pass through coordination with zinc powder after Diamines salicylide Schiff 's base modification
Bond is closed, and more stable is attached in graphene network structure.Schiff is tied by pi-electron in C=N double bond and metal surface
It closes, along with stable complex (such as following formula) is easily formed with zinc containing the salicylide Schiff 's base of-OH, similarly graphene oxide
In active oxy group coordination can also occur with zinc, metal surface can also be adsorbed on to preventing the corruption of metal
Erosion.
Graphene or graphene oxide after will be surface modified be added into common ring as a kind of novel anti-corrosion material
The new coating prepared in oxygen anticorrosive paint not only has the screen of the cathodic protection effect of epoxy zinc-enriched paint, glass-flake coating
Effect is covered, using the interaction between its surface functional group and polymeric matrix molecule, makes its shape between polymeric matrix
At effective interface cohesion, achieve the effect that in the base evenly dispersed；It is modified simultaneously to be easier to pass through coordinate bond with zinc powder
In conjunction with more stable is attached in graphene network structure, reduces the usage amount of zinc powder；Graphene oxide, graphite after modification
Alkene is easier to be adsorbed in metal surface, increases the adhesion of coating.Coating zinc powder usage amount of the invention is few, has good toughness, attached
Put forth effort the features such as strong, water-tolerant, hardness are high, antiseptic property is good.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
The measuring method of common antiseptic property is usually the measuring method and copper accelerated acetic acid salt spray of resistance to neutral salt spray performance
Test method, spraying apparatus that is all time-consuming and needing special manufacture, is further improved.Coastal primary equipment metal is anti-
Corruption faces severe harsh environment, and the test method of antiseptic property will also improve therewith.
It is tested in the present invention using antiseptic property of the following methods to coating, comprising the following steps:
(1) impregnate solution preparation: sodium chloride is dissolved in distilled water, dissolve obtain colourless solution, make concentration 45 ~
55g/L configures the PH of solution in 6.0 ~ 7.0 ranges；And the dichloride copper of sufficient amount is added in salting liquid, make its concentration
0.25~0.30g/L；And adding enough glacial acetic acid in salting liquid with the solution pH value for guaranteeing preparation is 3.0 ~ 3.1.
(2) when measuring, the coating prepared is coated on tinplate surface, is placed at room temperature for 3 ~ 7d.Sample board is made, then will
Sample board is completely soaked to be impregnated below testing liquid liquid level, timing sampling observation.After the test, sample is taken out, is being cleaned
Preceding 0.5 ~ 1h of drying.Test specimen is no more than in 25 ~ 40 DEG C of clean circulating waters in temperature and lightly cleans or impregnates, immediately after
Sample is dried up, erosion profile is observed.
Embodiment one
(1) graphene is dispersed in a solvent, Diamines salicylide Schiff 's base, graphene and Diamines salicylide Schiff 's base is added
Molar ratio be 1:3, ultrasonic 0.5h, isolated Diamines salicylide Schiff 's base modification graphene；
(2) graphite of Diamines salicylide Schiff 's base modification is obtained after purifying the graphite ene product of modification described in step (1)
Alkene disperses the graphene for modifying later in toluene, what the Diamines salicylide Schiff 's base that preparation mass concentration is 5% was modified
The pre-dispersed slurry of graphene,；
(3) mass parts are pressed by 18 parts of E-44 epoxy resin and mixed solvent (dimethylbenzene, n-butanol, propylene glycol methyl ether acetate, body
Product is than 5:3:1) 20 parts be added in paint mixing tank after mixing with high-speed mixer, open high-speed mixer, sequentially add silane
1.2 parts of coupling agent KH550,1.3 parts of levelling agent isophorone, 9 parts of iron oxide red, 12 parts of mica powder, 5 parts of bentonite, after mixing evenly
The fineness of mill base is ground to 30 μm or less with three-roll grinder；
(4) it is subsequently placed in paint mixing tank；High-speed mixer is opened, 15 parts of zinc powder and Diamines salicylide west that mesh number is 1000 is added
High speed (3000 r/min) agitation grinding 10 min, 4 parts of the pre-dispersed slurry of the base-modified graphene of Buddhist supplies solvent and is adjusted to former
It is formulated solid content, is filtered with 100 mesh filter screens, then curing agent 10,15 parts of diluent are added into solution, after mixing, is obtained
The grapheme modified metal anti-corrosive paint of Diamines salicylide Schiff 's base.
Non-volatile content measurement is carried out by the regulation of GB/T 1725-2007, is carried out by the regulation of GB/T 1724-1979
Fineness measurement, the measurement of time is dried by the regulation of GB/T 1728-1979.The coating prepared is coated on tinplate
Surface is placed at room temperature for 3 days, it is spare that sample board is made.Appearance of film is visually observed in the case where scattering sunlight, by GB/T 1733-1933
First law regulation carry out Water Resistance Test, by GB/T 9274-1988 immersion law regulation carry out acid resisting test, by GB/T
The regulation of 1771-2007 carries out salt fog resistance test, and infusion method test method sees above described.Coating in 1 the present embodiment of table
Technical indicator；
Table 1
G-SB coating is the above-mentioned grapheme modified metal anti-corrosive paint of Diamines salicylide Schiff 's base in table 1, and GO-SB coating is upper
State the grapheme modified metal anti-corrosive paint of Diamines salicylide Schiff 's base.
Comparative example
(1) mass parts are pressed by 18 parts of E-44 epoxy resin and mixed solvent (dimethylbenzene/n-butanol/propylene glycol methyl ether acetate, body
Product is added in paint mixing tank than 5/3/1) 20 parts with high-speed mixer after mixing, is opened high-speed mixer, is sequentially added silane
1.2 parts of coupling agent KH550,1.3 parts of levelling agent isophorone, 9 parts of iron oxide red, 12 parts of mica powder, 5 parts of bentonite, after mixing evenly
The fineness of mill base is ground to 30 μm or less with three-roll grinder；
(4) it is subsequently placed in paint mixing tank；High-speed mixer is opened, 15 parts of the zinc powder and mass concentration that addition mesh number is 1000 are 5%
Pre-dispersed 4 parts of slurry of graphene (non-modified processing), 10 min of high speed (3000 r/min) agitation grinding, supply solvent adjustment
It to original formulation solid content, is filtered with 100 mesh filter screens, then curing agent 10,15 parts of diluent is added into solution, after mixing,
Obtain graphene metal anti-corrosive paint.
Non-volatile content measurement is carried out by the regulation of GB/T 1725-2007, is carried out by the regulation of GB/T 1724-1979
Fineness measurement, the measurement of time is dried by the regulation of GB/T 1728-1979.The coating prepared is coated on tinplate
Surface is placed at room temperature for 3 days, it is spare that sample board is made.Appearance of film is visually observed in the case where scattering sunlight, by GB/T 1733-1933
First law regulation carry out Water Resistance Test, by GB/T 9274-1988 immersion law regulation carry out acid resisting test, by GB/T
The regulation of 1771-2007 carries out salt fog resistance test, and infusion method test method sees above described.Coating in 2 the present embodiment of table
Technical indicator；
Table 2
The technology for comparing the visible modified more unmodified graphene epoxy zinc-enriched paint of graphene coating of Tables 1 and 2 data refers to
It marks excellent.
Embodiment two
(1) graphene is dispersed in a solvent, Diamines salicylide Schiff 's base, graphene and Diamines salicylide Schiff 's base is added
Molar ratio be 1:4, ultrasonic 0.7h, isolated Diamines salicylide Schiff 's base modification graphene；
(2) graphite of Diamines salicylide Schiff 's base modification is obtained after purifying the graphite ene product of modification described in step (1)
Alkene will be modified later graphene and be dispersed in cyclohexanol or ethyl alcohol, the western Buddhist of Diamines salicylide that preparation mass concentration is 36%
The pre-dispersed slurry of base-modified graphene；
(3) by mass parts by 16-20 part of E-12 epoxy resin and mixed solvent (toluene, dimethylbenzene, ketone are according to volume ratio 1:2:
1 ratio mixing) 17 parts be added in paint mixing tank after mixing with high-speed mixer, open high-speed mixer, sequentially add point
KH5701 parts of powder, 1 part of levelling agent isophorone, 8 parts of iron oxide red, 10 parts of mica powder, functional filler silica 1 part, stirring
The fineness of mill base is ground to 30 μm or less with three-roll grinder after uniformly；
(4) it is subsequently placed in paint mixing tank；High-speed mixer is opened, 13 parts of zinc powder and Diamines salicylide west that mesh number is 900 is added
1 part of the pre-dispersed slurry of the base-modified graphene of Buddhist, high speed (3000 r/min) stir 10 min, supply solvent and be adjusted to original formulation
Solid content is filtered with 90 mesh filter screens, then 3 parts of curing agent, 5 parts of diluent are added into solution, after mixing, obtains Diamines
The grapheme modified metal anti-corrosive paint of salicylide Schiff 's base.Non-volatile content survey is carried out by the regulation of GB/T 1725-2007
It is fixed, fineness measurement is carried out by the regulation of GB/T 1724-1979, the survey of time is dried by the regulation of GB/T 1728-1979
It is fixed.The coating prepared is coated on tinplate surface, 3 days is placed at room temperature for, it is spare that sample board is made.Visually in the case where scattering sunlight
Appearance of film is observed, Water Resistance Test is carried out by the first law regulation of GB/T 1733-1933, by the immersion of GB/T 9274-1988
Law regulation carries out acid resisting test, carries out salt fog resistance test by the regulation of GB/T 1771-2007, infusion method test method is shown in
It is described previously.The technical indicator of coating in 3 the present embodiment of table；
Table 3
Embodiment three
(1) graphene oxide is dispersed in a solvent, Diamines salicylide Schiff 's base, graphene oxide and Diamines bigcatkin willow is added
The molar ratio of aldehyde Schiff 's base is 1:6, the graphene oxide that ultrasonic 2h, isolated Diamines salicylide Schiff 's base are modified；
(2) modification of Diamines salicylide Schiff 's base will be obtained after the graphene oxide purification of products of modification described in step (1)
Graphene oxide will be modified later graphene oxide and be dispersed in methyl alcohol, the Diamines salicylide that preparation mass concentration is 20%
The pre-dispersed slurry of graphene oxide of Schiff 's base modification；
(3) mass parts are pressed by 25 parts of 20 parts of E-20 epoxy resin and mixed solvent (toluene, dimethylbenzene volume ratio are 1:2) at a high speed
Blender is added in paint mixing tank after mixing, opens high-speed mixer, sequentially adds 2 parts of Silane coupling agent KH550, levelling agent
3 parts of isophorone, 10 parts of iron oxide red, 15 parts of mica powder, 5 parts of titanium dioxide, 5 parts of barium sulfate, after mixing evenly will with three-roll grinder
The fineness of mill base is ground to 30 μm or less；
(4) it is subsequently placed in paint mixing tank；High-speed mixer is opened, it is 13 parts of 1100 zinc powder and the western Buddhist of Diamines salicylide that mesh number, which is added,
9 parts of the pre-dispersed slurry of base-modified graphene or graphene oxide, high speed (3000 r/min) stir 10 min, supply solvent tune
It is whole to arrive original formulation solid content, it is filtered, then 20 parts of curing agent, 23 parts of diluent are added into solution, is uniformly mixed with 110 mesh filter screens
Afterwards, obtain that Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal anti-corrosive paint.
Non-volatile content measurement is carried out by the regulation of GB/T 1725-2007, is carried out by the regulation of GB/T 1724-1979
Fineness measurement, the measurement of time is dried by the regulation of GB/T 1728-1979.The coating prepared is coated on tinplate
Surface is placed at room temperature for 3 days, it is spare that sample board is made.Appearance of film is visually observed in the case where scattering sunlight, by GB/T 1733-1933
First law regulation carry out Water Resistance Test, by GB/T 9274-1988 immersion law regulation carry out acid resisting test, by GB/T
The regulation of 1771-2007 carries out salt fog resistance test, and infusion method test method sees above described.Coating in 4 the present embodiment of table
Technical indicator；
Table 4
Example IV
(1) graphene oxide is dispersed in a solvent, Diamines salicylide Schiff 's base, graphene oxide and Diamines bigcatkin willow is added
The molar ratio of aldehyde Schiff 's base is 1:6, the graphene oxide that ultrasonic 2h, isolated Diamines salicylide Schiff 's base are modified；
(2) modification of Diamines salicylide Schiff 's base will be obtained after the graphene oxide purification of products of modification described in step (1)
Graphene oxide will be modified later graphene oxide and be dispersed in methyl alcohol, the Diamines salicylide that preparation mass concentration is 20%
The pre-dispersed slurry of graphene oxide of Schiff 's base modification；
(3) mass parts are pressed by 25 parts of 20 parts of E-20 epoxy resin and mixed solvent (toluene, dimethylbenzene volume ratio are 1:2) at a high speed
Blender is added in paint mixing tank after mixing, opens high-speed mixer, sequentially adds 2 parts of Silane coupling agent KH550, levelling agent
3 parts of isophorone, 10 parts of iron oxide red, 15 parts of mica powder, 5 parts of titanium dioxide, 5 parts of barium sulfate, after mixing evenly will with three-roll grinder
The fineness of mill base is ground to 30 μm or less；
(4) it is subsequently placed in paint mixing tank；High-speed mixer is opened, it is 23 parts of 1100 zinc powder and the western Buddhist of Diamines salicylide that mesh number, which is added,
Pre-dispersed 9 parts of slurry of graphene oxide base-modified of graphene oxide or oxidation, high speed (3000 r/min) stir 10 min, mend
Sufficient solvent is adjusted to original formulation solid content, is filtered with 110 mesh filter screens, then 20 parts of curing agent, 23 parts of diluent are added into solution,
After mixing, obtain that Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal anti-corrosive paint.
Non-volatile content measurement is carried out by the regulation of GB/T 1725-2007, is carried out by the regulation of GB/T 1724-1979
Fineness measurement, the measurement of time is dried by the regulation of GB/T 1728-1979.The coating prepared is coated on tinplate
Surface is placed at room temperature for 3 days, it is spare that sample board is made.Appearance of film is visually observed in the case where scattering sunlight, by GB/T 1733-1933
First law regulation carry out Water Resistance Test, by GB/T 9274-1988 immersion law regulation carry out acid resisting test, by GB/T
The regulation of 1771-2007 carries out salt fog resistance test, and infusion method test method sees above described.Coating in 5 the present embodiment of table
Technical indicator；
Table 5
The similar performance of the coating prepared in embodiment three and example IV, but the content of zinc powder has a long way to go, it can be seen that
In the present invention in the identical situation of coating property, the content of zinc powder is that lower limit value can reach ideal effect.Compared to existing
There is the usage amount present invention of zinc powder in technology to can be effectively reduced the usage amount of zinc powder.
The present invention will be surface modified after graphene or graphene oxide as a kind of novel anti-corrosion material, addition
Entering the new coating prepared in common corrosion-resistant epoxy paint not only has the cathodic protection effect of epoxy zinc-enriched paint, glass squama
The screen effect of piece coating makes itself and polymer using the interaction between its surface functional group and polymeric matrix molecule
Effective interface cohesion is formed between matrix, is achieved the effect that in the base evenly dispersed；It is modified simultaneously to be easier to and zinc powder
It is combined by coordinate bond, more stable is attached in graphene network structure, reduces the usage amount of zinc powder；Oxidation stone after modification
Black alkene, graphene are easier to be adsorbed in metal surface, increase the adhesion of coating.Coating zinc powder usage amount of the invention is few, has
The features such as good toughness, adhesive force are strong, water-tolerant, hardness are high, antiseptic property is good.
The present invention is not limited to above-mentioned specific embodiment, and the invention may be variously modified and varied.All foundations
Technical spirit of the invention should be included in the present invention to embodiment of above any modification, equivalent replacement, improvement and so on
Protection scope.
Claims (10)
1. a kind of Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal anti-corrosive paint, which is characterized in that press
Parts by weight include following components: 16-20 parts of epoxy resin, 1-2 parts of dispersing agent, 1-3 parts of levelling agent, 13-23 parts of zinc powder, Diamines
Salicylide Schiff 's base modification graphene or graphene oxide it is slurry 1-9 parts pre-dispersed, 3-20 parts of curing agent.
2. a kind of Diamines salicylide Schiff 's base according to claim 1 is grapheme modified or graphene oxide anti-corrosion of metal
Coating, which is characterized in that the mass concentration of the graphene or the pre-dispersed slurry of graphene oxide is 5-36%.
3. a kind of Diamines salicylide Schiff 's base according to claim 1 is grapheme modified or graphene oxide anti-corrosion of metal
Coating, which is characterized in that the method for modifying of the graphene or graphene oxide the following steps are included:
(1) graphene or graphene oxide are dispersed in a solvent, Diamines salicylide Schiff 's base is added, it is ultrasonic, isolated
The graphene or graphene oxide crude product of Diamines salicylide Schiff 's base modification；
(2) Diamines salicylide west will be obtained after the graphene of modification described in step (1) or the purification of graphene oxide crude product
Buddhist base-modified graphene or graphene oxide.
4. a kind of Diamines salicylide Schiff 's base according to claim 3 is grapheme modified or graphene oxide anti-corrosion of metal
Coating, which is characterized in that the molar ratio of graphene described in step (1) or graphene oxide and Diamines salicylide Schiff 's base is
1:3-6。
5. a kind of Diamines salicylide Schiff 's base according to claim 4 is grapheme modified or graphene oxide anti-corrosion of metal
Coating, which is characterized in that the pre-dispersed solvent used is one of toluene, cyclohexanol, ethyl alcohol, methanol or a variety of.
6. a kind of Diamines salicylide Schiff 's base according to claim 1 is grapheme modified or graphene oxide anti-corrosion of metal
Coating, which is characterized in that by weight further include 8-10 parts of iron oxide red, 10-15 parts of mica powder, 5-23 parts of diluent, functionality
1-10 parts of filler, 17-25 parts of mixed solvent.
7. a kind of Diamines salicylide Schiff 's base according to claim 6 is grapheme modified or graphene oxide anti-corrosion of metal
Coating, which is characterized in that the functional filler is one of bentonite, silica, titanium dioxide, barium sulfate or a variety of mixed
Close object.
8. a kind of Diamines salicylide Schiff 's base according to claim 6 is grapheme modified or graphene oxide anti-corrosion of metal
Coating, which is characterized in that the mixed solvent is toluene, dimethylbenzene, alcohols, ketone, two or more in esters
Mixture.
9. a kind of Diamines salicylide Schiff 's base according to claim 1 is grapheme modified or graphene oxide anti-corrosion of metal
Coating, which is characterized in that the partial size of the zinc powder is 900-1100 mesh.
10. a kind of Diamines salicylide Schiff 's base according to claim 1 is grapheme modified or graphene oxide metal is anti-
Rotten coating, which is characterized in that the epoxy average value of the epoxy resin is one of 0.12,0.20,0.44 or a variety of.
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