CN109971316A - A kind of water-base epoxy fullerene anticorrosive paint, preparation method - Google Patents
A kind of water-base epoxy fullerene anticorrosive paint, preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of water-base epoxy fullerene anticorrosive paints, preparation method.Including component A and B component；Component A includes the following composition of weight percent meter: the first aqueous epoxy curing agent 10~20%, fullerene slurry 3~5%, graphene slurry 1~2%, titanium dioxide 5~8%, carbon black 0.1~0.2%, aqueous zinc phosphate 2~5%, dispersing agent 0.3~0.8%, defoaming agent 0.3~0.6%, corrosion inhibiter 0.5~1%, aqueous organobentonite 0.3~0.5%, fumed silica 0.2~0.4%, aqueous wax liquor 2~4%, blanc fixe 10~20%, silica flour 10~20%, conductive mica powder 20~35%, cosolvent 1~2%, deionized water 6.2~7.3%；B component is aqueous epoxy resin emulsion.Such product has very excellent wearability, anti-corrosive properties, electric conductivity, chemical resistance, impact flexibility and excellent application property.
Description
Technical field
The present invention relates to a kind of water-base epoxy fullerene anticorrosive paints, preparation method, more particularly to a kind of using rich
The coating that alkene improves aqueous epoxy resins anti-corrosion effect is strangled, technical field of aqueous paint is belonged to.
Background technique
With gradually increasing for people's environmental consciousness, water-based anticorrosive paint develops oneself important directions as paint development
And research hotspot.Epoxy coating adhesive force height, fine corrosion resistance, excellent performance are not only applied in solvent type anti-corrosion
It finds full expression in material, also sufficiently applies in water-based anticorrosive paint.Since epoxy resin has excellent adhesive force, heat steady
Qualitative, anticorrosive property, chemical-resistant, insulating properties etc. can solidify with a variety of curing agent, can be as needed using flexile
Formula, these excellent properties of epoxy coating make epoxy resin occupy leading position, epoxy in anticorrosive paint as Qi Ji
Resin also becomes the anticorrosive paint resin that current number of applications is most, application range is most wide.Most of epoxy resin are not
It is dissolved in water, the coating industrially used at present is largely solvent based coating, and conventional solution-type coating is mostly with aromatic hydrocarbons, esters, alcohol
The disadvantages of class, ketone etc. are used as solvent, but organic solvent is inflammable, explosive, toxic brings inconvenience to storage and transportation and construction, and
And volatile matter is directly discharged into air, environmental pollution is compared with type, with the enhancing of people's environmental consciousness, without organic solvent or low waves
The novel anticorrosion coating such as green coatings such as powdery paints, the solventless coatings and water paint quilt in succession of hair property organic compound
Exploitation.Powdery paints is because condition of cure is more harsh, to limit its development.Solventless epoxy coating is applied in solvent free
Material field is that comparison is successful, only in recent years the hypotoxicity of reactive diluent and curing agent in terms of by
Arrived challenge, improving among；And waterborne epoxy coatings is other than the plurality of advantages for adhering to solvent based coating, to raising
Performance reduces pollution, expansion application etc. development.
Fullerene (C60) is a kind of newfound industrial material, its characteristic: 1, hardness is also harder than diamond；2, firmware degree
(ductility) is 100 times stronger than steel；3, it can be conductive, and electric conductivity is stronger than copper, and weight only has 1/6th of copper；4, its ingredient is
Carbon, so can be refined from waste.
C60 has the football structure of ideal symmetrical, reaction degeneracy with higher on its electron energy level.Theoretical calculation
Show that the electron energy level degeneracy of C60 molecule reaches as high as five weights.The lowest unoccupied molecular orbital (LUMO) of C60 is triple
The tlu state of degeneracy, so that C60 has very high electronegativity, it can receive electronics and form the anion of negatively charged son.Highly
Structural symmetry combines with molecular orbit degeneracy, so that C60 molecule has redox property very rich.
Due to C60 molecule ionization potential with higher (the first ionization energy of C60 is about 7.6eV), it is, in general, that
The electrochemical oxidation of C60 is more difficult, although also someone reports the electrochemistry irreversible oxidation reaction of C60 and C70, more often
What is seen is the electrochemical reduction of fullerene.
C60 is also easy to that electrochemical hydrogenation reaction occurs.Electrochemical charge reaction can occur by hydrogen for C60 electrode, and
The C60Hx of generation can be discharged with very high efficiency.Odd (Birch) reduction reaction of the uncle of fullerene and catalytic hydrogenation obtain
Product it is very much, have C60H18, C60H36, C60H56 and completely hydrogenated C60H60 etc., there are also the hydrogenation products of C70
C70H46.The plus hydrogenated conjunction object of fullerene is highly stable, has broad application prospects.It safely can largely be collected using them
With storage hydrogen property, as storage hydrogen material, this can apply the purifying in hydrogen, absorption, hydrogen combustion engine and
In hydrogen-air-fuel battery.Fullerene is to the storage of hydrogen and is released to the compression of Study of Hydrogen, purifying, heat pump and refrigeration
New method opens gate.
Fullerene is the 4 of carbon after diamond, graphite and Linear Carbon (carbyne) in discovery in 1985
Kind crystal habit.C60 molecule has armaticity, is dissolved in benzene in red sauce.It can make graphite with resistance heating graphite rod or arc process
The methods of evaporation is made.C60 has lubricity, is likely to become super lubricant.Metal-doped C60 has superconductivity, is to have development
The superconductor of future.C60 is also possible to be applied in many fields such as semiconductor, catalyst, accumulator material and drug.
C60 molecule can and metal bonding, can also be combined with nonmetallic anion.When alkali metal atom and C60 are combined, electronics from
Metallic atom is gone on C60 molecule, can form the MxC60 with superconductivity, and wherein M is K, Rb, Cs；X is to be doped into alkali metal
The number of atom.K3C60 is superconductor in 18K or less, is conductor in 18K or more, is doped into atomicity up to 6, K6C60 is exhausted
Edge body.C60 is the substance that existing scientific value has application prospect again, and there also have in fields such as life science, medicine, astrophysics to be fixed
Meaning.Carbon 60 (C60) and carbon 70 (C70) are most common, and are capable of the fullerene of volume production, and the member of fullerene is also
C28,C32,C240,C540.C78, C82, C84, C90, C96 etc. also have the other shapes such as tubulose.
Unconventional fullerene is extremely important in fullerene research although unstable in structure.Because on the one hand
Many unconventional fullerenes are the precursor and intermediate product for synthesizing conventional fullerene, study its structure and property for understanding fowler
The formation mechenism of alkene is extremely important；On the other hand the isomer number of unconventional fullerene is nearly the 100 of conventional fullerene
Times, if it is possible to carrying out modification to fullerene by certain mode settles out it, then is tantamount to open a new material
The gate of treasure-house.2000, the scientific research personnel of molecular nanostructure and key lab, nanotechnology institute during Japan's work,
When finding two metal scandiums being placed in Fullerene Carbon cage for the first time, it can effectively stablize unconventional fullerene C66(Nature,
408,426,2000).After returning to China, the scientist of they and Xiamen University cooperates, and synthesizes to separate and characterize and pass through
External Cl atom and the unconventional fullerene derivate C50Cl10(Science 304,699-699,2004 settled out).
Laboratory scientific research personnel has synthesized in succession again embeds fullerene Sc2C2 C68 by the stabilization of packet metal carbides in fullerene
The unconventional fullerene derivate C64H4 of (Angew. Chem. Int. ed. 45,2107,2006) and external hydrogen atom
(J. Am. Chem. Soc. 128,6605,2006).These results illustrate that unconventional fullerene can be in several ways
It settles out, lays a good foundation for research fullerene structure feature and the more fullerene-based materials of exploration.Fullerene is only due to it
Special structure and chemical physical property, produces far-reaching influence to chemistry, physics, material science, shows in application aspect
Tempting prospect.With the continuous deepening of research, Spectra of Carbon Clusters will bring great riches to the mankind.
Summary of the invention
Invention broadly provides a kind of water-base epoxy wear-proof anticorrosive paint containing fullerene, is utilized fullerene
Spherical shape, spherical structure, high rigidity, high tenacity, high conduction performance substantially enhance the wearability, electric conductivity, impact of coating
Toughness and antiseptic property.It is widely used in practicing the product tables such as oil-piping, crude oil storage tank, refined oil storage tank, automobile, engineering machinery
The protection in face.
A kind of water-base epoxy fullerene anticorrosive paint, includes component A and B component；
Wherein,
Component A includes following composition in percentage by weight:
First aqueous epoxy curing agent 10~20%, fullerene slurry 3~5%, graphene starch 1~2%, titanium dioxide 5~8%, carbon black 0.1
~0.2%, aqueous zinc phosphate 2~5%, dispersing agent 0.3~0.8%, defoaming agent 0.3~0.6%, corrosion inhibiter 0.5~1%, aqueous organic
Bentonite 0.3~0.5%, fumed silica 0.2~0.4%, aqueous wax liquor 2~4%, blanc fixe 10~20%, silica flour
10~20%, conductive mica powder 20~35%, cosolvent 1~2%, deionized water 6.2~7.3%；
B component is aqueous epoxy resin emulsion；
The weight ratio of component A and B component is 100:40~80.
Cosolvent is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol
The alcohol ethers solvent such as monomethyl ether acetate, ethyl alcohol, n-butanol or isopropanol.
In one embodiment, the fullerene content in fullerene slurry is 10~16wt%.
In one embodiment, the preparation method of fullerene slurry is: preparing containing 0.3~0.5mol/L
K2Cr2O7With the aqueous solution of the HCl of 1.2~1.5mol/L, the fullerene of 0.5~0.8g/L is added in aqueous solution, stirs evenly
Afterwards, 3~5h is reacted under the conditions of 82~86 DEG C to filter out solid after reaction and cleaned with deionized water, and dry, obtain
To the fullerene of surface active；Using acetone as reaction dissolvent, wherein be added 2~5wt% surface active fullerene, 5~
Second aqueous epoxy curing agent of 8wt%N, N- dihydroxy ethyl -3- amido methyl acrylate and 10~15wt%, add 0.8~
1.0wt% Catalyzed by p-Toluenesulfonic Acid agent after being uniformly dispersed under ultrasound condition, is evaporated under reduced pressure under the conditions of 60~65 DEG C and removes solvent
Afterwards, then at N25~8h is stirred under protective condition under the conditions of 40~45 DEG C to be reacted, after the reaction was completed, is cleaned instead with ethyl alcohol
Object, and vacuum drying are answered, the fullerene of hyperbranched modification is obtained；Prepare again the fullerene containing the hyperbranched modification of 10~16wt%,
The aqueous solution of 1~1.5wt% sodium polycarboxylate dipersant after being uniformly dispersed, obtains fullerene slurry.
In one embodiment, the aqueous epoxy resin emulsion is the modification E51 epoxy resin of ethenyl blocking
Lotion.
In one embodiment, the preparation method of the modification E51 epoxy resin latex of the ethenyl blocking includes
Following steps: polyalcohol, isocyanates are added into reactor step 1, organotin catalysts are added, and in nitrogen protection
Under, 1~3h of reaction is carried out under the conditions of 82~88 DEG C, chain extender is added the reaction was continued 0.5~1h, obtain performed polymer；Wherein
- the OH of polyalcohol the offer ,-NCO of isocyanates offer, chain extender molar ratio 5:6~8:1.2~1.6；Step 2, by pre-polymerization
Body, E51 epoxy resin, methyl methacrylate, azodiisobutyronitrile are according to weight ratio 1:6~8:0.5~0.8:0.05~0.2
Mixing, then under nitrogen protection, 0.5~1.5h of reaction is carried out under the conditions of 80~85 DEG C, add the poly- methyl of ethenyl blocking
Phenyl siloxane continues to react 1.5~2h of end capping reaction, the weight of ethenyl blocking polymethylphenylsiloxane and performed polymer
Measuring ratio is 0.2:2~3；After reaction, neutralizer is added to be neutralized, adds deionized water and be vigorously stirred, is obtained
Lotion；Deionized water and the additional amount of neutralizer are 12~14 times and 0.05~0.1 times of the weight of performed polymer.
In one embodiment, the organotin catalysts are dibutyl tin dilaurates.
In one embodiment, the chain extender is l, 4- butanediol, neopentyl glycol, ethylene glycol, a contracting diethyl two
Alcohol, glycerol, maleic anhydride, trimethylolpropane, ethylenediamine, diethylenetriamine, triethylene tetramine or dihydromethyl propionic acid
One or more of mixture.
In one embodiment, neutralizer is triethylamine, methylamine or triethanolamine.
The preparation method of water-base epoxy fullerene anticorrosive paint, includes the following steps:
Step 1, by the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter cosolvent be added production cylinder in, use
400~600 revs/min are stirred 5 minutes；
Aqueous organobentonite, fumed silica, aqueous wax liquor is added, using 400~600 revs/min in step 2 while stirring
Stirring 5 minutes；
Titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate is added, using 600~800 in step 3 while stirring
Rev/min stirring 10 minutes；
Fineness is ground to 30 microns using sand mill by step 4；
Step 5 is slowly added into conductive mica powder using 400~600 revs/min while stirring, is stirred using 1000~1200 revs/min
25~30 minutes；
Step 6, using 600~800 revs/min be slowly added into while stirring graphene slurry, fullerene starch, using 800~1000 turns/
Divide stirring 40~60 minutes.
Beneficial effect
Such product has very excellent wearability, anti-corrosive properties, electric conductivity, chemical resistance, impact flexibility and excellent applies
Work, disposable coating reach 150 microns of not saggings；
In the present invention, it is the important component for improving epoxy coating corrosion resistance that the fullerene of use, which is starched, since fullerene has
Conductive, spherical structure, high rigidity substantially enhance wearability, electric conductivity, impact flexibility and the antiseptic property of coating；
Meanwhile aqueous zinc phosphate is used as corrosion-resistant filling, improve the anticorrosive property of coating；Using conductive mica powder, base
In its electric conductivity, is matched with other fillers, improve coating antiseptic；In addition, when preparing fullerene slurry, by making
It is directly added into aqueous epoxy curing agent during standby, using its spherical structure, epoxy hardener is embedded in spherical structure, is led to
The crosslinking curing for crossing epoxy hardener and epoxy resin acts on, and directly fullerene is embedded in coating, improves the attached of coating
Put forth effort, while N is carried out to the surface of fullerene, it is long-term to improve it for N- dihydroxy ethyl -3- amido methyl acrylate graft modification
Stability when storage makes fullerene slurry by steadily saving, and keeps its Anticorrosive Character；Preparing aqueous epoxy resins cream
In liquid, by lotion hydridization Polyurethane can be improved the adhesive force of coating, while by lotion first with acrylic acid list
Body is blocked by Polyurethane performed polymer and cross linking of epoxy resin, then with ethenyl blocking polymethylphenylsiloxane, Ke Yiti
The high compatibility with fullerene slurry, keeps coating more wear resistant.
Specific embodiment
Embodiment 1
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (6520 U.S.'s Hexion).
Embodiment 2
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (6520 U.S.'s Hexion).
Embodiment 3
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (6520 U.S.'s Hexion).
Embodiment 4
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (6520 U.S.'s Hexion).
Embodiment 5
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (6520 U.S.'s Hexion).
Embodiment 6
Wherein, the preparation method of fullerene slurry:
Prepare the K containing 0.3mol/L2Cr2O7With the aqueous solution of the HCl of 1.2mol/L, the richness of 0.5g/L is added in aqueous solution
It strangles alkene and reacts 3h under the conditions of 82 DEG C after mixing evenly, after reaction, solid is filtered out and is cleaned with deionized water, and is dried
It is dry, obtain the fullerene of surface active；Using acetone as reaction dissolvent, wherein be added 2wt% surface active fullerene,
Second aqueous epoxy curing agent of 5wt%N, N- dihydroxy ethyl -3- amido methyl acrylate and 10wt%, adds 0.8wt% to first
Benzene sulfonic acid catalyst after being uniformly dispersed under ultrasound condition, is evaporated under reduced pressure under the conditions of 60 DEG C except after solvent, then at N2Ceiling
5h is stirred under part under the conditions of 40 DEG C to be reacted, after the reaction was completed, reactant, and vacuum drying is cleaned with ethyl alcohol, is surpassed
The fullerene of branched modification；Prepare again the fullerene containing the hyperbranched modification of 10wt%, 1wt% sodium polycarboxylate dipersant it is water-soluble
Liquid after being uniformly dispersed, obtains fullerene slurry.
Second aqueous epoxy curing agent (the 701 fatty amine lotion of Ep ilink of A ir Products company)
Sodium polycarboxylate dipersant (Nantong City Han Tai Chemical Co., Ltd. HT-5050)
The preparation method of aqueous epoxy resin emulsion: polyalcohol, isocyanates are added into reactor step 1, and February is added
Dilaurylate, and under nitrogen protection, reaction 1h is carried out under the conditions of 82 DEG C, adds chain extender l, 4- butanediol continues
0.5h is reacted, performed polymer is obtained；- NCO, the chain extender molar ratio 5:6 of-OH, isocyanates offer that wherein polyalcohol provides:
1.2；Step 2, by performed polymer, E51 epoxy resin, methyl methacrylate, azodiisobutyronitrile according to weight ratio 1:6:0.5:
0.05 mixing, then under nitrogen protection, reaction 0.5h is carried out under the conditions of 80 DEG C, add ethenyl blocking polymethyl-benzene base silicon
Oxygen alkane continues to react end capping reaction 1.5h, and the weight ratio of ethenyl blocking polymethylphenylsiloxane and performed polymer is 0.2:
2；After reaction, neutralizer triethylamine is added to be neutralized, adds deionized water and be vigorously stirred, obtains lotion；It goes
The additional amount of ionized water and neutralizer is 12 times and 0.05 times of the weight of performed polymer.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (self-control).
Embodiment 7
Wherein, the preparation method of fullerene slurry:
Prepare the K containing 0.5mol/L2Cr2O7With the aqueous solution of the HCl of 1.5mol/L, the richness of 0.8g/L is added in aqueous solution
It strangles alkene and reacts 5h under the conditions of 86 DEG C after mixing evenly, after reaction, solid is filtered out and is cleaned with deionized water, and is dried
It is dry, obtain the fullerene of surface active；Using acetone as reaction dissolvent, wherein be added 5wt% surface active fullerene,
Second aqueous epoxy curing agent of 8wt%N, N- dihydroxy ethyl -3- amido methyl acrylate and 15wt%, adds 1.0wt% to first
Benzene sulfonic acid catalyst after being uniformly dispersed under ultrasound condition, is evaporated under reduced pressure under the conditions of 65 DEG C except after solvent, then at N2Ceiling
8h is stirred under part under the conditions of 45 DEG C to be reacted, after the reaction was completed, reactant, and vacuum drying is cleaned with ethyl alcohol, is surpassed
The fullerene of branched modification；The water of the fullerene containing the hyperbranched modification of 16wt%, 1.5wt% sodium polycarboxylate dipersant is prepared again
Solution after being uniformly dispersed, obtains fullerene slurry.
Second aqueous epoxy curing agent (the 701 fatty amine lotion of Ep ilink of A ir Products company)
Sodium polycarboxylate dipersant (Nantong City Han Tai Chemical Co., Ltd. HT-5050)
The preparation method of aqueous epoxy resin emulsion: polyalcohol, isocyanates are added into reactor step 1, and February is added
Dilaurylate, and under nitrogen protection, reaction 3h is carried out under the conditions of 88 DEG C, adds chain extender l, 4- butanediol continues
1h is reacted, performed polymer is obtained；- NCO, the chain extender molar ratio 5:8 of-OH, isocyanates offer that wherein polyalcohol provides:
1.6；Step 2, by performed polymer, E51 epoxy resin, methyl methacrylate, azodiisobutyronitrile according to weight ratio 1:8:
0.8:0.2 mixing, then under nitrogen protection, carry out reaction 1.5h under the conditions of 85 DEG C, add ethenyl blocking polymethyl-benzene
Radical siloxane continues to react end capping reaction 2h, and the weight ratio of ethenyl blocking polymethylphenylsiloxane and performed polymer is
0.2:3；After reaction, neutralizer triethylamine is added to be neutralized, adds deionized water and be vigorously stirred, obtains cream
Liquid；Deionized water and the additional amount of neutralizer are 14 times and 0.1 times of the weight of performed polymer.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (self-control).
Embodiment 8
Wherein, the preparation method of fullerene slurry:
Prepare the K containing 0.4mol/L2Cr2O7With the aqueous solution of the HCl of 1.3mol/L, the richness of 0.6g/L is added in aqueous solution
It strangles alkene and reacts 4h under the conditions of 85 DEG C after mixing evenly, after reaction, solid is filtered out and is cleaned with deionized water, and is dried
It is dry, obtain the fullerene of surface active；Using acetone as reaction dissolvent, wherein be added 3wt% surface active fullerene,
Second aqueous epoxy curing agent of 6wt%N, N- dihydroxy ethyl -3- amido methyl acrylate and 12wt%, adds 0.9wt% to first
Benzene sulfonic acid catalyst after being uniformly dispersed under ultrasound condition, is evaporated under reduced pressure under the conditions of 62 DEG C except after solvent, then at N2Ceiling
6h is stirred under part under the conditions of 42 DEG C to be reacted, after the reaction was completed, reactant, and vacuum drying is cleaned with ethyl alcohol, is surpassed
The fullerene of branched modification；The water of the fullerene containing the hyperbranched modification of 12wt%, 1.2wt% sodium polycarboxylate dipersant is prepared again
Solution after being uniformly dispersed, obtains fullerene slurry.
Second aqueous epoxy curing agent (the 701 fatty amine lotion of Ep ilink of A ir Products company)
Sodium polycarboxylate dipersant (Nantong City Han Tai Chemical Co., Ltd. HT-5050)
The preparation method of aqueous epoxy resin emulsion: polyalcohol, isocyanates are added into reactor step 1, and February is added
Dilaurylate, and under nitrogen protection, reaction 2h is carried out under the conditions of 85 DEG C, adds chain extender l, 4- butanediol continues
0.6h is reacted, performed polymer is obtained；- NCO, the chain extender molar ratio 5:7 of-OH, isocyanates offer that wherein polyalcohol provides:
1.3；Step 2, by performed polymer, E51 epoxy resin, methyl methacrylate, azodiisobutyronitrile according to weight ratio 1:7:0.6:
0.1 mixing, then under nitrogen protection, reaction 1.2h is carried out under the conditions of 82 DEG C, add ethenyl blocking polymethyl-benzene base silicon
Oxygen alkane continues to react end capping reaction 1.6h, and the weight ratio of ethenyl blocking polymethylphenylsiloxane and performed polymer is 0.2:
2.2；After reaction, neutralizer triethylamine is added to be neutralized, adds deionized water and be vigorously stirred, obtains lotion；
Deionized water and the additional amount of neutralizer are 13 times and 0.07 times of the weight of performed polymer.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (self-control).
Reference examples 1
Difference with embodiment 5 is: conductive mica powder not being added, weight is replaced by aqueous zinc phosphate.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, it is stirred using 400~600 revs/min, is stirred 25~30 minutes using 1000~1200 revs/min；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (6520 U.S.'s Hexion).
Reference examples 2
Difference with embodiment 5 is that fullerene slurry is not added, and weight is starched by graphene and substituted.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry while stirring using 600~800 revs/min, using 800~1000 revs/min of stirrings 40~60
Minute, obtain A component.
B component uses aqueous epoxy resin emulsion (6520 U.S.'s Hexion).
Reference examples 3
Difference with embodiment 8 is: not using N in the preparation of fullerene slurry, N- dihydroxy ethyl -3- amido methyl acrylate is repaired
Decorations.
Wherein, the preparation method of fullerene slurry:
Prepare the K containing 0.4mol/L2Cr2O7With the aqueous solution of the HCl of 1.3mol/L, the richness of 0.6g/L is added in aqueous solution
It strangles alkene and reacts 4h under the conditions of 85 DEG C after mixing evenly, after reaction, solid is filtered out and is cleaned with deionized water, and is dried
It is dry, obtain the fullerene of surface active；Using acetone as reaction dissolvent, wherein be added 3wt% surface active fullerene and
The second aqueous epoxy curing agent of 12wt% adds 0.9wt% Catalyzed by p-Toluenesulfonic Acid agent, after being uniformly dispersed under ultrasound condition,
It is evaporated under reduced pressure under the conditions of 62 DEG C after removing solvent, then at N26h is stirred under protective condition under the conditions of 42 DEG C to be reacted, instead
After the completion of answering, reactant, and vacuum drying are cleaned with ethyl alcohol, obtains modified fullerene；The richness modified containing 12wt% is prepared again
The aqueous solution for strangling alkene, 1.2wt% sodium polycarboxylate dipersant after being uniformly dispersed, obtains fullerene slurry.
Second aqueous epoxy curing agent (the 701 fatty amine lotion of Ep ilink of A ir Products company)
Sodium polycarboxylate dipersant (Nantong City Han Tai Chemical Co., Ltd. HT-5050)
The preparation method of aqueous epoxy resin emulsion: polyalcohol, isocyanates are added into reactor step 1, and February is added
Dilaurylate, and under nitrogen protection, reaction 2h is carried out under the conditions of 85 DEG C, adds chain extender l, 4- butanediol continues
0.6h is reacted, performed polymer is obtained；- NCO, the chain extender molar ratio 5:7 of-OH, isocyanates offer that wherein polyalcohol provides:
1.3；Step 2, by performed polymer, E51 epoxy resin, methyl methacrylate, azodiisobutyronitrile according to weight ratio 1:7:0.6:
0.1 mixing, then under nitrogen protection, reaction 1.2h is carried out under the conditions of 82 DEG C, add ethenyl blocking polymethyl-benzene base silicon
Oxygen alkane continues to react end capping reaction 1.6h, and the weight ratio of ethenyl blocking polymethylphenylsiloxane and performed polymer is 0.2:
2.2；After reaction, neutralizer triethylamine is added to be neutralized, adds deionized water and be vigorously stirred, obtains lotion；
Deionized water and the additional amount of neutralizer are 13 times and 0.07 times of the weight of performed polymer.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (self-control).
Reference examples 4
Difference with embodiment 8 is: aqueous epoxy resin emulsion is handled without Polyurethane hydridization.
Wherein, the preparation method of fullerene slurry:
Prepare the K containing 0.4mol/L2Cr2O7With the aqueous solution of the HCl of 1.3mol/L, the richness of 0.6g/L is added in aqueous solution
It strangles alkene and reacts 4h under the conditions of 85 DEG C after mixing evenly, after reaction, solid is filtered out and is cleaned with deionized water, and is dried
It is dry, obtain the fullerene of surface active；Using acetone as reaction dissolvent, wherein be added 3wt% surface active fullerene,
Second aqueous epoxy curing agent of 6wt%N, N- dihydroxy ethyl -3- amido methyl acrylate and 12wt%, adds 0.9wt% to first
Benzene sulfonic acid catalyst after being uniformly dispersed under ultrasound condition, is evaporated under reduced pressure under the conditions of 62 DEG C except after solvent, then at N2Ceiling
6h is stirred under part under the conditions of 42 DEG C to be reacted, after the reaction was completed, reactant, and vacuum drying is cleaned with ethyl alcohol, is surpassed
The fullerene of branched modification；The water of the fullerene containing the hyperbranched modification of 12wt%, 1.2wt% sodium polycarboxylate dipersant is prepared again
Solution after being uniformly dispersed, obtains fullerene slurry.
Second aqueous epoxy curing agent (the 701 fatty amine lotion of Ep ilink of A ir Products company)
Sodium polycarboxylate dipersant (Nantong City Han Tai Chemical Co., Ltd. HT-5050)
The preparation method of aqueous epoxy resin emulsion: step 1, by E51 epoxy resin, methyl methacrylate, two isobutyl of azo
Nitrile is mixed according to weight ratio 7:0.6:0.1, then under nitrogen protection, is carried out reaction 1.2h under the conditions of 82 DEG C, added ethylene
Base sealing end polymethylphenylsiloxane continues to react end capping reaction 1.6h, ethenyl blocking polymethylphenylsiloxane and pre-
The weight ratio of aggressiveness is 0.2:2.2；After reaction, neutralizer triethylamine is added to be neutralized, adds deionized water progress
It is vigorously stirred, obtains lotion；Deionized water and the additional amount of neutralizer are 13 times and 0.07 times of the weight of performed polymer.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (self-control).
Reference examples 5
Difference with embodiment 8 is: aqueous epoxy resin emulsion shows to be handled by ethenyl blocking.
Wherein, the preparation method of fullerene slurry:
Prepare the K containing 0.4mol/L2Cr2O7With the aqueous solution of the HCl of 1.3mol/L, the richness of 0.6g/L is added in aqueous solution
It strangles alkene and reacts 4h under the conditions of 85 DEG C after mixing evenly, after reaction, solid is filtered out and is cleaned with deionized water, and is dried
It is dry, obtain the fullerene of surface active；Using acetone as reaction dissolvent, wherein be added 3wt% surface active fullerene,
Second aqueous epoxy curing agent of 6wt%N, N- dihydroxy ethyl -3- amido methyl acrylate and 12wt%, adds 0.9wt% to first
Benzene sulfonic acid catalyst after being uniformly dispersed under ultrasound condition, is evaporated under reduced pressure under the conditions of 62 DEG C except after solvent, then at N2Ceiling
6h is stirred under part under the conditions of 42 DEG C to be reacted, after the reaction was completed, reactant, and vacuum drying is cleaned with ethyl alcohol, is surpassed
The fullerene of branched modification；The water of the fullerene containing the hyperbranched modification of 12wt%, 1.2wt% sodium polycarboxylate dipersant is prepared again
Solution after being uniformly dispersed, obtains fullerene slurry.
Second aqueous epoxy curing agent (the 701 fatty amine lotion of Ep ilink of A ir Products company)
Sodium polycarboxylate dipersant (Nantong City Han Tai Chemical Co., Ltd. HT-5050)
The preparation method of aqueous epoxy resin emulsion: polyalcohol, isocyanates are added into reactor step 1, and February is added
Dilaurylate, and under nitrogen protection, reaction 2h is carried out under the conditions of 85 DEG C, adds chain extender l, 4- butanediol continues
0.6h is reacted, performed polymer is obtained；- NCO, the chain extender molar ratio 5:7 of-OH, isocyanates offer that wherein polyalcohol provides:
1.3；Step 2, by performed polymer, E51 epoxy resin, methyl methacrylate, azodiisobutyronitrile according to weight ratio 1:7:0.6:
0.1 mixing, then under nitrogen protection, reaction 2.8h is carried out under the conditions of 82 DEG C；After reaction, be added neutralizer triethylamine into
Row neutralizes, and adds deionized water and is vigorously stirred, obtains lotion；Deionized water and the additional amount of neutralizer are performed polymers
13 times of weight and 0.07 times.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added in production cylinder, using 400~
600 revs/min are stirred 5 minutes；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (self-control).
Reference examples 6
Difference with embodiment 8 is that when preparing fullerene slurry, the second aqueous epoxy curing agent is not added, but is directly added
Enter into component A.
Wherein, the preparation method of fullerene slurry:
Prepare the K containing 0.4mol/L2Cr2O7With the aqueous solution of the HCl of 1.3mol/L, the richness of 0.6g/L is added in aqueous solution
It strangles alkene and reacts 4h under the conditions of 85 DEG C after mixing evenly, after reaction, solid is filtered out and is cleaned with deionized water, and is dried
It is dry, obtain the fullerene of surface active；Using acetone as reaction dissolvent, wherein be added 3wt% surface active fullerene,
6wt%N, N- dihydroxy ethyl -3- amido methyl acrylate, add 0.9wt% Catalyzed by p-Toluenesulfonic Acid agent, disperse under ultrasound condition
After uniformly, it is evaporated under reduced pressure under the conditions of 62 DEG C after removing solvent, then at N26h is stirred under protective condition under the conditions of 42 DEG C to carry out
Reaction, after the reaction was completed, cleans reactant, and vacuum drying with ethyl alcohol, obtains the fullerene of hyperbranched modification；Prepare again containing
The aqueous solution of the fullerene of the hyperbranched modification of 12wt%, 1.2wt% sodium polycarboxylate dipersant, after being uniformly dispersed, obtains fullerene
Slurry.
Second aqueous epoxy curing agent (the 701 fatty amine lotion of Ep ilink of A ir Products company)
Sodium polycarboxylate dipersant (Nantong City Han Tai Chemical Co., Ltd. HT-5050)
The preparation method of aqueous epoxy resin emulsion: polyalcohol, isocyanates are added into reactor step 1, and February is added
Dilaurylate, and under nitrogen protection, reaction 2h is carried out under the conditions of 85 DEG C, adds chain extender l, 4- butanediol continues
0.6h is reacted, performed polymer is obtained；- NCO, the chain extender molar ratio 5:7 of-OH, isocyanates offer that wherein polyalcohol provides:
1.3；Step 2, by performed polymer, E51 epoxy resin, methyl methacrylate, azodiisobutyronitrile according to weight ratio 1:7:0.6:
0.1 mixing, then under nitrogen protection, reaction 1.2h is carried out under the conditions of 82 DEG C, add ethenyl blocking polymethyl-benzene base silicon
Oxygen alkane continues to react end capping reaction 1.6h, and the weight ratio of ethenyl blocking polymethylphenylsiloxane and performed polymer is 0.2:
2.2；After reaction, neutralizer triethylamine is added to be neutralized, adds deionized water and be vigorously stirred, obtains lotion；
Deionized water and the additional amount of neutralizer are 13 times and 0.07 times of the weight of performed polymer.
Using above-mentioned raw material proportioning, it is prepared by the following method:
1, the first aqueous epoxy curing agent, the second aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter and cosolvent are added
Enter to produce in cylinder, be stirred 5 minutes using 400~600 revs/min；The additional amount of second aqueous epoxy curing agent is surface active
4 times of the weight of fullerene；
2, aqueous organobentonite, fumed silica, aqueous wax liquor are added while stirring, using 400~600 revs/min of stirrings 5
Minute；
3, titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate are added while stirring, using 600~800 revs/min
Stirring 10 minutes.
4, fineness is ground to 30 microns using sand mill；
5, be slowly added into conductive mica powder while stirring using 400~600 revs/min, using 1000~1200 revs/min stirring 25~
30 minutes；
6, it is slowly added into graphene slurry, fullerene slurry while stirring using 600~800 revs/min, is stirred using 800~1000 revs/min
It mixes 40~60 minutes, obtains A component.
B component uses aqueous epoxy resin emulsion (self-control).
Reference examples 7
Anticorrosive paint disclosed in ZL201510516233.1.
Reference examples 8
Anticorrosive paint disclosed in ZL201410115127.8.
Coating in Examples 1 to 8 and reference examples 1~8 is subjected to coating test, dry plate is realized: according to component A: component B=
100:40-80 is matched, and the adjustment of spray viscosity is carried out using deionized-distilled water, spray viscosity is adjusted to 30-40S
(T-4 glasss) spray 2 layers, and dry plate is placed from dry 48 hours detection traditional performances in 25 DEG C of insulating boxs, as a result as shown in table 1, table 2.
In order to test the long-time stability of coating, above-mentioned waterborne epoxy coatings is packed with iron sheet, stores 18 in 30 DEG C
A month, coating property test is carried out again, as a result as shown in table 3, table 4.
Table 1
Table 2
Table 3
Table 4
By Experimental Comparison analysis of illustrating above, the water-base epoxy conduction anti-corrosion of conductive mica powder production is combined using graphene slurry
Painting conductive can reach 109-1010Ω.cm2, salt fog resistance is logical can reach 4000 hours or more, but still there are wearabilities
Energy is poor, resistance to acid and alkali is general.After fullerene slurry is added, wear-resisting property is greatly promoted, and paint film loss is only 0.008 gram, conductive
Performance reaches 107-108Ω.cm2While salt spray resistance has reached 5500h, resistance to acid and alkali is there has also been being obviously improved, simultaneously
Toughness is promoted, and impact resistance reaches 65cm.By the comparison of embodiment 6 and embodiment 5 as can be seen that use was prepared
Fullerene slurry and aqueous epoxy resin emulsion have the advantages that preferably to promote antiseptic property, adhesive force；By embodiment 8 and right
1 compared to as can be seen that the effect of conductive mica powder can effectively improve the antiseptic property of coating as usual；Pass through 8 He of embodiment
Reference examples 2 are as can be seen that fullerene slurry in terms of improving coating abrasion performance and antiseptic property, has apparent effect；Pass through reality
Example 8 and reference examples 3 are applied as can be seen that carrying out N to the surface of fullerene, the grafting of N- dihydroxy ethyl -3- amido methyl acrylate changes
Property, stability when its long-term storage is improved, the phenomenon that coating storage is reunited later is avoided the occurrence of, keeps fullerene slurry logical
It is saved after steadily, and keeps its Anticorrosive Character；By embodiment 8 and reference examples 4 as can be seen that preparing aqueous epoxy resins
In lotion, by lotion hydridization Polyurethane the adhesive force of coating can be improved；It can be seen by embodiment 8 and reference examples 5
Out, by lotion first with acrylic monomers by Polyurethane performed polymer and cross linking of epoxy resin, then with the poly- first of ethenyl blocking
Base phenyl siloxane is blocked, and the compatibility with fullerene slurry can be improved, keep coating more wear resistant；By embodiment 8 and right
6 as can be seen that the spherical structure that addition aqueous epoxy curing agent can use graphene will be consolidated when preparing fullerene slurry as usual
When agent is fixed on structure, in paint solidification, epoxy resin and curing agent and fullerene is formed into stable consolidated structures, mentioned
High adhesion force.Waterborne epoxy coatings provided by the invention be widely used in practice oil-piping, crude oil storage tank, refined oil storage tank, automobile,
The protection of the product surfaces such as engineering machinery.
Claims (8)
1. a kind of water-base epoxy fullerene anticorrosive paint, includes component A and B component；
Wherein,
Component A includes following composition in percentage by weight:
First aqueous epoxy curing agent 10~20%, fullerene slurry 3~5%, graphene starch 1~2%, titanium dioxide 5~8%, carbon black 0.1
~0.2%, aqueous zinc phosphate 2~5%, dispersing agent 0.3~0.8%, defoaming agent 0.3~0.6%, corrosion inhibiter 0.5~1%, aqueous organic
Bentonite 0.3~0.5%, fumed silica 0.2~0.4%, aqueous wax liquor 2~4%, blanc fixe 10~20%, silica flour
10~20%, conductive mica powder 20~35%, cosolvent 1~2%, deionized water 6.2~7.3%
B component is aqueous epoxy resin emulsion；
The weight ratio of component A and B component is 100:40~80.
2. water-base epoxy fullerene anticorrosive paint according to claim 1, which is characterized in that cosolvent is selected from ethylene glycol
Monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl alcohol, n-butanol
Or the alcohol ethers solvent such as isopropanol.
3. water-base epoxy fullerene anticorrosive paint according to claim 1, which is characterized in that in the fullerene slurry
Fullerene content be 10~16wt%.
4. water-base epoxy fullerene anticorrosive paint according to claim 3, which is characterized in that the fullerene slurry
Preparation method is: preparing the K containing 0.3~0.5mol/L2Cr2O7With the aqueous solution of the HCl of 1.2~1.5mol/L, in aqueous solution
The middle fullerene that 0.5~0.8g/L is added reacts 3~5h after mixing evenly under the conditions of 82~86 DEG C, after reaction, will
Solid is filtered out and is cleaned with deionized water, and is dried, and the fullerene of surface active is obtained；Using acetone as reaction dissolvent, at it
Fullerene, the 5~8wt%N of the middle surface active that 2~5wt% is added, N- dihydroxy ethyl -3- amido methyl acrylate and 10~
The second aqueous epoxy curing agent of 15wt% adds 0.8~1.0wt% Catalyzed by p-Toluenesulfonic Acid agent, disperses under ultrasound condition equal
After even, it is evaporated under reduced pressure under the conditions of 60~65 DEG C after removing solvent, then at N25 are stirred under the conditions of 40~45 DEG C under protective condition
~8h is reacted, and after the reaction was completed, is cleaned reactant, and vacuum drying with ethyl alcohol, is obtained the fullerene of hyperbranched modification；Again
The aqueous solution of the fullerene containing the hyperbranched modification of 10~16wt%, 1~1.5wt% sodium polycarboxylate dipersant is prepared, dispersion is equal
After even, fullerene slurry is obtained.
5. water-base epoxy fullerene anticorrosive paint according to claim 1, which is characterized in that the water-base epoxy tree
Fat liquor is the modification E51 epoxy resin latex of ethenyl blocking.
6. water-base epoxy fullerene anticorrosive paint according to claim 5, which is characterized in that the ethenyl blocking
The preparation method of modification E51 epoxy resin latex include the following steps: step 1, polyalcohol, isocyanates are added to reaction
In device, organotin catalysts are added, and under nitrogen protection, carries out 1~3h of reaction under the conditions of 82~88 DEG C, adds chain extension
Agent the reaction was continued 0.5~1h, obtains performed polymer；- NCO, the chain extender of-OH, isocyanates offer that wherein polyalcohol provides rub
You are than 5:6~8:1.2~1.6；Step 2 presses performed polymer, E51 epoxy resin, methyl methacrylate, azodiisobutyronitrile
It mixes according to weight ratio 1:6~8:0.5~0.8:0.05~0.2, then under nitrogen protection, is reacted under the conditions of 80~85 DEG C
0.5~1.5h adds ethenyl blocking polymethylphenylsiloxane and continues to react 1.5~2h of end capping reaction, vinyl
The weight ratio for blocking polymethylphenylsiloxane and performed polymer is 0.2:2~3；After reaction, neutralizer is added to be neutralized,
It adds deionized water to be vigorously stirred, obtains lotion；Deionized water and the additional amount of neutralizer are the weight of performed polymer
12~14 times and 0.05~0.1 times.
7. water-base epoxy fullerene anticorrosive paint according to claim 6, which is characterized in that described is organotin catalyzed
Agent is dibutyl tin dilaurate；The chain extender is l, 4- butanediol, neopentyl glycol, ethylene glycol, diglycol, sweet
One in oil, maleic anhydride, trimethylolpropane, ethylenediamine, diethylenetriamine, triethylene tetramine or dihydromethyl propionic acid
Kind or several mixtures；Neutralizer is triethylamine, methylamine or triethanolamine.
8. the preparation method of the described in any item water-base epoxy fullerene anticorrosive paints of claim 1~7, which is characterized in that
Include the following steps:
Step 1, by the first aqueous epoxy curing agent, dispersing agent, defoaming agent, corrosion inhibiter cosolvent be added production cylinder in, use
400~600 revs/min are stirred 5 minutes；
Aqueous organobentonite, fumed silica, aqueous wax liquor is added, using 400~600 revs/min in step 2 while stirring
Stirring 5 minutes；
Titanium dioxide, carbon black, blanc fixe, silica flour, aqueous zinc phosphate is added, using 600~800 in step 3 while stirring
Rev/min stirring 10 minutes；
Fineness is ground to 30 microns using sand mill by step 4；
Step 5 is slowly added into conductive mica powder using 400~600 revs/min while stirring, is stirred using 1000~1200 revs/min
25~30 minutes；
Step 6, using 600~800 revs/min be slowly added into while stirring graphene slurry, fullerene starch, using 800~1000 turns/
Divide stirring 40~60 minutes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698946A (en) * | 2019-09-17 | 2020-01-17 | 湖州市南浔联谊喷涂厂 | Superstrong anti-corrosion marine water-based paint and preparation method thereof |
| CN111793405A (en) * | 2020-07-31 | 2020-10-20 | 江苏华夏制漆科技有限公司 | Waterborne epoxy graphene zinc-containing anticorrosive primer |
| CN112011270A (en) * | 2020-08-28 | 2020-12-01 | 江苏华夏制漆科技有限公司 | Waterborne epoxy anticorrosive paint containing modified E51 epoxy and fullerene |
| CN115836115A (en) * | 2020-05-13 | 2023-03-21 | 石墨创新技术有限公司 | Composition for coating, coating and method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497636A (en) * | 2013-09-07 | 2014-01-08 | 中国科学院合肥物质科学研究院 | Waterborne epoxy zinc-rich paint modified by nanometer conductive carbon material and preparation method thereof |
| CN105086760A (en) * | 2015-08-20 | 2015-11-25 | 成都拜迪新材料有限公司 | Preparation method of waterborne epoxy graphene antiseptic primer |
-
2018
- 2018-05-10 CN CN201810440482.0A patent/CN109971316B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497636A (en) * | 2013-09-07 | 2014-01-08 | 中国科学院合肥物质科学研究院 | Waterborne epoxy zinc-rich paint modified by nanometer conductive carbon material and preparation method thereof |
| CN105086760A (en) * | 2015-08-20 | 2015-11-25 | 成都拜迪新材料有限公司 | Preparation method of waterborne epoxy graphene antiseptic primer |
Non-Patent Citations (1)
| Title |
|---|
| 朱靖: "多壁碳纳米管接枝超支化聚（胺-酯）", 《化工进展》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698946A (en) * | 2019-09-17 | 2020-01-17 | 湖州市南浔联谊喷涂厂 | Superstrong anti-corrosion marine water-based paint and preparation method thereof |
| CN110698946B (en) * | 2019-09-17 | 2021-11-26 | 广东嘉盛环保高新材料股份有限公司 | Superstrong anti-corrosion marine water-based paint and preparation method thereof |
| CN115836115A (en) * | 2020-05-13 | 2023-03-21 | 石墨创新技术有限公司 | Composition for coating, coating and method thereof |
| CN111793405A (en) * | 2020-07-31 | 2020-10-20 | 江苏华夏制漆科技有限公司 | Waterborne epoxy graphene zinc-containing anticorrosive primer |
| CN112011270A (en) * | 2020-08-28 | 2020-12-01 | 江苏华夏制漆科技有限公司 | Waterborne epoxy anticorrosive paint containing modified E51 epoxy and fullerene |
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