CN104910752B - A kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof - Google Patents
A kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof Download PDFInfo
- Publication number
- CN104910752B CN104910752B CN201510317422.6A CN201510317422A CN104910752B CN 104910752 B CN104910752 B CN 104910752B CN 201510317422 A CN201510317422 A CN 201510317422A CN 104910752 B CN104910752 B CN 104910752B
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- graphene
- component
- nano composite
- anticorrosion coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof；It is 1 by quality ratio:0.25‐1:0.5 component of A, B two is agitated uniform rear obtained；In parts by mass, component A includes epoxy resin 40-60, levelling agent 1-5, defoamer 1-5, filler 10-20, wetting dispersing agent 1-5, the first solvent 20-40；Component B includes curing agent 30-50, polyaniline in eigenstate graphene composite material 10-30, the second solvent 30-50.Polyaniline in eigenstate of the present invention and metal formation passivating film, ensure that the individual layer or few number of plies of graphene disperse, block the formation of graphene conductive network, suppress the generation of electrochemical corrosion from molecular level, physical shielding, chemical preservation effect are provided simultaneously, make the coating that there is outstanding Corrosion Protection, high temperature resistant, hardness are high, and preparation method is simply controllable, production cost is low, is conducive to industrialized production.
Description
Technical field
The present invention relates to a kind of anticorrosive paint, more particularly to a kind of polyaniline graphene nano composite anticorrosion coating and its
Preparation method, belongs to materials synthesis and Paint preparation technology technical field.
Background technology
Metal erosion refers to that metal material surface and environment occur chemistry and electrochemical reaction and make the hydraulic performance decline of material.
Metal erosion can cause huge loss, and one of most simple maximally effective anticorrosion means are exactly to coat one layer in metal surface to prevent
Corrosion resistant coating so that there is one layer of barrier metal surface with environment.At present, the demand in global anticorrosive paint market quickly increases
It is long, particularly in fields such as oil and gas industry, power industry, industrial circle and infrastructures.
Since the polyaniline films for reporting electrochemical polymerization on stainless steel of DeBerry in 1985 have passivation with
Afterwards, the research report of polyaniline anticorrosion is continued to bring out.At present, the commodity report of external existing industrialization.Domestic Hunan intrinsic safety
Ya great new materials Co., Ltd has formed the production capacity of polyaniline anti-corrosive paint, is applied as domestic earliest anticorrosive polyaniline
Material produces and sells enterprise.Polyaniline is a kind of new anticorrosion material, metal surface can be made to occur passivation phenomenon, in gold
Metal surface generates stable oxide；With metal formation compound, its oxidizing potential is increased, suppress oxidation reaction；
A direction and electron transmission electric field in opposite direction are produced, hinders electronics to be transmitted to oxidation material；Form one layer of polymeric screen
Barrier, realizes physical shielding and barrier.The above-mentioned property of polyaniline shows that its anticorrosion mechanism is mainly chemical attack, can replace
It is added to for poisonous heavy metal chromium system and lead system anticorrosion filler in anticorrosive paint and plays a role.
Chinese patent CN104449340A discloses one kind and uses Polyaniline emulsion, and adds a series of color stuffing preparation
For aqueous high tenacity anticorrosive paint.However, containing heavy metal bichromate in its color stuffing, certain damage can be caused to environment
Evil；In addition, its formula contains hydrochloric acid, the presence of chlorion can bring the risk of metal spot corrosion.Chinese patent CN104293075A
Take microemulsion method and prepare polyaniline, then add methyl methacrylate to the polyaniline micro-emulsion of gained again, polymerization is anti-
Should after obtain modified polyphenyl amine latexes, last blending epoxy, water, various auxiliary agents.The polyaniline that microemulsion method is obtained is to receive
Meter level is other, it is easy to scattered.But microemulsion method needs substantial amounts of surfactant, the latter needs cleaning for a long time to remove, otherwise
Paint film property can be impacted；Polymethyl methacrylate modified polyaniline is used, the latter can be improved to solvent, epoxy resin
Compatibility, but multiple polymerisation, step is relatively complicated.
Graphene has unique performance, turns into global focus and study hotspot at present.Graphene is one
Plant by sp2The two dimensional crystal material of hydbridized carbon atoms composition, with slightly wavy layered structure, it is considered to be composition stone
The basic component units of the allotropes such as ink, CNT, fullerene.The intensity of the graphene of graphene is up to 130GPa,
It is one of best material of the mechanical property found so far, its thermal conductivity reaches 5000W/ (mK), is good heat carrier.Graphite
The unique carrier properties of alkene, make its electron mobility reach 2 × 105Cm2/ (VS), more than 100 times of silicon, and little with
Temperature change and change.Graphene thermal stability is good, excellent electric conductivity, high hardness the advantages of it is applied in coating,
And achieve preferable application effect.There is research (Prasai D, Tuberquia J C, Harl R R, et al.Graphene:
corrosion‐inhibiting coating.ACS Nano,2012,6(2):1102-1108.) show to use chemical vapor deposition
Graphene film prepared by area method, can make metal erosion slow down 20 times.Researcher (Yu, Y.H., et al., High-
performance polystyrene/graphene‐based nanocomposites with excellent anti‐
corrosion properties.Polymer Chemistry,2014.5(2):P.535-550. in-situ emulsion polymerization) is used
The graphene oxide (pv-GO) being modified through p-phenylenediamine/4- vinyl benzoic acids is added in polystyrene (PS) by method to be obtained
Simultaneously coating is made in pv-GO/PS nano composite materials.Compared with pure polystyrene, film anticorrosion erosion efficiency is brought up to by 37.90%
99.53%.It can be seen that, if graphene is used as into anticorrosive packing, it can be provided more than conventional fillers such as mica powder, aluminium powder, glass flakes
Outstanding physical shielding performance., can based on the above-mentioned description for polyaniline and graphene, it is believed that both synergies
Outstanding physics and chemical preservation corrosion energy are provided to paint film simultaneously.
However, still to there are some technical problems urgently to be resolved hurrily for application of the graphene in anticorrosive coating at present.Stone
Black alkene is using mainly there is two kinds of trial means in corrosion-resistant field, and the first is graphene is existed in the way of chemical vapor deposition
Metal surface forms coated film.But this coated film is in prolonged anti corrosion test, uneven corrosion is occurred in that
Phenomenon, or even corrosion also serious (Schriver M, Regan W, Gannett W J, et than proof gold metal surface
al.Graphene as a long‐term metal oxidation barrier:worse than nothing.ACS
Nano,2013,7(7):5763‐5768.).The reason for this phenomenon occurs is likely to be that graphite ene coatings are not perfect,
And its high conductivity promotes the process of electrochemical corrosion.Another trial means that graphene is applied in corrosion-resistant field, be
Graphene is mixed in polymeric material.This method can effectively improve the mechanical property of polymeric material, to hot steady
Qualitative and chemical stability etc..But the addition of graphene is when reaching certain value, the polymeric material of insulation is led originally
Several orders of magnitude can be also electrically improved, this can but bring the side effect for promoting to corrode.Especially there is flaw in paint film, metal-
During graphene-external environment formation conductive path, corrosion promotes effect particularly evident.Analyzed from the principle of this phenomenon, this shows
The appearance of elephant needs to meet three conditions：There is electrical potential difference, graphene and metal formation conductive path, the external world with metal in graphene
Environment contains corrosive substance.Accordingly, it would be desirable to take specific aim measure to three above factor.
Chinese patent CN103173095A discloses a kind of Zinc-rich epoxy anticorrosion paint of graphene-containing, graphene, zinc powder
Weight/mass percentage composition sum with filler is 60-80%.The addition of graphene causes film thickness to reduce, and zinc content is also significantly
Reduction.The specific surface area of graphene is very big, has great mutual stack (stacking) to be inclined to.In that patent, graphite
Alkene does not obtain further processing and is added among coating, then it easily occurs to reunite in dispersion process, stacked again
(re-stacking) performance of self performance is influenceed.Chinese invention patent application CN102604533A discloses a kind of based on poly-
The anticorrosive paint and preparation method of aniline and graphene composite material.The invention thinks that graphene radius-thickness ratio height, pliability are good, profit
In raising paint film physical preservation performance, and the conductive polyaniline for being supported on graphene can provide electrochemical anti-corrosive；The two
Synergy mechanism cause the coating that there is excellent metal erosion barrier propterty；The anticorrosive paint can realize metal base
Passivation and inhibition, while avoiding the use of the heavy metals such as the chromium that can cause environmental pollution.It is negative using conductive polyaniline
It is loaded on graphene, can effectively strengthens the electric conductivity of polyaniline/graphene complex.It is such as poly- in some polymeric materials
Carbonic ester, thermoplastic polyurethane etc., conduction percolation threshold of the graphene in system most preferably shield external substance than reaching
Addition during performance is small, it means that gained paint film can be while conductive and shielding properties.In well dispersed feelings
Under condition, the electrically conductive composite can build three-dimensional conductive network in paint film, form huge conductive path.This just meets above
The corrosion promotes the first two condition of effect, and when flaw, conductive path occurs in paint film, (such as electrolyte is molten with extraneous corrosive deposit
Liquid) when directly contacting, then three conditions are met simultaneously, it is most likely that the effect that corrosion promotes is presented.There are research (Sun, W., et
al.,Inhibiting the Corrosion‐Promotion Activity of Graphene.Chemistry of
Materials,2015.27(7):P.2367-2373. graphene) is wrapped up using Silane coupling agent KH550 and is used in poly-
In vinyl butyral anticorrosive paint, this is contrasted with the polyvinyl butyral resin anticorrosive paint containing pure graphene.
When being tested using electrochemical impedance spectroscopy, the cut that paint film first is marked into certain length exposes metal, and pure graphite is contained after three days
The impedance of the polyvinyl butyral resin anticorrosive paint of alkene is only that the polyvinyl butyral resin anti-corrosion containing KH550 modified graphenes is applied
/ 20th of material.
The content of the invention
The purpose of the present invention be for graphene anticorrosive paint application in technical problem there is provided a kind of insulation, profit
In resistance film physical damage, good endurance, the polyaniline graphene nano composite anticorrosion coating of high comprehensive performance.
The present invention also aims to provide, a kind of production cost is low, technique is simple, easily realize the poly- of industrialized production
The preparation method of aniline graphene nano composite anticorrosion coating.
Polyaniline is a kind of new anticorrosion material, and metal surface can be made to occur passivation phenomenon, looked unfamiliar in metal watch
Into stable oxide；With metal formation compound, its oxidizing potential is increased, suppress oxidation reaction；Produce one
Direction and electron transmission electric field in opposite direction, hinder electronics to be transmitted to oxidation material；One layer of polymeric barrier is formed, thing is realized
Reason shielding and barrier.The advantages of graphene thermal stability is good, hardness is high, mechanical performance is excellent makes it be answered in anticorrosive paint
With, and achieve preferable application effect.
Electric conductivity doped polyaniline is prepared under sour environment, the conductive polyaniline of inorganic acid doping is often molten
Solubility is relatively low in agent system；Can improve its solubility using organic macromolecule acid, so obtained from doped polyaniline still
It is conductive.Product is placed in progress dedoping reaction in alkaline environment by the present invention by the dedoping technique that alkalizes, you can
Obtain insulating properties polyaniline in eigenstate.Its solubility in dicyandiamide solution is of a relatively high, and polyaniline molecule chain is preferably unfolded
And closed with epoxy resin-matrix bear building-up.After polyaniline in eigenstate parcel graphene formation compound, it can ensure on a molecular scale
The individual layer of graphene or few number of plies are scattered in epoxy resin substrate, keep the excellent properties and performance physics of graphene in itself
Shielding action, and chemical preservation effect can be provided with passive metal, the conductive network of metal-graphite alkene-graphene is blocked, is entered
One step suppresses electrochemical corrosion.Anti-corrosive paint of epoxy resin is one of traditional ripe anticorrosive paint system, epoxy resin attachment
Power is strong, and the paint film after solidification has close molecular structure, and phenyl ring and ehter bond property are stable, it is possible to for chemicals ring
Border, forms the strong barrier of isolation external environment.Polyaniline in eigenstate graphene composite material is added to epoxy resin anti-corrosion
In coating, the advantage of the epoxy coating not only retained, and further increase paint film strength, be provided simultaneously with physics screen
Cover, chemical preservation erosion performance.
To reach above-mentioned purpose, the present invention is achieved through the following technical solutions：
A kind of polyaniline graphene nano composite anticorrosion coating, is uniformly mixed obtained by component A and component B；It is described
Component A and component B are 1 by quality ratio:0.25‐1:0.5；
In terms of mass fraction, component A composition of raw materials composition is：
In terms of mass fraction, component B composition of raw materials composition is：
Curing agent 30-50；
Polyaniline in eigenstate graphene composite material 10-20；
Second solvent 30-50；
Described curing agent is polyamide curing agent, polyethers amine hardener, liquid fat race polyamine curing agent or liquid
Pnenolic aldehyde amine hardener；
Described levelling agent be silicone Levaslip466, alkyl-modified organosiloxane,X 043、The Hes of X 080One or both of X 073；
Described defoamer is organic silicone4000th, organic silicone4006th, organic silicone4010 Hes
Fluorine-containing brokenly bubble polymer solution4050 one or two；
Described wetting dispersing agent isPON S 596、‐PON S 606、WS
4187、The Hes of-PON 154- PON DB 50 one or two；
Described polyaniline in eigenstate graphene composite material, which is made by the steps, to be obtained：
1) synthesis of doped polyaniline graphene composite material：Graphene is added in hydrochloric acid solution, and surpassed
Sound cell pulverization, adds aniline after being uniformly dispersed, is uniformly mixed at 0-5 DEG C, obtain mixed liquor A；The concentration of aniline is controlled to be
0.05-0.35mol/L, graphene concentration is 0.5-5mg/mL, and concentration of hydrochloric acid is 0.1-1mol/L；Oxidant is dissolved into hydrochloric acid
Mixed liquid B is obtained after solution；Mixed liquid B is added in mixed solution A, is uniformly mixed at 0-5 DEG C, reaction 6-24 is small
When, centrifugation, washing obtain doped polyaniline graphene composite material；The oxidant is iron chloride, ammonium persulfate or over cure
The amount ratio of the material of sour potassium, oxidant and aniline is 1:0.5‐1:2；
2) the alkalization dedoping of polyaniline in eigenstate graphene composite material：By doped polyaniline graphene composite material
It is added in ammonia spirit, uniform, stirring 4-12 hours is stirred at room temperature, centrifugation, washing obtain eigenstate polyphenyl after drying
Amine graphene composite material.
Further to realize the object of the invention, it is preferable that described epoxy resin is epoxy resin E51, epoxy resin
E44, epoxy resin E42, epoxy resin E35, epoxy resin E31, epoxy resin E20 one or two.
Preferably, described filler is micaceous iron oxide scale, mica flake, talcum powder, aerosil, dicalcium powder
With the one or two of nano-aluminium oxide.
Preferably, the first described solvent is ethyl acetate, butyl acetate, toluene, n-butanol, dimethylbenzene, N- methyl pyrroles
One or both of pyrrolidone and N,N-dimethylformamide.
Preferably, the second described solvent is toluene, n-butanol, dimethylbenzene, 1-METHYLPYRROLIDONE and N, N- dimethyl
One or both of formamide.
Preferably, the step 1) doped polyaniline graphene composite material synthesis in, ultrasonic cell disrupte when
Between be 10-60 minutes.
Preferably, the step 1) the mixing speed being uniformly mixed twice be 100-200rpm.
Preferably, the concentration of the ammonia spirit is 0.1-1mol/L.
Preferably, the speed stirred at room temperature is 100-200rpm.
The preparation method of the polyaniline graphene nano composite anticorrosion coating, is carried out as follows：
1) component A preparation：Under the protection of nitrogen, epoxy resin and first are sequentially added by formula rate to reactor
In solvent, high-speed stirred；Levelling agent, defoamer, filler, wetting dispersing agent are sequentially added after dispersed by formula rate to continue
High-speed stirred 0.5-2 hours, dispersed and finely ground rear discharging, sealing is kept in dark place in the cool；
2) component B preparation：Under the protection of nitrogen, curing agent and eigenstate are sequentially added by formula rate to reactor
Polyaniline graphene composite material, stirring at low speed；It is molten by formula rate addition second in the state of being kept stirring for after dispersed
Agent, is uniformly dispersed and is discharged after finely ground, sealing is kept in dark place in the cool；
3) it is 1 to weigh mass ratio:0.25‐1:0.5 component A and component B, after being uniformly mixed, stands 30 minutes, obtains
To polyaniline graphene nano composite anticorrosion coating.
Compared with prior art, the present invention has following prominent effect：
1) in polyaniline graphene nano composite anticorrosion coating of the present invention, doped polyaniline graphene nano is answered
Condensation material is made in the way of in-situ polymerization, using alkalization dedoping technique, i.e., dedoping reaction system is carried out in alkaline environment
Obtain insulating properties polyaniline in eigenstate graphene nanocomposite material.The polyaniline-coated graphene-structured of gained, from molecular level
On ensure that the individual layer or few number of plies of graphene disperse, polyaniline graphene nanocomposite material can be improved in dicyandiamide solution
The compatibility of solubility, raising and coating system, is conducive to graphene to be uniformly dispersed in paint-based bottom to play its mechanical property
Can, metal-graphite alkene-graphene conductive network is effectively blocked, further suppresses the generation of electrochemical corrosion.This is nano combined
Material can in coating stable dispersion, neither influence coating, paint film appearance, be also conducive to the performance of composite property.
2) in nano-composite corrosion proof paint of the present invention, on the one hand graphene improves the mechanical property of resin, separately
On the one hand form isolation layer and physical shielding effect is provided, the cavity that can fill up paint film prevents corrosive medium from entering Metal Substrate
Body；And polyaniline can prevent the electric charge transfer in corrosion process and ion diffusion, and its amido knot with metal formation passivating film
Structure will participate in the cross-linking reaction of Curing Process of Epoxy, further increase the compactness of paint film.The two synergy causes
The Corrosion Protection of the coating is lifted well.
3) resin solid content height, the viscosity for inventing described polyaniline graphene nano composite anticorrosion coating are low, prepare and apply
The use of curing agent and solvent can be reduced during material, VOC is reduced.
4) polyaniline graphene nano composite anticorrosion coating of the present invention is free of heavy metal component, and application is more
Extensively, practicality is stronger.
5) the preparation process step of polyaniline graphene composite material and nano-composite corrosion proof paint of the present invention is few,
Operation is mainly temperature control and liquid agitation, and technological process is simple；To pressure and no requirement (NR), therefore to instrument and equipment requirement
Low, generally conventional container and paint production plant can reach the requirement, be adapted to large-scale production.
Brief description of the drawings
Fig. 1 is Q235 and embodiment 1-6 Tafel polarization curve.
Embodiment
With reference to embodiment, the invention will be further described, it is necessary to which explanation, embodiment is not constituted to the present invention
The limitation of claimed scope.
Embodiment 1：
In terms of mass fraction, component A composition of raw materials composition is：
In terms of mass fraction, component B composition of raw materials composition is：
Polyamide curing agent 48；
Polyaniline in eigenstate graphene composite material 10；
Dimethylbenzene 42.
Polyaniline graphene nano composite anticorrosion coating is prepared as follows：
(1) polyaniline in eigenstate graphene composite material is prepared
1) graphene is added in hydrochloric acid solution, ultrasonic cell disrupte 10 minutes adds aniline, in 0- after being uniformly dispersed
5 DEG C are uniformly mixed with 200rpm speed.Wherein, concentration of aniline is 0.05mol/L, and graphene concentration is 0.5mg/mL,
Concentration of hydrochloric acid is 0.1mol/L.Oxidant is dissolved into certain density hydrochloric acid solution, is added into containing aniline, graphene
Hydrochloric acid solution in, be uniformly mixed, reacted 24 hours with 200rpm speed at 0-5 DEG C, centrifugation, washing are mixed for three times
Miscellaneous state polyaniline graphene composite material.
2) doped polyaniline graphene composite material is added in the ammonia spirit that concentration is 0.1mol/L, at room temperature
Stirred 4 hours with 100rpm speed, centrifugation, washing three times obtain polyaniline in eigenstate graphene composite material after drying.Its
Middle oxidant is iron chloride, and the amount ratio with the material of aniline is 1:0.5.
(2) polyaniline graphene nano composite anticorrosion coating is prepared
1) component A preparation：Under the protection of nitrogen, to reactor by formula rate sequentially add epoxy resin E51 and
Dimethylbenzene, high-speed stirred；After dispersed dimethyl silicone polymer Silic 308A, organic silicone are sequentially added by formula rate4000th, micaceous iron oxide scale, talcum powder,‐PON S 596、WS 4187, continues at a high speed
Stirring 2 hours, dispersed and finely ground rear discharging, sealing is kept in dark place in the cool.
2) component B preparation：Under the protection of nitrogen, to reactor by formula rate sequentially add polyamide curing agent with
Polyaniline in eigenstate graphene composite material, stirring at low speed；After dispersed, added in the state of being kept stirring for by formula rate
Dimethylbenzene, is uniformly dispersed and is discharged after finely ground, sealing is kept in dark place in the cool.
3) it is 1 to weigh mass ratio:0.25 component A and component B, after being uniformly mixed, stands 30 minutes, obtains polyphenyl
Amine graphene nano composite anticorrosion coating.
Embodiment 2：
In terms of mass fraction, component A composition of raw materials composition is：
In terms of mass fraction, component B composition of raw materials composition is：
Polyaniline graphene nano composite anticorrosion coating is prepared as follows：
(1) polyaniline in eigenstate graphene composite material is prepared
1) graphene is added in hydrochloric acid solution, ultrasonic cell disrupte 30 minutes adds aniline, in 0- after being uniformly dispersed
5 DEG C are uniformly mixed with 200rpm speed.Wherein, concentration of aniline is 0.09mol/L, and graphene concentration is 0.8mg/mL,
Concentration of hydrochloric acid is 0.3mol/L.Oxidant is dissolved into certain density hydrochloric acid solution, is added into containing aniline, graphene
Hydrochloric acid solution in, be uniformly mixed, reacted 18 hours with 200rpm speed at 0-5 DEG C, centrifugation, washing are mixed for three times
Miscellaneous state polyaniline graphene composite material.
2) doped polyaniline graphene composite material is added in the ammonia spirit that concentration is 0.3mol/L, at room temperature
Stirred 4 hours with 100rpm speed, centrifugation, washing three times obtain polyaniline in eigenstate graphene composite material after drying.Its
Middle oxidant is ammonium persulfate, and the amount ratio with the material of aniline is 1:1.
(2) polyaniline graphene nano composite anticorrosion coating is prepared
1) component A preparation：Under the protection of nitrogen, epoxy resin E51, two are sequentially added by formula rate to reactor
Toluene and n-butanol, high-speed stirred；Sequentially added after dispersed by formula rateX 073、
X043, organic silicone4006th, micaceous iron oxide scale, nano-aluminium oxide,- PON S 596, continue
High-speed stirred 1 hour, dispersed and finely ground rear discharging, sealing is kept in dark place in the cool.
2) component B preparation：Under the protection of nitrogen, to reactor by formula rate sequentially add polyethers amine hardener with
Polyaniline in eigenstate graphene composite material, stirring at low speed；After dispersed, added in the state of being kept stirring for by formula rate
Dimethylbenzene and 1-METHYLPYRROLIDONE, are uniformly dispersed and are discharged after finely ground, sealing is kept in dark place in the cool.
3) it is 1 to weigh mass ratio:0.25 component A and component B, after being uniformly mixed, stands 30 minutes, obtains polyphenyl
Amine graphene nano composite anticorrosion coating.
Embodiment 3：
In terms of mass fraction, component A composition of raw materials composition is：
In terms of mass fraction, component B composition of raw materials composition is：
Polyaniline graphene nano composite anticorrosion coating is prepared as follows：
(1) polyaniline in eigenstate graphene composite material is prepared
1) graphene is added in hydrochloric acid solution, ultrasonic cell disrupte 45 minutes adds aniline, in 0- after being uniformly dispersed
5 DEG C are uniformly mixed with 200rpm speed.Wherein, concentration of aniline is 0.19mol/L, and graphene concentration is 2mg/mL, salt
Acid concentration is 0.5mol/L.Oxidant is dissolved into certain density hydrochloric acid solution, is added into containing aniline, graphene
In hydrochloric acid solution, it is uniformly mixed, is reacted 12 hours with 200rpm speed at 0-5 DEG C, is centrifuged, washs three times and adulterated
State polyaniline graphene composite material.
2) doped polyaniline graphene composite material is added in the ammonia spirit that concentration is 0.5mol/L, at room temperature
Stirred 8 hours with 100rpm speed, centrifugation, washing three times obtain polyaniline in eigenstate graphene composite material after drying.Its
Middle oxidant is one kind of potassium peroxydisulfate, and the amount ratio with the material of aniline is 1:1.1.
(2) polyaniline graphene nano composite anticorrosion coating is prepared
1) component A preparation：Under the protection of nitrogen, epoxy resin E44, first are sequentially added by formula rate to reactor
Benzene and n-butanol, high-speed stirred；Sequentially added after dispersed by formula rateX 080, fluorine-containing brokenly bubble polymer
Solution4050th, micaceous iron oxide scale, aerosil,- PON S 606, continue high-speed stirred 0.5
Hour, dispersed and finely ground rear discharging, sealing is kept in dark place in the cool.
2) component B preparation：Under the protection of nitrogen, by formula rate liquid fat race is sequentially added to reactor polynary
Amine hardener and polyaniline in eigenstate graphene composite material, stirring at low speed；After dispersed, in the state of being kept stirring for by with
Square ratio adds 1-METHYLPYRROLIDONE and n-butanol, is uniformly dispersed and is discharged after finely ground, sealing is kept in dark place in the cool.
3) it is 1 to weigh mass ratio:0.4 component A and component B, after being uniformly mixed, stands 30 minutes, obtains polyphenyl
Amine graphene nano composite anticorrosion coating.
Embodiment 4：
In terms of mass fraction, component A composition of raw materials composition is：
In terms of mass fraction, component B composition of raw materials composition is：
Polyaniline graphene nano composite anticorrosion coating is prepared as follows：
(1) polyaniline in eigenstate graphene composite material is prepared
1) graphene is added in hydrochloric acid solution, ultrasonic cell disrupte 60 minutes adds aniline, in 0- after being uniformly dispersed
5 DEG C are uniformly mixed with 200rpm speed.Wherein, concentration of aniline is 0.32mol/L, and graphene concentration is 3.2mg/mL,
Concentration of hydrochloric acid is 0.8mol/L.Oxidant is dissolved into certain density hydrochloric acid solution, is added into containing aniline, graphene
Hydrochloric acid solution in, be uniformly mixed, reacted 12 hours with 200rpm speed at 0-5 DEG C, centrifugation, washing are mixed for three times
Miscellaneous state polyaniline graphene composite material.
2) doped polyaniline graphene composite material is added in the ammonia spirit that concentration is 0.8mol/L, at room temperature
Stirred 8 hours with 100rpm speed, centrifugation, washing three times obtain polyaniline in eigenstate graphene composite material after drying.Its
Middle oxidant is iron chloride, ammonium persulfate, one kind of potassium peroxydisulfate, and the amount ratio with the material of aniline is 1:1.2.
(2) polyaniline graphene nano composite anticorrosion coating is prepared
1) component A preparation：Under the protection of nitrogen, epoxy resin E51, ring are sequentially added by formula rate to reactor
Oxygen tree fat E20,1-METHYLPYRROLIDONE and n-butanol, high-speed stirred；Sequentially added after dispersed by formula rateX 073, organic silicone401st, micaceous iron oxide scale, dicalcium powder,‐PON S 606、WS 4187, continues high-speed stirred 1 hour, and dispersed and finely ground rear discharging, sealing is kept in dark place in the cool.
2) component B preparation：Under the protection of nitrogen, to reactor by formula rate sequentially add polyamide curing agent with
Polyaniline in eigenstate graphene composite material, stirring at low speed；After dispersed, added in the state of being kept stirring for by formula rate
DMF and n-butanol, are uniformly dispersed and are discharged after finely ground, sealing is kept in dark place in the cool.
3) it is 1 to weigh mass ratio:0.5 component A and component B, after being uniformly mixed, stands 30 minutes, obtains polyphenyl
Amine graphene nano composite anticorrosion coating.
Embodiment 5：
In terms of mass fraction, component A composition of raw materials composition is：
In terms of mass fraction, component B composition of raw materials composition is：
Liquid pnenolic aldehyde amine hardener 40；
Polyaniline in eigenstate graphene composite material 30；
Dimethylbenzene 30.
Polyaniline graphene nano composite anticorrosion coating is prepared as follows：
(1) polyaniline in eigenstate graphene composite material is prepared
1) graphene is added in hydrochloric acid solution, ultrasonic cell disrupte 45 minutes adds aniline, in 0- after being uniformly dispersed
5 DEG C are uniformly mixed with 200rpm speed.Wherein, concentration of aniline is 0.35mol/L, and graphene concentration is 5mg/mL, salt
Acid concentration is 1mol/L.Oxidant is dissolved into certain density hydrochloric acid solution, the salt containing aniline, graphene is added into
In acid solution, it is uniformly mixed, is reacted 6 hours with 200rpm speed at 0-5 DEG C, centrifugation, washing obtains doped three times
Polyaniline graphene composite material.
2) by doped polyaniline graphene composite material be added to concentration be 1mol/L ammonia spirit in, at room temperature with
100rpm speed is stirred 6 hours, centrifugation, washing three times, and polyaniline in eigenstate graphene composite material is obtained after drying.Wherein
Oxidant is hydrogen peroxide, and the amount ratio with the material of aniline is 1:2.
(2) polyaniline graphene nano composite anticorrosion coating is prepared
1) component A preparation：Under the protection of nitrogen, epoxy resin E44, ring are sequentially added by formula rate to reactor
Oxygen tree fat E20, DMF and dimethylbenzene, high-speed stirred；After dispersed silicone is sequentially added by formula rate
Levaslip466, organic silicone4000th, micaceous iron oxide scale, mica flake,‐PON 154、WS 4187, continues high-speed stirred 1 hour, and dispersed and finely ground rear discharging, sealing is kept in dark place in the cool.
2) component B preparation：Under the protection of nitrogen, the solidification of liquid phenolic aldehyde amine is sequentially added by formula rate to reactor
Agent and polyaniline in eigenstate graphene composite material, stirring at low speed；After dispersed, by formula rate in the state of being kept stirring for
Dimethylbenzene is added, is uniformly dispersed and is discharged after finely ground, sealing is kept in dark place in the cool.
3) it is 1 to weigh mass ratio:0.4 component A and component B, after being uniformly mixed, stands 30 minutes, obtains polyphenyl
Amine graphene nano composite anticorrosion coating.
Embodiment 6
In terms of mass fraction, component A composition of raw materials composition is：
In terms of mass fraction, component B composition of raw materials composition is：
Polyethers amine hardener 50；
Polyaniline in eigenstate graphene composite material 11；
Dimethylbenzene 39.
Polyaniline graphene nano composite anticorrosion coating is prepared as follows：
(1) polyaniline in eigenstate graphene composite material is prepared
1) graphene is added in hydrochloric acid solution, ultrasonic cell disrupte 40 minutes adds aniline, in 0- after being uniformly dispersed
5 DEG C are uniformly mixed with 200rpm speed.Wherein, concentration of aniline is 0.25mol/L, and graphene concentration is 2.5mg/mL,
Concentration of hydrochloric acid is 1mol/L.Oxidant is dissolved into certain density hydrochloric acid solution, is added into containing aniline, graphene
In hydrochloric acid solution, it is uniformly mixed, is reacted 12 hours with 200rpm speed at 0-5 DEG C, is centrifuged, washs three times and adulterated
State polyaniline graphene composite material.
2) by doped polyaniline graphene composite material be added to concentration be 1mol/L ammonia spirit in, at room temperature with
100rpm speed is stirred 6 hours, centrifugation, washing three times, and polyaniline in eigenstate graphene composite material is obtained after drying.Wherein
Oxidant is ammonium persulfate, and the amount ratio with the material of aniline is 1:1.2.
(2) polyaniline graphene nano composite anticorrosion coating is prepared
1) component A preparation：Under the protection of nitrogen, epoxy resin E51, ring are sequentially added by formula rate to reactor
Oxygen tree fat E31, dimethylbenzene, high-speed stirred；Sequentially added after dispersed by formula rateX 073, organosilicon
Ketone4010th, micaceous iron oxide scale, aerosil,- PON S 606, continue high-speed stirred 1 small
When, dispersed and finely ground rear discharging, sealing is kept in dark place in the cool.
2) component B preparation：Under the protection of nitrogen, to reactor by formula rate sequentially add polyethers amine hardener with
Polyaniline in eigenstate graphene composite material, stirring at low speed；After dispersed, added in the state of being kept stirring for by formula rate
Dimethylbenzene, is uniformly dispersed and is discharged after finely ground, sealing is kept in dark place in the cool.
3) it is 1 to weigh mass ratio:0.4 component A and component B, after being uniformly mixed, stands 30 minutes, obtains polyphenyl
Amine graphene nano composite anticorrosion coating.
Brown, surface light after polyaniline graphene nano composite coating film-forming made from above-described embodiment 1~6
It is sliding.The product of above-described embodiment 1~6 is subjected to performance test.According to following standard, to prepared polyaniline graphene nano
Composite coating makes a service test：
The non-volatile content of coating is determined by GB/T 1725-2007；
The viscosity of coating is determined by GB/T 10247-2008；
Film thickness is determined by GB/T 13452.2-2008；
Hardness of paint film is determined by GB/T 6739-2006；
The water resistance of resin paint film is determined by GB 5209-1985；
The resistance to acids and bases of paint film is determined by GB 9274-1988；
The resistance to neutral salt spray of paint film is determined by GB 1771-2007；
Obtain result of the test as shown in table 1：
The polyaniline graphene nano composite coating performance test results of table 1
The data of table 1 are illustrated：The storage stability of polyaniline graphene nano composite coating of the present invention is good；Do not wave
Stimulating food content is high in the solid content of 60% coating described above, and viscosity illustrates that the viscosity of coating is low in below 30s, high-solid lower-viscosity
Coating VOC it is lower, more conducively environmental protection；Have benefited from dedoping technique so that polyaniline graphene nanometer composite is scattered equal
Even, close with resin-bonded, graphene is able to play its mechanical property well, and the hardness of paint film is 5H, and hardness is more typically prevented
Rotten paint film (B-3H) is much higher, is conducive to resistance physical damage, durability more preferable；Water resistance, resistance to acids and bases, the resistance to neutrality of paint film
Salt spray test has excellent effect, illustrates that the weatherability of paint film is strong, can still continue to play anticorrosion work in acid or alkali environment
With.
Wherein, the material of test plate (panel) is Q235 low-carbon steel, according to《GBT 9271-1988 paint and varnish standard test plate (panel)s》In
Polishing method making sheet, size is 80*60*1mm.
According to《Corrosion electrochemistry principle》Chapter 6, in " 6.1.2 steady state measurements and metasable state measuring method ", carry out strong pole
Change measurement, i.e. Tafel polarization curves to test.Concrete operations are as follows：Lead to Autolab PGSTAT30 electrochemical operations in Switzerland ten thousand
Stand progress, using Q235 steel plates as working electrode, using Ag/AgCl electrodes as reference electrode, using graphite electrode as to electrode.Put up
After three-electrode system, treat that OCP is stable (amplitude of variation is no more than 10mV in i.e. 10 minutes), using OCP ± 500mV as
Potential range, with 0.5mV/S velocity scanning, to obtain electric current-potential response curve.Tafel analyses finally are carried out to curve,
Obtain corrosion potential and corrosion current.
Table 2Q235 and embodiment 1-6 Tafel polarization curve result
Table 2, Fig. 1 the data obtaineds show that the test plate (panel) corrosion potential for scribbling paint film is substantially offset to positive direction, is illustrated in heating power
On, sample is less prone to corrosion reaction；Corrosion current has the reduction of the 6-7 order of magnitude, illustrates, kinetically, to try
The corrosion reaction speed of sample is more slowly.
The step of above-described embodiment 1-6 polyaniline graphene nano composite coating preparation process, is few, and operation is mainly temperature
Control and liquid agitation, technological process are simple, to pressure and no requirement (NR), therefore require low, generally conventional container to instrument and equipment
And production of resins equipment can reach the requirement, it is adapted to large-scale production.
Claims (10)
1. a kind of polyaniline graphene nano composite anticorrosion coating, it is characterised in that：It is uniformly mixed by component A and component B
It is made；The component A and component B are 1 by quality ratio:0.25‐1:0.5；
In terms of mass fraction, component A composition of raw materials composition is：
In terms of mass fraction, component B composition of raw materials composition is：
Curing agent 30-50；
Polyaniline in eigenstate graphene composite material 10-20；
Second solvent 30-50；
Described curing agent is polyamide curing agent, polyethers amine hardener, liquid fat race polyamine curing agent or liquid phenolic aldehyde
Amine hardener；
Described levelling agent be silicone Levaslip466, alkyl-modified organosiloxane,X 043、The Hes of X 080One or both of X 073；
Described defoamer is organic silicone4000th, organic silicone4006th, organic silicone4010 and fluorine-containing
Brokenly bubble polymer solution4050 one or two；
Described wetting dispersing agent is‐PON S 596、‐PON S 606、WS
4187、The Hes of-PON 154- PON DB 50 one or two；
Described polyaniline in eigenstate graphene composite material, which is made by the steps, to be obtained：
1) synthesis of doped polyaniline graphene composite material：Graphene is added in hydrochloric acid solution, and carried out ultrasonic thin
Born of the same parents crush, and add aniline after being uniformly dispersed, are uniformly mixed at 0-5 DEG C, obtain mixed liquor A；It is 0.05- to control concentration of aniline
0.35mol/L, graphene concentration is 0.5-5mg/mL, and concentration of hydrochloric acid is 0.1-1mol/L；Oxidant is dissolved into hydrochloric acid solution
After obtain mixed liquid B；Mixed liquid B is added in mixed solution A, is uniformly mixed at 0-5 DEG C, is reacted 6-24 hours, from
The heart, washing, obtain doped polyaniline graphene composite material；The oxidant be iron chloride, ammonium persulfate or potassium peroxydisulfate,
The amount ratio of the material of oxidant and aniline is 1:0.5‐1:2；
2) the alkalization dedoping of polyaniline in eigenstate graphene composite material：Doped polyaniline graphene composite material is added
Into ammonia spirit, uniform, stirring 4-12 hours is stirred at room temperature, centrifugation, washing obtain polyaniline in eigenstate stone after drying
Black alkene composite.
2. polyaniline graphene nano composite anticorrosion coating according to claim 1, it is characterised in that described asphalt mixtures modified by epoxy resin
Fat is epoxy resin E51, epoxy resin E44, epoxy resin E42, epoxy resin E35, epoxy resin E31, epoxy resin E20
It is one or two kinds of.
3. polyaniline graphene nano composite anticorrosion coating according to claim 1, it is characterised in that described filler is
Micaceous iron oxide scale, mica flake, talcum powder, aerosil, dicalcium powder and one kind of nano-aluminium oxide or two
Kind.
4. polyaniline graphene nano composite anticorrosion coating according to claim 1, it is characterised in that described first is molten
Agent is in ethyl acetate, butyl acetate, toluene, n-butanol, dimethylbenzene, 1-METHYLPYRROLIDONE and N,N-dimethylformamide
It is one or two kinds of.
5. polyaniline graphene nano composite anticorrosion coating according to claim 1, it is characterised in that described second is molten
Agent is one or both of toluene, n-butanol, dimethylbenzene, 1-METHYLPYRROLIDONE and N,N-dimethylformamide.
6. polyaniline graphene nano composite anticorrosion coating according to claim 1, it is characterised in that the step 1) mix
In the synthesis of miscellaneous state polyaniline graphene composite material, the time of ultrasonic cell disrupte is 10-60 minutes.
7. polyaniline graphene nano composite anticorrosion coating according to claim 1, it is characterised in that the step 1)
The mixing speed being uniformly mixed twice is 100-200rpm.
8. polyaniline graphene nano composite anticorrosion coating according to claim 1, it is characterised in that the ammonia spirit
Concentration be 0.1-1mol/L.
9. polyaniline graphene nano composite anticorrosion coating according to claim 1, it is characterised in that described to stir at room temperature
The speed mixed is 100-200rpm.
10. the preparation method of any one of the claim 1-9 polyaniline graphene nano composite anticorrosion coatings, it is characterised in that
Carry out as follows：
1) component A preparation：Under the protection of nitrogen, epoxy resin and the first solvent are sequentially added by formula rate to reactor
In, high-speed stirred；Levelling agent, defoamer, filler, wetting dispersing agent are sequentially added after dispersed by formula rate to continue at a high speed
Stirring 0.5-2 hours, dispersed and finely ground rear discharging, sealing is kept in dark place in the cool；
2) component B preparation：Under the protection of nitrogen, curing agent and eigenstate polyphenyl are sequentially added by formula rate to reactor
Amine graphene composite material, stirring at low speed；After dispersed, the second solvent is added by formula rate in the state of being kept stirring for,
It is uniformly dispersed and is discharged after finely ground, sealing is kept in dark place in the cool；
3) it is 1 to weigh mass ratio:0.25‐1:0.5 component A and component B, after being uniformly mixed, stands 30 minutes, is gathered
Aniline graphene nano composite anticorrosion coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510317422.6A CN104910752B (en) | 2015-06-10 | 2015-06-10 | A kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510317422.6A CN104910752B (en) | 2015-06-10 | 2015-06-10 | A kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104910752A CN104910752A (en) | 2015-09-16 |
| CN104910752B true CN104910752B (en) | 2017-08-25 |
Family
ID=54080214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510317422.6A Active CN104910752B (en) | 2015-06-10 | 2015-06-10 | A kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104910752B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020082330A1 (en) * | 2018-10-26 | 2020-04-30 | 苏州吉人高新材料股份有限公司 | Epoxy composite coating and preparation method therefor |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201520466D0 (en) * | 2015-11-20 | 2016-01-06 | Applied Biomimetic As | Method of preparing membranes |
| CN105400373B (en) * | 2015-12-16 | 2018-02-02 | 常州大学 | A kind of anticorrosive paint and preparation method containing graphene/removing impurities polyaniline |
| CN105400374A (en) * | 2015-12-21 | 2016-03-16 | 深圳市嘉达高科产业发展有限公司 | Anticorrosive coating and preparation method thereof |
| CN105482645A (en) * | 2016-01-19 | 2016-04-13 | 武汉工程大学 | Anticorrosive polyaniline/silicon carbide/graphene composite coating and preparation method thereof |
| CN105504693B (en) * | 2016-01-19 | 2017-11-14 | 武汉工程大学 | A kind of carborundum/sulfonated graphene/polyaniline complex abrasion-proof anticorrosive paint and preparation method thereof |
| CN105778709A (en) * | 2016-03-10 | 2016-07-20 | 天津市烯腾科技有限公司 | Electrostatic conductive and corrosion-resistant epoxy resin-graphene coating and preparation method thereof |
| CN105820708B (en) * | 2016-04-14 | 2019-01-04 | 常州光辉新材料研究所有限公司 | It is a kind of to include graphene/polyaniline/attapulgite composite material anticorrosive paint and preparation method thereof |
| CN105778088B (en) * | 2016-05-09 | 2017-11-03 | 青岛大学 | A kind of graphene/polyaniline nanometer stick array composite and preparation method and application |
| CN106047073B (en) * | 2016-07-19 | 2018-05-22 | 无锡市烯翔新材料科技有限公司 | A kind of graphene oxide based high-temp-resistant bicomponent epoxy resin coating |
| CN108373746B (en) * | 2016-11-17 | 2020-07-10 | 中国科学院宁波材料技术与工程研究所 | Graphene epoxy composite anticorrosive paint, and preparation method and application thereof |
| CN106433405A (en) * | 2016-11-25 | 2017-02-22 | 中山摩尔化学工业有限公司 | Polyaniline graphene anti-corrosion coating and preparation method thereof |
| CN106833318A (en) * | 2017-03-13 | 2017-06-13 | 陈洋 | The compound impregnating varnish of generator stator core |
| CN108034331A (en) * | 2017-12-13 | 2018-05-15 | 马晓洁 | A kind of graphene-based multicomponent corrosion-resistant epoxy paint and preparation method thereof, application and application method |
| CN108059798A (en) * | 2018-01-11 | 2018-05-22 | 厦门中凯新材石墨烯科技有限公司 | A kind of graphene light curable conductive resin and preparation method thereof |
| GB2572764B (en) * | 2018-04-09 | 2023-06-07 | Applied Graphene Mat Uk Ltd | Corrosion protection for metallic substrates |
| CN109957272A (en) * | 2019-03-03 | 2019-07-02 | 东北石油大学 | A kind of preparation method of anticorrosive packing, anticorrosive paint and the two |
| CN110791167A (en) * | 2019-06-18 | 2020-02-14 | 西北工业大学 | Graphene heavy-duty anticorrosive coating, preparation method thereof and heavy-duty anticorrosive coating |
| CN110746826A (en) * | 2019-09-25 | 2020-02-04 | 界首市金龙机械设备有限公司 | High salt spray resistance rust prevention method for grain machinery |
| WO2021181189A1 (en) * | 2020-03-07 | 2021-09-16 | ALIBAKHSHI Eiman | A weathering-resistant nanocomposite coating |
| CN111378363A (en) * | 2020-03-23 | 2020-07-07 | 南京诚赢集约建材科技有限公司 | Graphene-containing asphalt formula and preparation method thereof |
| 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 |
| CN112375415B (en) * | 2020-11-12 | 2021-12-17 | 厦门大学 | Preparation method and application of graphene-based composite material anti-corrosion auxiliary agent |
| CN112724787B (en) * | 2021-01-07 | 2022-06-28 | 江南大学 | Preparation method of polyaniline modified graphene oxide/hydroxylated boron nitride composite epoxy coating |
| CN114874685B (en) * | 2021-02-05 | 2023-07-14 | 贵州电网有限责任公司 | Anticorrosive paint applicable to acidic environment as well as preparation method and application thereof |
| CN114874678B (en) * | 2021-02-05 | 2023-07-14 | 贵州电网有限责任公司 | Secondary repair polyaniline-based composite anticorrosive paint and preparation method and application thereof |
| CN113122109B (en) * | 2021-04-19 | 2021-12-24 | 江阴大手印精密材料科技发展有限公司 | High-hardness corrosion-resistant alloy steel for offshore wind power bolt bar and preparation method thereof |
| CN113999560A (en) * | 2021-11-15 | 2022-02-01 | 童文娟 | Semiconductive shielding material for coating and preparation method thereof |
| CN114525051B (en) * | 2021-12-31 | 2022-10-21 | 镇江银海镍铬化工有限公司 | Anticorrosive conductive coating and preparation method thereof |
| CN114605891A (en) * | 2022-03-21 | 2022-06-10 | 华南理工大学 | Waterborne two-component epoxy zinc-rich coating and preparation method and application thereof |
| CN114921973A (en) * | 2022-06-06 | 2022-08-19 | 宁波腾安新材料科技有限公司 | Infrared stealth high-performance military tent and preparation method thereof |
| CN115636935A (en) * | 2022-11-09 | 2023-01-24 | 东北大学 | Graphene-loaded high-corrosion-resistance nano polyaniline microsphere and preparation method thereof |
| CN115895404A (en) * | 2022-11-21 | 2023-04-04 | 安徽神剑新材料股份有限公司 | Salt-fog-resistant powder coating and preparation method thereof |
| CN115820079A (en) * | 2022-12-29 | 2023-03-21 | 常州市碳索新材料科技有限公司 | Graphene magnetic ring powder coating and preparation method thereof |
| CN116254036B (en) * | 2023-05-15 | 2023-09-15 | 牛墨石墨烯应用科技有限公司 | Preparation method of graphene carbon nanotube heat conduction slurry |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101166528B1 (en) * | 2011-07-29 | 2012-07-19 | 주식회사 엘엠에스 | Graphene laminate comprising dopants and preparation method of the same |
| CN102604533A (en) * | 2012-03-14 | 2012-07-25 | 哈尔滨工程大学 | Polyaniline-graphene composite based anticorrosive paint and preparation method thereof |
| CN105086754B (en) * | 2013-03-06 | 2017-06-16 | 常州第六元素材料科技股份有限公司 | A kind of bi-component Graphene anticorrosive paint |
| CN103311428B (en) * | 2013-06-14 | 2015-08-19 | 哈尔滨工业大学 | A kind of preparation method of graphene/polyaniline thermal electric film |
| CN104031433B (en) * | 2014-06-09 | 2016-03-09 | 大连理工大学 | Low conduction crystalline flake graphite alkene matrix material, its preparation method and application thereof |
| CN104293075B (en) * | 2014-10-28 | 2016-08-24 | 张海红 | A kind of modified polyphenyl amine type anticorrosive paint and preparation method thereof |
-
2015
- 2015-06-10 CN CN201510317422.6A patent/CN104910752B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020082330A1 (en) * | 2018-10-26 | 2020-04-30 | 苏州吉人高新材料股份有限公司 | Epoxy composite coating and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104910752A (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104910752B (en) | A kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof | |
| CN105238207B (en) | A kind of conductive multifunctional anticorrosive coating of high performance super-amphiphobic and preparation method thereof | |
| CN102634276B (en) | Heavy-duty anticorrosive polyaniline coating and preparation method thereof | |
| CN104974642B (en) | A kind of preparation method of Nano-composite electric conduction anticorrosive paint | |
| Zhang et al. | Study on the synthesis of PANI/CNT nanocomposite and its anticorrosion mechanism in waterborne coatings | |
| CN109836919A (en) | A kind of functional graphene oxide corrosion-inhibiting coating and its preparation process | |
| CN112724787B (en) | Preparation method of polyaniline modified graphene oxide/hydroxylated boron nitride composite epoxy coating | |
| CN107964097A (en) | The ternary nano composite material preparation method and application of redox graphene, ferroso-ferric oxide and polyaniline | |
| CN105482645A (en) | Anticorrosive polyaniline/silicon carbide/graphene composite coating and preparation method thereof | |
| CN102732128B (en) | Nanometer polyaniline anticorrosive coating and preparation method therefor | |
| CN107400441A (en) | Graphene modified waterborne epoxy anticorrosive paint preparation technology | |
| CN107760205B (en) | Water-based carbon steel surface treating agent based on polypyrrole/graphene composite material | |
| CN110330865A (en) | Modified anti-corrosion primer of a kind of graphene and preparation method thereof | |
| CN105111434B (en) | A kind of composite of aniline and graphene, preparation method and applications | |
| CN106590089A (en) | Water-based potassium silicate zinc-rich primer used for surface treatment of long-acting anti-microbial section steel structures and preparation method of water-based potassium silicate zinc-rich primer | |
| CN1935911B (en) | Bottom-surface-in-one fluorocarbon enamelled paint and its preparing method | |
| CN106496553B (en) | Carbon nano-tube/poly aniline composite material with electrochemical anti-corrosive effect, preparation method and application | |
| Assassi et al. | Synthesis, characterizations and application of polyaniline-paint as anticorrosion agent | |
| CN105504693A (en) | Silicon carbide/sulfonated graphene/polyaniline composite wear-resistant anticorrosive paint and preparation method thereof | |
| Wang et al. | Phosphorylated polymer/anionic surfactant doped polypyrrole in waterborne epoxy matrix toward enhanced mechanical and chemical resistance | |
| Han et al. | Highly dispersed polyaniline/graphene oxide composites for corrosion protection of polyvinyl chloride/epoxy powder coatings on steel | |
| CN107245145A (en) | The preparation method and application of pyrroles's aniline and its modified anti-corrosive coating | |
| CN109880488A (en) | A kind of Diamines salicylide Schiff 's base is grapheme modified or graphene oxide metal anti-corrosive paint | |
| CN105860060B (en) | A kind of three-dimensional cross-linked attapulgite/graphene/polyaniline composite anti-corrosion material and preparation method thereof | |
| CN113549387A (en) | Modified epoxy resin coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200617 Address after: Room 102, door 7, No. 95, 4th Street, economic and Technological Development Zone, Binhai New Area, Tianjin Patentee after: Tianjin HaoTu Environmental Protection Technology Co., Ltd Address before: 510640 Tianhe District, Guangdong, No. five road, No. 381, Patentee before: SOUTH CHINA University OF TECHNOLOGY |