CN106752673A - Hexagonal boron nitride epoxy composite anticorrosive paint, its preparation method and application - Google Patents
Hexagonal boron nitride epoxy composite anticorrosive paint, its preparation method and application Download PDFInfo
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- CN106752673A CN106752673A CN201611009592.9A CN201611009592A CN106752673A CN 106752673 A CN106752673 A CN 106752673A CN 201611009592 A CN201611009592 A CN 201611009592A CN 106752673 A CN106752673 A CN 106752673A
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- boron nitride
- hexagonal boron
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of hexagonal boron nitride epoxy composite anticorrosive paint, its preparation method and application.The anticorrosive paint is mainly made up of hexagonal boron nitride, polyaniline nano fiber, epoxy resin, decentralized medium, coating additive, epoxy curing agent and solvent etc..The hexagonal boron nitride epoxy composite anticorrosive paint that the present invention is provided has excellent storage stability; it is difficult the advantages of sinking to the bottom; and it is preparation process is simple, with low cost; it is suitable for scale production; and by coating barrier property that it is formed is excellent, anti-corrosion property persistently can have good application prospect in the industries such as chemical industry, oil, electric power, ship, light textile, storage, traffic, space flight.
Description
Technical field
Present invention relates particularly to a kind of hexagonal boron nitride epoxy composite anticorrosive paint, its preparation method and application, belong to painting
Material technical field.
Background technology
According to statistics, about 100,000,000 tons of the metal scrapped is corroded in the whole world every year, accounts for the 20%~40% of annual production；And with
The acceleration of industrialized process, being on the rise of etching problem estimates that the steel equipment that the whole world is scrapped by corrosion every year is suitable
In the 30% of annual production, serious economic loss is caused.Corrosion can also bring casualties, environmental pollution, the resource wave of heaviness
The harm such as take, the development for hindering new technology is, the loss that increased natural resources.Therefore, metal erosion is to national economy and society
The serious harm for causing that can live increasingly recognizes attention by people.
At present, face coat paint-on technique is (for example：Organic coating and inorganic coating) be corrosion protection general measure, have
It is organic coating preparation process is simple, with low cost, it is widely used the advantages of suitable for scale production.Organic coating is to metal
Protective action mainly include physical barrier, passivation, the protection of antirust filler, the effect such as cathodic protection.But, organic coating material
Material is not a perfect obstruct system, and the hole of coating generation can be made due to the strand gap of polymer itself, and
The hole that solvent volatilization is produced in coating process turns into the main thoroughfare that the corrosive mediums such as steam, salt fog penetrate into.In order to delay corruption
The generation of erosion, typically contains the heavy metal compounds such as chromium or lead as corrosion inhibitor, to marine environment and people in anticorrosive paint
Class health is affected greatly.With the enhancing of people's awareness of environment protection and health, the friendly heavy metal free of development environment it is nontoxic
Antirust color stuffing anticorrosive paint turns into the inexorable trend of paint development.
The discovery of Graphene causes the attention of academia and industrial circle, and is used widely in paint field.As
The hexagonal boron nitride of one of two-dimensional material family member, has similar structure to Graphene；Have simultaneously excellent chemistry and
Heat endurance, hydrophobicity, barrier, heat conductivity lubricity and mechanical property.Hexagonal boron nitride has insulating properties, if will
Hexagonal boron nitride is used in coating, will show more preferable corrosion resistance than Graphene.But directly add hexagonal boron nitride
To in high molecular polymer or resin, hexagonal boron nitride is susceptible to due to π-πconjugation and Van der Waals force suction-operated
Reunite, and be difficult in dispersed high molecular polymer or resin, cause micropore still to exist, the protection effect of the coating of formation
Difference.
The content of the invention
It is a primary object of the present invention to providing a kind of hexagonal boron nitride epoxy composite anticorrosive paint, its preparation method and answering
With to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of hexagonal boron nitride epoxy composite anticorrosive paint is the embodiment of the invention provides, it includes hexagonal boron nitride, gathers
The components such as aniline nano-fiber, epoxy resin, decentralized medium, coating additive, epoxy curing agent and solvent.
It is more preferred, in the hexagonal boron nitride epoxy composite anticorrosive paint content of hexagonal boron nitride be 0.5~
2wt%.
More preferred, the content of middle polyaniline nano fiber is in the hexagonal boron nitride epoxy composite anticorrosive paint
0.25%wt~1wt%.
In some preferred embodiments, the hexagonal boron nitride epoxy composite anticorrosive paint includes：
Component one, comprising：
Also, component one is 100 with the quality of component two:10~100:80.
The embodiment of the present invention additionally provides a kind of preparation method of hexagonal boron nitride epoxy composite anticorrosive paint, and it includes：
Hexagonal boron nitride and polyaniline nano fiber are dispersed in solvent, hexagonal boron nitride dispersion liquid is obtained, it
The hexagonal boron nitride dispersion liquid is well mixed with epoxy resin, auxiliary agent and solvent afterwards, forms component one；
And, there is provided epoxy curing agent as component two, or, by epoxy curing agent with solvent dilute and shape
Into component two.
The embodiment of the present invention additionally provides the application of the hexagonal boron nitride epoxy composite anticorrosive paint.
For example, the embodiment of the present invention additionally provides the coating formed by the hexagonal boron nitride epoxy composite anticorrosive paint.
For example, the embodiment of the present invention additionally provides a kind of preparation method of coating, including：By the hexagonal boron nitride epoxy
The component one of composite anticorrosion coating carries out film forming treatment after uniformly mixing with component two, then through cold curing, forms the coating.
Compared with prior art, the hexagonal boron nitride epoxy composite anticorrosive paint that the present invention is provided has bin stability
It is good, it is difficult the advantages of sinking to the bottom, it is preparation process is simple, with low cost, it is suitable for scale production, and the coating barrier formed by it
Energy is excellent, anti-corrosion property persistently can have well in the industries such as chemical industry, oil, electric power, ship, light textile, storage, traffic, space flight
Application prospect.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of a kind of poly- butylaniline nanofiber used in the embodiment of the present invention 1.
Fig. 2 a-2b are respectively the six side's nitrogen processed without poly- butylaniline nanofiber dispersion in the embodiment of the present invention 1
Change boron dispersion photo in a solvent and the hexagonal boron nitride dispersion in a solvent processed by poly- butylaniline nanofiber
Photo.
The TEM figures and 1~embodiment of embodiment 3 that Fig. 3 a-3d are respectively the pure epoxy coating of comparative example 1 obtain hexagonal boron nitride
The TEM figures of epoxy composite coating,.
Fig. 4 is existed by the pure epoxy coating of comparative example 1 and 1~embodiment of embodiment 3 obtain hexagonal boron nitride epoxy composite coating
Mass fraction is potential polarization curve (bode) figure of the ac impedance spectroscopy after being soaked 120 days in 3.5wt%NaCl solution.
Fig. 5 obtains hexagonal boron nitride epoxy composite coating by the pure epoxy coating of comparative example 1 and 1~embodiment of embodiment 3
OCP is with soak time change curve.
Fig. 6 obtains hexagonal boron nitride epoxy composite coating by the pure epoxy coating of comparative example 1 and 1~embodiment of embodiment 3
Water absorption rate curve map.
Specific embodiment
In view of deficiency of the prior art, inventor is able to propose of the invention through studying for a long period of time and largely put into practice
Technical scheme.The technical scheme, its implementation process and principle etc. will be further explained as follows.
In the embodiment of the present invention provide a kind of hexagonal boron nitride epoxy composite anticorrosive paint, its include hexagonal boron nitride,
The components such as polyaniline nano fiber, epoxy resin, decentralized medium, coating additive, epoxy curing agent and solvent.
It is more preferred, in the hexagonal boron nitride epoxy composite anticorrosive paint content of hexagonal boron nitride be 0.5~
2wt%.
More preferred, the content of middle polyaniline nano fiber is in the hexagonal boron nitride epoxy composite anticorrosive paint
0.25%wt~1wt%.
In some preferred embodiments, the hexagonal boron nitride epoxy composite anticorrosive paint includes：
Component one, comprising：
Also, component one is 100 with the quality of component two:10~100:80.
Before using the hexagonal boron nitride epoxy composite anticorrosive paint, component one can uniformly be mixed with component two,
Carry out into the operation such as film process again afterwards.
Further, described hexagonal boron nitride includes hexagonal boron nitride nanosheet, hexagonal boron nitride micron film, six side's nitrogen
Change boron nanobelt, few layer hexagonal boron nitride (2~5 layers), multilayer hexagonal boron nitride (5~9 layers), hexagonal boron nitride quantum dot and
The derivative (hexagonal boron nitride of chemical modification) of these hexagonal boron nitride class materials, but the nitridation of not limited to this, preferably six sides
Boron nanometer sheet.
Further, the thickness of described hexagonal boron nitride is preferably≤20nm, it is furthermore preferred that thickness≤10nm.
Further, the material of the polyaniline nano fiber may be selected from the polyphenyl of polyaniline or side chain containing substituted base
Amine, it is preferred that the substitution base includes methyl, ethyl, propyl group or butyl, it is preferred that polyphenyl of the side chain containing substituted base
Amine includes any one of polyortho methylaniline, poly- o ethyl aniline, poly- neighbour's propyl group aniline, poly- butylaniline or two or more
Combination, but not limited to this.
Further, a diameter of 10~300nm of the polyaniline nano fiber, preferably a diameter of 10~100nm.
Further, the length of the polyaniline nano fiber is 0.5~5 μm, and preferred length is 0.5~2 μm.
Further, the polyaniline of foregoing polyaniline or side chain containing substituted base is polyaniline in eigenstate.
Further, stating epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy tree
Fat, methylol bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F types epoxy resin, modified nylon epoxy resin, line style phenol formaldehyde (PF) ring
Oxygen tree fat, orthoresol formaldehyde epoxy resin, aliphatic glycidyl ether epoxy resin, glycidol epoxy-type epoxy resin, shrink
Any one in the epoxy resin such as glycerine amine type or two or more combinations, but not limited to this.
Further, the epoxy curing agent is solid including polyamide-based curing agent, anacardol curing agent and imidazoles
Any one in agent or two or more combinations, but not limited to this.
Further, the coating additive may also include one or more in anti-settling agent, defoamer or levelling agent.
Wherein, the anti-settling agent includes any one in aerosil, polyamide wax and organobentonite or two
Plant the combination of the above, but not limited to this.
Wherein, the defoamer includes dimethicone, ether ester compound, modified mineral oil, polyethoxy glycerol ether, small
Molecular metal organic matter and silicon modified organic polymer, but not limited to this.
Wherein, the levelling agent includes butyl glycol ether, cellaburate, polyacrylate, silicone oil, hydroxylmethyl cellulose
Any one in element, polydimethylsiloxane, PSI and modified organic silicon compound or two or more groups
Close, but not limited to this.
Further, the solvent includes toluene, dimethylbenzene, acetone, tetrahydrofuran, ethanol, ethyl acetate and dimethyl
Any one in sulfoxide or two or more combinations, but not limited to this.
The embodiment of the present invention additionally provides a kind of preparation method of hexagonal boron nitride epoxy composite anticorrosive paint, including：
Hexagonal boron nitride and polyaniline nano fiber are dispersed in solvent, hexagonal boron nitride dispersion liquid is obtained, it
The hexagonal boron nitride dispersion liquid is well mixed with epoxy resin, auxiliary agent and solvent afterwards, forms component one；
And, there is provided epoxy curing agent as component two, or, by epoxy curing agent with solvent dilute and shape
Into component two.
In some more specific embodiment, the preparation method may comprise steps of：
Weigh a certain amount of hexagonal boron nitride to be scattered in solvent with polyaniline nano fiber, agitated or ultrasound obtains six
Square boron nitride dispersion；
The hexagonal boron nitride dispersion liquid is added in epoxy resin, auxiliary agent and solvent, is stirred 10~60 minutes, be obtained
Well mixed component one；
Add a certain amount of solvent to be diluted epoxy curing agent, obtain component two.
It is more preferred, in the hexagonal boron nitride dispersion liquid, the quality of hexagonal boron nitride and polyaniline nano fiber
Than being 1:10~10:1.
The embodiment of the present invention additionally provides the application of the hexagonal boron nitride epoxy composite anticorrosive paint.
For example, the embodiment of the present invention additionally provides the coating formed by the hexagonal boron nitride epoxy composite anticorrosive paint.
For example, the embodiment of the present invention additionally provides a kind of preparation method of coating, including：By the hexagonal boron nitride epoxy
The component one of composite anticorrosion coating carries out film forming treatment after uniformly mixing with component two, then through cold curing, forms the coating.
In some more specific embodiment, after can component two be mixed with component one, film process is carried out into, and
Normal temperature cure more than 7 days, obtains hexagonal boron nitride epoxy composite coating.
Wherein, the mode into film process can be coating, spin coating, spraying, printing etc., but not limited to this.
Foregoing hexagonal boron nitride epoxy composite coating can significantly extend such when the matrix surfaces such as metal are applied to
The service life of matrix.
In a more specific case study on implementation, a kind of preparation method of hexagonal boron nitride epoxy composite coating includes following
Step：
(1) aniline monomer is dissolved in 1M hydrochloric acid, is afterwards added in above-mentioned solution simultaneously the ammonium persulfate of equimolar amounts
24 hours are stood at room temperature, polyaniline nano fiber is obtained after filtering, washing, hydration hydrazinolysis doping is added afterwards, with distillation
Water washing 3 times, polyaniline in eigenstate nanofiber is obtained after drying.
(2) weigh a certain amount of hexagonal boron nitride to be scattered in solvent with polyaniline nano fiber obtained in step (1), shape
Into polyaniline nano fiber/hexagonal boron nitride dispersion liquid, wherein, polyaniline nano fiber and hexagonal boron nitride mass ratio are 1:10
~10:1.
(3) polyaniline nano fiber/hexagonal boron nitride dispersion liquid is added in epoxy resin, auxiliary agent and solvent,
Stirring 10~60 minutes, obtains well mixed component one.
(4) epoxy curing agent is diluted with solvent, obtains component two.
Further, aforementioned component two is well mixed and is applied to be formed on matrix by a certain percentage with component one and applied
Layer, normal temperature cure can form hexagonal boron nitride epoxy composite coating in 7 days.
Stirring, dispersion above can use general high-speed stirred and mixing and dispersing device, such as supersonic wave cleaning machine, ultrasound
Ripple cell disruptor, homogenizer and mechanical agitator etc..
The present invention in hexagonal boron nitride epoxy composite anticorrosive paint by adding a small amount of dispersed polyaniline nano
Fiber and hexagonal boron nitride (especially hexagonal boron nitride two-dimensional nano piece), can be obviously improved the barrier property of formed coating
With anti-corrosion property energy.Its mechanism may is that：First, polyaniline nano fiber can make passivation of metal surfaces, protection oxidation is formed
Layer, while the electric conductivity of polyaniline nano fiber can be with causing corrosion potential migration, so as to reduce corrosion of metal speed；Its
Two, hexagonal boron nitride (preferably hexagonal boron nitride two-dimensional nano piece) dispersed are so that it is parallel overlapping in composite coating
Distribution, produces labyrinth effect, can increase substantially the barrier property of coating, reduces coating crack, extension corrosive medium diffusion
Passage, and then delay metal erosion；(the preferably wiener of hexagonal boron nitride two third, polyaniline nano fiber and hexagonal boron nitride
Rice piece) it is compound after, both are cooperateed with, and the foregoing premium properties of polyaniline nano fiber and hexagonal boron nitride is not interfered with not only, also
The dispersiveness of hexagonal boron nitride can be greatly improved, dispersion can be more uniformly distributed in the epoxy, and then make the coating to be formed
Protection effect that is more fine and close, being significantly improved.
Hexagonal boron nitride epoxy composite anticorrosive paint of the invention and the epoxy composite coating that is formed by it are in chemical industry, stone
There is good application prospect in the industries such as oil, electric power, ship, light textile, storage, traffic, space flight.
Below in conjunction with the technical solution of the present invention is further explained the explanation of accompanying drawing and some embodiments.
Embodiment 1
(1) by the poly- butylaniline nanofibers of 0.047g, (pattern is as shown in figure 1, and can refer to method previously system
It is standby), 0.18g hexagonal boron nitride nanosheets (thickness about 3~5nm) be dispersed in 40mL tetrahydrofurans, ultrasound 1 hour is equal to mixing
It is even to obtain hexagonal boron nitride dispersion liquid, the hexagonal boron nitride dispersion liquid is added to 30g epoxy resin (model E44, purchase afterwards
Make a concerted effort resin processing plant in Jiangsu Wujiang), 2g levelling agents, 2g anti-settling agents, in 3g defoamers and middle 8g dimethylbenzene reagent, stirred using machinery
Mix 30 minutes, make various material mixings uniform, obtain component one.
(2) by 7.5g polyamide 6s 50, the well mixed prepared component two of 6g xylene solutions.
(3) component one is directly mixed with component two, using homogenizer, is stirred 30 minutes, that is, obtained containing 0.5wt%
The epoxy composite coating of hexagonal boron nitride.
(4) gained hexagonal boron nitride epoxy composite coating is sprayed on plain steel, after after solvent volatilization, obtains thickness
About 20 microns of hexagonal boron nitride epoxy composite coating.
Embodiment 2
(1) 0.095g polyortho methylanilines nanofiber (diameter about 10nm, about 0.8 μm of length), the sides of 0.38g six are nitrogenized
Ultrasound obtains hexagonal boron nitride in 1 hour to well mixed during boron nanobelt (thickness about 8~10nm) is dispersed in 80mL tetrahydrofurans
Dispersion liquid, is added to 30g epoxy resin (bisphenol-s epoxy resin, methylol Bisphenol F by the hexagonal boron nitride dispersion liquid afterwards
Type epoxy resin or A Hydrogenated Bisphenol A F type epoxy resin etc.), 2g levelling agents (polydimethylsiloxane or PSI
Deng), 2g anti-settling agents (polyamide wax or organic swelling etc.), 3g polyethers defoamer and middle 8g toluene reagent (model E44, purchase
Make a concerted effort resin processing plant in Jiangsu Wujiang) in, using mechanical agitation 30 minutes, make various material mixings uniform, obtain component one.
(2) 7.5g polyamide 6s 50 are well mixed with 6g toluene solutions and component two is obtained.
(3) component one is pressed with component two and is directly mixed, using homogenizer, stirred 30 minutes, that is, contained
The epoxy composite coating of 1.0wt% hexagonal boron nitrides.
(4) gained hexagonal boron nitride epoxy composite coating is sprayed on plain steel, after after solvent volatilization, obtains thickness
About 20 microns of hexagonal boron nitride epoxy composite coating.
Embodiment 3
(1) by 0.19g polyphenylethyl amine nanofiber (diameter about 100nm, about 0.7 μm of length), the few side's nitrogen of layer six of 0.75g
Change boron powder to be dispersed in 150mL tetrahydrofurans, ultrasound is well mixed for 1 hour, hexagonal boron nitride dispersion liquid is obtained, afterwards by institute
State hexagonal boron nitride dispersion liquid and be added to 30g epoxy resin (orthoresol formaldehyde epoxy resin, aliphatic glycidyl ether asphalt mixtures modified by epoxy resin
Fat, glycidol epoxy-type epoxy resin or glycidyl amine type epoxy resin etc.), 2g levelling agents (polyacrylate or silicone oil
Deng), 2g anti-settling agents (aerosil etc.), in 3g silicon modified organic polymer class defoamers and middle 8g dimethylbenzene reagent, make
With mechanical agitation 30 minutes, make various material mixings uniform, obtain component one.
(2) 7.5g polyamide 6s 50 are well mixed with 6g xylene solutions and component two is obtained.
(3) component one is pressed with component two and is directly mixed, using homogenizer, stirred 30 minutes, that is, contained
The epoxy composite coating of 2.0wt% hexagonal boron nitrides.
(4) gained hexagonal boron nitride epoxy composite coating is sprayed on plain steel, after after solvent volatilization, obtains thickness
About 20 microns of hexagonal boron nitride epoxy composite coating.
Comparative example 1
(1) by 30g epoxy resin (with embodiment 1), 2g levelling agents (with embodiment 1), 2g anti-settling agents (with embodiment 1),
3g defoamers (with embodiment 1) are dissolved in 8g dimethylbenzene reagents, using mechanical agitation 30 minutes, obtain component one.
(2) 7.5g polyamide 6s 50 are well mixed with 6g xylene solutions and component two is obtained.
(3) component one is pressed with component two and is directly mixed, using homogenizer, stirred 30 minutes, that is, obtain pure epoxy
Coating.
(4) resulting pure epoxy coating is sprayed on plain steel, after after solvent volatilization, obtaining thickness, to be about 20 micro-
The pure epoxy coating of rice.
Comparative example 2：The comparative example is substantially the same manner as Example 1, but the poly- fourth in component one is instead of with polyaniline purchased in market
Base aniline nano-fiber.
Fig. 2 a be the present embodiment 1 in without poly- butylaniline nanofiber dispersion process hexagonal boron nitride dispersion liquid
Photo, Fig. 2 b be the present embodiment 1 in a kind of photo of typical hexagonal boron nitride dispersion liquid, wherein hexagonal boron nitride is by poly- fourth
Base aniline decentralized processing.It can be seen that, without poly- butylaniline nanofiber dispersion process hexagonal boron nitride dispersion liquid
Through occurring significantly to precipitate, and the hexagonal boron nitride dispersion liquid that the present embodiment 1 is processed by poly- butylaniline nanofiber dispersion
Without obvious sediment, this shows that poly- butylaniline nanofiber can be such that hexagonal boron nitride is uniformly dispersed in solvent.
Comparative example 1 is respectively referring to Fig. 3 a-3d obtain the typical hexagonal boron nitride that pure epoxy coating and embodiment 1-3 are obtained
The TEM figures of epoxy composite coating.Result shows：Pure epoxy coating surface is smooth, no significant defect；The typical case that embodiment 1 is obtained
There are many equally distributed white portions, predominantly hexagonal boron nitride in hexagonal boron nitride epoxy composite coating surface, this shows
The presence of poly- butylaniline nanofiber reduces hexagonal boron nitride aggregation in the epoxy, promotes hexagonal boron nitride in ring
It is scattered in oxygen tree fat；However as the increase of hexagonal boron nitride doping content, surface occur white aggregation zone (such as Fig. 3 c and
3d).And the Cross Section Morphology of the hexagonal boron nitride epoxy composite coating that comparative example 2 is obtained and the TEM figures of section show, in coating
Hexagonal boron nitride has substantially reunion, skewness.
Six sides of the different boron nitride contents that pure epoxy coating and embodiment 1-3 are obtained are obtained by comparative example 1 referring to Fig. 4
Ac impedance spectroscopy of the boron nitride epoxy composite coating after being soaked 120 days during mass fraction is 3.5wt%NaCl solution
Bode schemes；Specifically, different content hexagonal boron nitride epoxy composite coating of the invention is soaked in 3.5wt%NaCl solution
120 days, in immersion process, handed over using the change and electrochemistry of Shanghai Chen Hua CHI660E electrochemical workstations monitoring OCP
Flow impedance is composed.Carrying out anti-corrosion property to pure epoxy coating described in comparative example 1 can test.As shown in Figure 4, pure epoxy coating is in immersion 50
After it, impedance magnitude is from 3.5 × 108Ωcm2It is reduced to 1.1 × 105Ωcm2, show that pure epoxy coating has failed.And this
The different boron nitride content hexagonal boron nitride epoxy composite coatings of invention still keep impedance value higher after soaking 120 days, especially
It is 0.5~1wt% hexagonal boron nitride epoxy composite coatings, and impedance magnitude is about 1.0 × 109Ωcm2；In addition, the present invention
Different boron nitride content hexagonal boron nitride epoxy composite coatings there is increased trend in immersion process middle impedance modulus value, this can
Can make passivation of metal surfaces and be formed with the presence of polyaniline nano fiber to protect oxide layer relevant.In the same way
The hexagonal boron nitride epoxy composite coating obtained to comparative example 2 is tested, and is as a result shown, it is similar to pure epoxy coating, warp
Impedance magnitude is also significantly reduced after the immersion of short time, and reduction amplitude is far longer than the hexagonal boron nitride epoxy of embodiment 1-3
Composite coating.
Referring to Fig. 5 by the pure epoxy coating of comparative example 1 and embodiment 1-3 in obtain the side of different boron nitride contents six nitridation
The OCP of boron epoxy composite coating is with soak time change curve；Result shows：With the extension of soak time, open circuit
Potential value is constantly reduced, and relative to and pure epoxy coating, the OCP of hexagonal boron nitride epoxy composite coating occurs just
Move, show that corrosion process is more difficult to occur.Hexagonal boron nitride epoxy composite coating is obtained to comparative example 2 using same way again is carried out
Test, as a result shows, although its corrosion resistance has the lifting of certain amplitude than pure epoxy coating, but still is much weaker than implementation
The hexagonal boron nitride epoxy composite coating of example 1-3.
Referring to the different boron nitride content hexagonal boron nitride rings that Fig. 6 is obtained by the pure epoxy coating of comparative example 1 and embodiment 1-3
The water absorption rate curve map of oxygen composite coating, the water absorption rate curve of coating can be divided into two stages：Initial period and water suction saturation
Stage, pure epoxy coating shows highest water absorption rate, about 1% after the saturation that absorbs water；And the different side's nitrogen of boron nitride content six
The water absorption rate for changing boron epoxy composite coating is substantially reduced compared with pure epoxy coating, and this shows dispersed hexagonal boron nitride in epoxy
Lamella blocking effect is formed in coating, it is suppressed that corrosive medium diffusion in the coating.Show from result above, hexagonal boron nitride
The excellent corrosion resistance of epoxy composite coating may mostly come from polyaniline nano fiber and hexagonal boron nitride nanosheet
Cooperative effect.Hexagonal boron nitride epoxy composite coating is obtained to comparative example 2 using same way again to test, and is as a result shown,
Its water absorption rate has the lifting of certain amplitude than pure epoxy coating, but also much worse than the hexagonal boron nitride ring of embodiment 1,2,3
Oxygen composite coating.
Embodiment 4：The present embodiment is substantially the same manner as Example 1, but is replaced with the hexagonal boron nitride micron film of thickness about 20nm
For the hexagonal boron nitride nanosheet in component one, and poly- neighbour's propyl group aniline nano-fiber is employed in component one, and (diameter is about
300nm or so, about 5 μm or so of length), the solvent used in component one and component two is acetone and dimethyl sulfoxide (DMSO).
Embodiment 5：The present embodiment is substantially the same manner as Example 2, but with the multilayer hexagonal boron nitride of thickness about 12~15nm
The hexagonal nanometer boron nitride band in component one is instead of, and polyaniline nano fiber is employed in component one, and (diameter about 150nm is left
The right side, 2 μm or so of length), the solvent used in component one and component two is ethanol and ethyl acetate.
Embodiment 6：The present embodiment is substantially the same manner as Example 3, but with hexagonal boron nitride quantum dot instead of component one
Few layer of hexagonal boron nitride.
Embodiment 7：The present embodiment is substantially the same manner as Example 1, but with the hydroxylating boron nitride nanometer of thickness about 5~8nm
Piece instead of the hexagonal boron nitride nanosheet in component one.
Embodiment 8：The present embodiment is substantially the same manner as Example 3, but is substituted with the fluorination boron nitride of thickness about 10~15nm
Few layer of hexagonal boron nitride in component one.
For each hexagonal boron nitride epoxy composite anticorrosive paint and composite coating that 4~embodiment of previous embodiment 8 is obtained,
The present inventor also using being tested with the same way of 1~embodiment of embodiment 3, as a result shows that these composite anti-corrosives are applied
Material is respectively provided with excellent storage stability, and these composite coatings for being formed also show excellent anticorrosion performance and barrier
Energy.
Embodiment described above is only used for helping the core concept for understanding the method for the present invention, and its description is more specific and detailed
Carefully, but can not therefore and be interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for the common skill of this area
For art personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to this hair
In bright protection domain.To various modifications of these embodiments it is clear that institute herein for one of skill in the art
The General Principle of definition can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore,
The protection domain of patent of the present invention should be determined by the appended claims, without limitation on these shown in this article examples, but
Meet the scope consistent with principles disclosed herein and feature.
Claims (10)
1. a kind of hexagonal boron nitride epoxy composite anticorrosive paint, it is characterised in that including：
Component one, comprising：
50~79wt% of epoxy resin,
0.5~2wt% of hexagonal boron nitride,
0.25~1wt% of polyaniline nano fiber,
0.5~5wt% of coating additive,
20~30wt% of solvent；
And, component two, comprising：
75~100wt% of epoxy curing agent,
0~25wt% of solvent；
Also, component one is 100 with the quality of component two:10~100:80.
2. the hexagonal boron nitride epoxy composite anticorrosive paint according to claim, it is characterised in that：The hexagonal boron nitride
Thickness for≤20nm, preferably≤10nm；And/or, the hexagonal boron nitride includes that hexagonal boron nitride nanosheet, six sides are nitrogenized
Boron micron film, hexagonal nanometer boron nitride band, the number of plies are 2~5 layers of few layer of hexagonal boron nitride, the side of multilayer six that the number of plies is 5~9 layers
Any one or any one derivative in boron nitride, hexagonal boron nitride quantum dot；Preferably, the hexagonal boron nitride is
Hexagonal boron nitride nanosheet；Preferably, the derivative is selected from the hexagonal boron nitride of chemical modification.
3. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that：The polyaniline nano
The material of fiber is selected from polyaniline or the polyaniline containing substituted base, it is preferred that the substitution base includes alkyl or amido, institute
Alkyl is stated including methyl, ethyl, propyl group or butyl, it is preferred that the polyaniline containing substituted base include polyortho methylaniline,
Any one in poly- o ethyl aniline, poly- neighbour's propyl group aniline, poly- butylaniline and poly-o-phenylenediamine or two or more combinations；
And/or, a diameter of 10~300nm of the polyaniline nano fiber, preferably 10~100nm, length are 0.5~5 μm, preferably
It is 0.5~2 μm.
4. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that：The epoxy resin bag
Include bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, methylol bisphenol f type epoxy resin, hydrogenation
Bisphenol f type epoxy resin, modified nylon epoxy resin, line style phenol formaldehyde (PF) epoxy resin, orthoresol formaldehyde epoxy resin, fat
Any one in the epoxy resin such as race's tetraglycidel ether epoxy resin, glycidol epoxy-type epoxy resin, glycidic amine type
Or two or more combinations；And/or, the epoxy curing agent includes polyamide-based curing agent, anacardol curing agent and miaow
Any one in azole curing agent or two or more combinations.
5. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that：The coating additive bag
Include any one in anti-settling agent, defoamer and levelling agent or two or more combinations；Preferably, the anti-settling agent includes gas phase
Any one in silica, polyamide wax and organobentonite or two or more combinations；Preferably, the defoamer bag
Include dimethicone, ether ester compound, modified mineral oil, polyethoxy glycerol ether, small molecule metallorganic and be modified organic
Silicon polymer；Preferably, the levelling agent includes butyl glycol ether, cellaburate, polyacrylate, silicone oil, methylol
In cellulose, polydimethylsiloxane, PSI and modified organic silicon compound any one or it is two or more
Combination.
6. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that：The solvent includes first
Any one in benzene, dimethylbenzene, acetone, tetrahydrofuran, ethanol, ethyl acetate and dimethyl sulfoxide (DMSO) or two or more groups
Close.
7. a kind of method for preparing hexagonal boron nitride epoxy composite anticorrosive paint any one of claim 1-6, its feature
It is to include：
Hexagonal boron nitride and polyaniline nano fiber are dispersed in solvent, hexagonal boron nitride dispersion liquid is obtained, afterwards will
The hexagonal boron nitride dispersion liquid is well mixed with epoxy resin, auxiliary agent and solvent, forms component one；
And, there is provided epoxy curing agent as component two, or, by epoxy curing agent with solvent dilute and formation group
Divide two.
8. the preparation method of hexagonal boron nitride epoxy composite anticorrosive paint according to claim 7, it is characterised in that：Institute
State in hexagonal boron nitride dispersion liquid, hexagonal boron nitride is 1 with the mass ratio of polyaniline nano fiber:10~10:1.
9. the coating that the hexagonal boron nitride epoxy composite anticorrosive paint as any one of claim 1-6 is formed.
10. a kind of preparation method of coating, it is characterised in that including：By hexagonal boron nitride any one of claim 1-6
The component one of epoxy composite anticorrosive paint carries out film forming treatment after uniformly mixing with component two, then through cold curing, forms described
Coating.
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| CN201611009592.9A CN106752673B (en) | 2016-11-17 | 2016-11-17 | Hexagonal boron nitride epoxy composite anticorrosive paint, preparation method and application |
| JP2019516501A JP6615411B1 (en) | 2016-11-17 | 2016-12-06 | Hexagonal boron nitride epoxy composite anticorrosion paint, its production method and application |
| PCT/CN2016/108682 WO2018090407A1 (en) | 2016-11-17 | 2016-12-06 | Hexagonal boron nitride epoxy composite anticorrosive coating and preparation method and application of same |
| US16/319,671 US10822501B2 (en) | 2016-11-17 | 2016-12-06 | Hexagonal boron nitride epoxy compound anticorrosive paint, and preparation method and use thereof |
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| CN201611009592.9A CN106752673B (en) | 2016-11-17 | 2016-11-17 | Hexagonal boron nitride epoxy composite anticorrosive paint, preparation method and application |
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