CN106752673B - Hexagonal boron nitride epoxy composite anticorrosive paint, preparation method and application - Google Patents
Hexagonal boron nitride epoxy composite anticorrosive paint, preparation method and application Download PDFInfo
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- CN106752673B CN106752673B CN201611009592.9A CN201611009592A CN106752673B CN 106752673 B CN106752673 B CN 106752673B CN 201611009592 A CN201611009592 A CN 201611009592A CN 106752673 B CN106752673 B CN 106752673B
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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, preparation method and applications.The anticorrosive paint is mainly made of hexagonal boron nitride, polyaniline nano fiber, epoxy resin, decentralized medium, coating additive, epoxy curing agent and solvent etc..Hexagonal boron nitride epoxy composite anticorrosive paint provided by the invention has excellent storage stability; it is not easy the advantages that sinking to the bottom; and preparation process is simple, low in cost; it is suitable for scale production; and excellent, anti-corrosion property persistently can have good application prospect in the industries such as chemical industry, petroleum, electric power, ship, light textile, storage, traffic, space flight by coating barrier property that it is formed.
Description
Technical field
Present invention relates particularly to a kind of hexagonal boron nitride epoxy composite anticorrosive paint, preparation method and applications, belong to painting
Expect technical field.
Background technique
According to statistics, the whole world corrodes about 100,000,000 tons of the metal scrapped every year, accounts for the 20%~40% of annual output；And with
The acceleration of industrialized process, being on the rise of etching problem, the steel equipment that the estimation whole world is scrapped by corrosion every year are suitable
In the 30% of annual output, serious economic loss is caused.Corrosion can also bring heavy casualties, environmental pollution, resource wave
The harm such as take, hinders the development of new technology, increases the loss of natural resources.Therefore, metal erosion is to national economy and society
It is seriously endangered caused by living and increasingly recognizes attention by people.
(such as: organic coating and inorganic coating) is the general measure of corrosion protection currently, surface covering paint-on technique, is had
The advantages that organic coating preparation process is simple, low in cost, suitable for scale production is widely used.Organic coating is to metal
Protective action mainly include physical barrier, passivation, the effects of the protection of antirust filler, cathodic protection.But organic coating material
Material is not a perfect barrier system, due to the hole that the strand gap of polymer itself can be such that coating generates, and
The hole that solvent volatilization generates in coating process becomes 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 affects greatly.With the enhancing of people's awareness of environment protection and health, the heavy metal free of development environment close friend it is nontoxic
Antirust pigments and fillers anticorrosive paint becomes 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 with graphene；Have simultaneously excellent chemistry and
Thermal stability, hydrophobicity, barrier property, heat conductivity lubricity and mechanical property.Hexagonal boron nitride has insulating properties, if will
Hexagonal boron nitride than graphene for that will show better corrosion resistance in coating.However hexagonal boron nitride is directly added
Into high molecular polymer or resin, hexagonal boron nitride is easy to happen due to π-πconjugation and Van der Waals force suction-operated
Reunite, and be difficult in evenly dispersed high molecular polymer or resin, causes micropore to still remain, the protection effect of the coating of formation
Difference.
Summary of the invention
The main purpose of the present invention is to provide a kind of hexagonal boron nitride epoxy composite anticorrosive paint, preparation method and answer
With to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of hexagonal boron nitride epoxy composite anticorrosive paints, it includes hexagonal boron nitride, gather
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 includes:
Also, the quality of component one and component two is 100:10~100:80.
The embodiment of the invention also provides a kind of preparation methods of hexagonal boron nitride epoxy composite anticorrosive paint comprising:
Hexagonal boron nitride and polyaniline nano fiber are dispersed in solvent, hexagonal boron nitride dispersion liquid is made, it
The hexagonal boron nitride dispersion liquid is uniformly mixed with epoxy resin, auxiliary agent and solvent afterwards, forms component one；
And provide epoxy curing agent as component two, alternatively, by epoxy curing agent with solvent dilution and shape
At component two.
The embodiment of the invention also provides the applications of the hexagonal boron nitride epoxy composite anticorrosive paint.
For example, the embodiment of the invention also provides the coatings formed by the hexagonal boron nitride epoxy composite anticorrosive paint.
For example, the embodiment of the invention also provides a kind of preparation methods of coating, comprising: by the hexagonal boron nitride epoxy
The component one and component two of composite anticorrosion coating carry out film process after evenly mixing, then through room temperature curing, form the coating.
Compared with prior art, hexagonal boron nitride epoxy composite anticorrosive paint provided by the invention has storage stability
It is good, it is not easy the advantages that sinking to the bottom, preparation process is simple, low in cost, coating barrier property suitable for scale production, and being formed by it
Energy is excellent, anti-corrosion property can persistently have well in the industries such as chemical industry, petroleum, electric power, ship, light textile, storage, traffic, space flight
Application prospect.
Detailed description of the invention
Fig. 1 is a kind of transmission electron microscope photo of the poly- butylaniline nanofiber used in the embodiment of the present invention 1.
Fig. 2 a-2b is the six side's nitrogen handled in the embodiment of the present invention 1 without poly- butylaniline nanofiber dispersion respectively
Change the dispersion of the dispersion photo of boron in a solvent and the hexagonal boron nitride by the processing of poly- butylaniline nanofiber in a solvent
Photo.
Fig. 3 a-3d is respectively the TEM figure and the obtained hexagonal boron nitride of 1~embodiment of embodiment 3 of 1 pure epoxy coating of comparative example
The TEM of epoxy composite coating schemes,.
Fig. 4 obtains hexagonal boron nitride epoxy composite coating by 1 pure epoxy coating of comparative example and 1~embodiment of embodiment 3 and exists
Mass fraction is potential polarization curve (bode) figure of the ac impedance spectroscopy after impregnating 120 days in 3.5wt%NaCl solution.
Fig. 5 obtains hexagonal boron nitride epoxy composite coating by 1 pure epoxy coating of comparative example and 1~embodiment of embodiment 3
Open circuit potential is with soaking time change curve.
Fig. 6 obtains hexagonal boron nitride epoxy composite coating by 1 pure epoxy coating of comparative example and 1~embodiment of embodiment 3
Water absorption rate curve graph.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
A kind of hexagonal boron nitride epoxy composite anticorrosive paint is provided in the embodiment of the present invention, it includes 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 includes:
Also, the quality of component one and component two is 100:10~100:80.
Before using the hexagonal boron nitride epoxy composite anticorrosive paint, component one can uniformly be mixed with component two,
Carry out the operation such as film process again later.
Further, the hexagonal boron nitride includes hexagonal boron nitride nanosheet, hexagonal boron nitride micron chip, 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 not limited to this, preferably six sides nitridation
Boron nanometer sheet.
Further, the thickness of the hexagonal boron nitride is preferably≤20nm, it is furthermore preferred that thickness≤10nm.
Further, the material of the polyaniline nano fiber can be selected from the polyphenyl that polyaniline or side chain contain substituent group
Amine, it is preferred that the substituent group includes methyl, ethyl, propyl or butyl, it is preferred that the side chain contains the polyphenyl of substituent group
Amine include polyortho methylaniline, poly- o ethyl aniline, poly- adjacent propyl aniline, poly- butylaniline any one or it is two or more
Combination, but not limited to this.
Further, the diameter of the polyaniline nano fiber is 10~300nm, and preferably diameter is 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 that aforementioned polyaniline or side chain contain substituent group is polyaniline in eigenstate.
Further, stating epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy tree
Rouge, methylol bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, modified nylon epoxy resin, line style phenol formaldehyde (PF) ring
Oxygen resin, o-cresol formaldehyde epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin, shrink
Any one in the epoxy resin such as glycerol amine type or two or more combinations, but not limited to this.
Further, the epoxy curing agent includes that polyamide-based curing agent, anacardol curing agent and imidazoles are solid
Any one in agent or two or more combinations, but not limited to this.
Further, the coating additive may also include one of anti-settling agent, defoaming agent or levelling agent or a variety of.
Wherein, the anti-settling agent includes any one in fumed silica, polyamide wax and organobentonite or two
Kind or more combination, but not limited to this.
Wherein, the defoaming agent include dimethicone, it is 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, polymethylphenylsiloxane and modified organic silicon compound or two or more groups
It closes, but not limited to this.
Further, the solvent includes toluene, dimethylbenzene, acetone, tetrahydrofuran, ethyl alcohol, ethyl acetate and dimethyl
Any one in sulfoxide or two or more combinations, but not limited to this.
The embodiment of the invention also provides a kind of preparation methods of hexagonal boron nitride epoxy composite anticorrosive paint, comprising:
Hexagonal boron nitride and polyaniline nano fiber are dispersed in solvent, hexagonal boron nitride dispersion liquid is made, it
The hexagonal boron nitride dispersion liquid is uniformly mixed with epoxy resin, auxiliary agent and solvent afterwards, forms component one；
And provide epoxy curing agent as component two, alternatively, by epoxy curing agent with solvent dilution and shape
At component two.
In some more specific embodiments, the preparation method be may comprise steps of:
It weighs a certain amount of hexagonal boron nitride and polyaniline nano fiber is scattered in solvent, it is agitated or ultrasonic obtain 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, is made
Uniformly mixed component one；
A certain amount of solvent is added in epoxy curing agent to be diluted, obtains component two.
It is more preferred, in the hexagonal boron nitride dispersion liquid, the quality of hexagonal boron nitride and polyaniline nano fiber
Than for 1:10~10:1.
The embodiment of the invention also provides the applications of the hexagonal boron nitride epoxy composite anticorrosive paint.
For example, the embodiment of the invention also provides the coatings formed by the hexagonal boron nitride epoxy composite anticorrosive paint.
For example, the embodiment of the invention also provides a kind of preparation methods of coating, comprising: by the hexagonal boron nitride epoxy
The component one and component two of composite anticorrosion coating carry out film process after evenly mixing, then through room temperature curing, form the coating.
In some more specific embodiments, after component two being mixed with component one, film process are carried out, and
Normal temperature cure 7 days or more, obtain hexagonal boron nitride epoxy composite coating.
Wherein, the mode of film process can be coating, spin coating, spraying, printing etc., but not limited to this.
Hexagonal boron nitride epoxy composite coating above-mentioned can substantially extend such when being applied to the matrix surfaces such as metal
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 later added to the ammonium persulfate of equimolar amounts in above-mentioned solution simultaneously
24 hours are stood at room temperature, polyaniline nano fiber is obtained after being filtered, washed, hydration hydrazinolysis doping is added later, with distillation
Water washing 3 times, polyaniline in eigenstate nanofiber is obtained after dry.
(2) it weighs polyaniline nano fiber made from a certain amount of hexagonal boron nitride and step (1) to be scattered in solvent, shape
At 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 uniformly mixed component one.
(4) epoxy curing agent is diluted with solvent, obtains component two.
Further, aforementioned component two and component one are mixed in a certain ratio uniformly and are applied to be formed on matrix and applied
Layer, can form hexagonal boron nitride epoxy composite coating in normal temperature cure 7 days.
General high-speed stirred and mixing and dispersing device can be used in the above stirring, dispersion, such as supersonic wave cleaning machine, ultrasound
Wave cell disruptor, high-speed mixer and mechanical agitator etc..
The present invention in hexagonal boron nitride epoxy composite anticorrosive paint by adding a small amount of evenly 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, formation protection oxidation
Layer, while the electric conductivity of polyaniline nano fiber can cause corrosion potential to migrate, to reduce corrosion of metal rate；Its
Two, hexagonal boron nitride (preferably hexagonal boron nitride two-dimensional nano piece) it is evenly dispersed so that it is overlapped in parallel in composite coating
Distribution generates labyrinth effect, can increase substantially the barrier property of coating, reduces coating crack, extends corrosive medium diffusion
Channel, and then delay metal erosion；Third, polyaniline nano fiber and hexagonal boron nitride (preferably two wiener of hexagonal boron nitride
Rice piece) it is compound after, the two collaboration, not only will not influence the aforementioned excellent performance of polyaniline nano fiber and hexagonal boron nitride, also
The dispersibility of hexagonal boron nitride can be greatly improved, can more uniformly be dispersed in the epoxy, and then makes 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 formed by it are in chemical industry, stone
It is had a good application prospect in the industries such as oil, electric power, ship, light textile, storage, traffic, space flight.
Below in conjunction with attached drawing and several embodiments the technical solution of the present invention is further explained explanation.
Embodiment 1
(1) by the poly- butylaniline nanofiber of 0.047g, (pattern is as shown in Figure 1, and can refer to method described above system
It is standby), 0.18g hexagonal boron nitride nanosheet (thickness about 3~5nm) be dispersed in 40mL tetrahydrofuran, 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 later
In Jiangsu Wujiang resultant force resin processing plant), 2g levelling agent, 2g anti-settling agent, in 3g defoaming agent and middle 8g dimethylbenzene reagent, stirred using machinery
It mixes 30 minutes, keeps various material mixings uniform, obtain component one.
(2) 7.5g polyamide 6 50,6g xylene solution are uniformly mixed obtained component two.
(3) component one is directly mixed with component two, using high-speed mixer, stirs 30 minutes to get to 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 the solvent is volatilized, obtains thickness
About 20 microns of hexagonal boron nitride epoxy composite coating.
Embodiment 2
(1) 0.095g polyortho methylaniline nanofiber (diameter about 10nm, about 0.8 μm of length), six side of 0.38g are nitrogenized
Boron nanobelt (thickness about 8~10nm) is dispersed in ultrasound 1 hour in 80mL tetrahydrofuran and obtains hexagonal boron nitride to uniformly mixed
The hexagonal boron nitride dispersion liquid is added to 30g epoxy resin (bisphenol-s epoxy resin, methylol Bisphenol F later by dispersion liquid
Type epoxy resin or A Hydrogenated Bisphenol A F type epoxy resin etc.), 2g levelling agent (polydimethylsiloxane or polymethylphenylsiloxane
Deng), 2g anti-settling agent (polyamide wax or organic swelling etc.), 3g polyethers defoaming agent and middle 8g toluene reagent (model E44, purchase
In Jiangsu Wujiang resultant force resin processing plant) in, using mechanical stirring 30 minutes, keep various material mixings uniform, obtains component one.
(2) 7.5g polyamide 6 50 is uniformly mixed with 6g toluene solution and component two is made.
(3) by component one and component two by directly mixing, using high-speed mixer, stirring 30 minutes is to get to containing
The epoxy composite coating of 1.0wt% hexagonal boron nitride.
(4) gained hexagonal boron nitride epoxy composite coating is sprayed on plain steel, after the solvent is volatilized, obtains thickness
About 20 microns of hexagonal boron nitride epoxy composite coating.
Embodiment 3
(1) 0.19g polyphenylethyl amine nanofiber (diameter about 100nm, about 0.7 μm of length), 0.75g are lacked into six side's nitrogen of layer
Change boron powder to be dispersed in 150mL tetrahydrofuran, is uniformly mixed within ultrasound 1 hour, hexagonal boron nitride dispersion liquid is obtained, later by institute
It states hexagonal boron nitride dispersion liquid and is added to 30g epoxy resin (o-cresol formaldehyde epoxy resin, aliphatic glycidyl ether asphalt mixtures modified by epoxy resin
Rouge, glycidyl ester epoxy resin or glycidyl amine type epoxy resin etc.), 2g levelling agent (polyacrylate or silicone oil
Deng), 2g anti-settling agent (fumed silica etc.), in 3g silicon modified organic polymer class defoaming agent and middle 8g dimethylbenzene reagent, make
With mechanical stirring 30 minutes, keeps various material mixings uniform, obtain component one.
(2) 7.5g polyamide 6 50 is uniformly mixed with 6g xylene solution and component two is made.
(3) by component one and component two by directly mixing, using high-speed mixer, stirring 30 minutes is to get to containing
The epoxy composite coating of 2.0wt% hexagonal boron nitride.
(4) gained hexagonal boron nitride epoxy composite coating is sprayed on plain steel, after the solvent is volatilized, 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 agent (with embodiment 1), 2g anti-settling agent (with embodiment 1),
3g defoaming agent (with embodiment 1) is dissolved in 8g dimethylbenzene reagent, using mechanical stirring 30 minutes, obtains component one.
(2) 7.5g polyamide 6 50 is uniformly mixed with 6g xylene solution and component two is made.
(3) component one is pressed with component two and is directly mixed, using high-speed mixer, stir 30 minutes to get pure epoxy is arrived
Coating.
(4) obtained pure epoxy coating is sprayed on plain steel, after the solvent is volatilized, obtaining thickness is about 20 micro-
The pure epoxy coating of rice.
Comparative example 2: the comparative example is substantially the same manner as Example 1, but with commercially available polyaniline instead of the poly- fourth in component one
Base aniline nano-fiber.
Fig. 2 a is the dispersion liquid of the hexagonal boron nitride handled in the present embodiment 1 without poly- butylaniline nanofiber dispersion
Photo, Fig. 2 b is a kind of photo of typical hexagonal boron nitride dispersion liquid in the present embodiment 1, and wherein hexagonal boron nitride passes through poly- fourth
Base aniline decentralized processing.It can be seen that without poly- butylaniline nanofiber dispersion handle hexagonal boron nitride dispersion liquid
Apparent precipitating is occurred, and the present embodiment 1 passes through the hexagonal boron nitride dispersion liquid of poly- butylaniline nanofiber dispersion processing
Without obvious sediment, this shows that poly- butylaniline nanofiber can be such that hexagonal boron nitride is uniformly dispersed in solvent.
It is respectively the typical hexagonal boron nitride that the obtained pure epoxy coating of comparative example 1 and embodiment 1-3 are obtained referring to Fig. 3 a-3d
The TEM of epoxy composite coating schemes.As the result is shown: pure epoxy coating surface is smooth, no significant defect；The typical case that embodiment 1 is obtained
There are many equally distributed white areas, predominantly hexagonal boron nitride, this shows hexagonal boron nitride epoxy composite coating surface
The presence of poly- butylaniline nanofiber reduces the aggregation of hexagonal boron nitride in the epoxy, promotes hexagonal boron nitride in ring
It is scattered in oxygen resin；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 hexagonal boron nitride epoxy composite coating and the TEM figure of slice that comparative example 2 is obtained are shown, in coating
Hexagonal boron nitride has obvious reunion, is unevenly distributed.
Six sides of pure epoxy coating and embodiment 1-3 different boron nitride contents obtained are obtained by comparative example 1 referring to fig. 4
Boron nitride epoxy composite coating is the ac impedance spectroscopy after impregnating 120 days in 3.5wt%NaCl solution in mass fraction
Bode figure；Specifically, different content hexagonal boron nitride epoxy composite coating of the invention is impregnated in 3.5wt%NaCl solution
It 120 days, in soaking process, is handed over using the variation and electrochemistry of Shanghai Chen Hua CHI660E electrochemical workstation monitoring open circuit potential
Flow impedance spectrum.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 impregnating 50
After it, impedance magnitude is from 3.5 × 108Ωcm2It is reduced to 1.1 × 105Ωcm2, show that pure epoxy coating is no longer valid.And this
The different boron nitride content hexagonal boron nitride epoxy composite coatings of invention still keep higher impedance value after impregnating 120 days, especially
It is 0.5~1wt% hexagonal boron nitride epoxy composite coating, and impedance magnitude is about 1.0 × 109Ωcm2；In addition to this, of the invention
Different boron nitride content hexagonal boron nitride epoxy composite coatings there is increased trend in soaking process middle impedance modulus value, this can
It can make passivation of metal surfaces with the presence of polyaniline nano fiber and be formed to protect oxide layer related.In the same way
The hexagonal boron nitride epoxy composite coating obtained to comparative example 2 is tested, the results show that it is similar to pure epoxy coating, warp
Impedance magnitude also has significant decrease after the immersion of short time, and reduction amplitude is far longer than the hexagonal boron nitride epoxy of embodiment 1-3
Composite coating.
It is nitrogenized referring to Fig. 5 by six side of different boron nitride contents obtained in 1 pure epoxy coating of comparative example and embodiment 1-3
The open circuit potential of boron epoxy composite coating is with soaking time change curve；As the result is shown: with the extension of soaking time, open circuit
Potential value constantly reduces, and relative to and pure epoxy coating, the open circuit potential of hexagonal boron nitride epoxy composite coating occur just
It moves, shows that corrosion process is more difficult to occur.The obtained hexagonal boron nitride epoxy composite coating of comparative example 2 is carried out using same way again
Test, although the results show that its corrosion resistance has the promotion of certain amplitude compared with pure epoxy coating, but still much it is weaker than implementation
The hexagonal boron nitride epoxy composite coating of example 1-3.
The different boron nitride content hexagonal boron nitride rings obtained referring to Fig. 6 by 1 pure epoxy coating of comparative example and embodiment 1-3
The water absorption rate curve graph of oxygen composite coating, the water absorption rate curve of coating can be divided into two stages: initial phase and water suction saturation
Stage, pure epoxy coating show highest water absorption rate, about 1% after water suction saturation；And six side's nitrogen of different boron nitride contents
The water absorption rate for changing boron epoxy composite coating is substantially reduced compared with pure epoxy coating, this shows evenly dispersed hexagonal boron nitride in epoxy
Lamella blocking effect is formed in coating, it is suppressed that the diffusion of corrosive medium in the coating.From the above result shows that, hexagonal boron nitride
The excellent corrosion resistance of epoxy composite coating may mostly come from polyaniline nano fiber and hexagonal boron nitride nanosheet
Synergistic effect.The obtained hexagonal boron nitride epoxy composite coating of comparative example 2 is tested using same way again, the results show that
Its water absorption rate has the promotion of certain amplitude compared with 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 chip of thickness about 20nm
Poly- adjacent propyl aniline nano-fiber is used for the hexagonal boron nitride nanosheet in component one, and in component one, and (diameter is about
300nm or so, about 5 μm of length or so), the solvent used in component one and component two is acetone and dimethyl sulfoxide.
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
Using polyaniline nano fiber instead of the hexagonal nanometer boron nitride band in component one, and in component one, (diameter about 150nm is left
The right side, 2 μm of length or so), the solvent used in component one and component two is ethyl alcohol 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 in 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 is instead of the hexagonal boron nitride nanosheet in component one.
Embodiment 8: the present embodiment is substantially the same manner as Example 3, but with the fluorination boron nitride of thickness about 10~15nm substitution
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 1~embodiment of embodiment, 3 same way, as a result shows that these composite anti-corrosives apply
Material all has excellent storage stability, and these composite coatings formed also show excellent anticorrosion performance and barrier property
Energy.
Embodiment described above is only used for the core concept for helping to understand method of the invention, and description is more specific and detailed
Carefully, but it cannot be understood as limitations on the scope of the patent of the present invention.It should be pointed out that for the common skill of this field
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 scope.Various modifications to these embodiments are for one of skill in the art it is clear that institute herein
The General Principle of definition can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore,
The scope of protection of the patent of the invention shall be subject to the appended claims, without limitation on these examples shown in this article, but
Meet the range consistent with principles disclosed herein and feature.
Claims (17)
1. a kind of hexagonal boron nitride epoxy composite anticorrosive paint, characterized by comprising:
Component one includes:
50 ~ 79wt% of epoxy resin,
0. 5 ~ 2 wt% of hexagonal boron nitride,
0. 25 ~ 1wt% of polyaniline nano fiber,
0.5 ~ 5 wt% of coating additive,
20 ~ 30 wt% of solvent, the sum of dosage of each component is 100wt% in component one；
And component two, include:
75 ~ 100wt% of epoxy curing agent,
0 ~ 25wt% of solvent；
Also, the quality of component one and component two is 100: 10 ~ 100: 80；
The thickness of the hexagonal boron nitride≤20 nm, and it is selected from hexagonal boron nitride nanosheet, hexagonal boron nitride micron chip, six sides
Boron nitride nanometer band, the number of plies are 2 ~ 5 layers and without 5 layers of few layer of hexagonal boron nitrides, six side of the multilayer nitridation that the number of plies is 5 ~ 9 layers
Any one or any one derivative in boron, hexagonal boron nitride quantum dot；
The material of the polyaniline nano fiber is selected from polyaniline or the polyaniline containing substituent group, and the substituent group is selected from alkane
Base or amido, the diameter of the polyaniline nano fiber are 10 ~ 300 nm, and length is 0.5 ~ 5 μm.
2. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: the hexagonal boron nitride
Thickness≤10 nm.
3. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: the hexagonal boron nitride
For hexagonal boron nitride nanosheet.
4. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: the alkyl includes first
Base, ethyl, propyl or butyl.
5. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: described to contain substituent group
Polyaniline include in polyortho methylaniline, poly- o ethyl aniline, poly- adjacent propyl aniline, poly- butylaniline and poly-o-phenylenediamine
Any one or two or more combinations.
6. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: the polyaniline nano
The diameter of fiber is 10 ~ 100 nm, and length is 0.5 ~ 5 μm.
7. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: the epoxy resin packet
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, o-cresol formaldehyde epoxy resin, fat
Race's tetraglycidel ether epoxy resin, glycidyl ester type epoxy resin, in glycidyl amine type epoxy resin any one or
Two or more combinations.
8. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: the epoxy resin is solid
Agent includes any one or two or more groups in polyamide-based curing agent, anacardol curing agent and imidazole curing agent
It closes.
9. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: the coating additive packet
Include any one in anti-settling agent, defoaming agent and levelling agent or two or more combinations.
10. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 9, it is characterised in that: the anti-settling agent packet
Include any one in fumed silica, polyamide wax and organobentonite or two or more combinations.
11. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 9, it is characterised in that: the defoaming agent packet
It is organic to include dimethicone, ether ester compound, modified mineral oil, polyethoxy glycerol ether, small molecule metallorganic or modification
Silicon polymer.
12. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 9, it is characterised in that: the levelling agent packet
It is organic to include butyl glycol ether, cellaburate, polyacrylate, silicone oil, hydroxymethyl cellulose, polydimethylsiloxane and modification
Any one in silicon compound or two or more combinations.
13. hexagonal boron nitride epoxy composite anticorrosive paint according to claim 1, it is characterised in that: the solvent includes
Any one in toluene, dimethylbenzene, acetone, tetrahydrofuran, ethyl alcohol, ethyl acetate and dimethyl sulfoxide or two or more groups
It closes.
14. a kind of method for preparing hexagonal boron nitride epoxy composite anticorrosive paint described in any one of claim 1-13, special
Sign is
Hexagonal boron nitride and polyaniline nano fiber are dispersed in solvent, hexagonal boron nitride dispersion liquid is made, later will
The hexagonal boron nitride dispersion liquid is uniformly mixed with epoxy resin, auxiliary agent and solvent, forms component one；
And provide epoxy curing agent as component two, alternatively, by epoxy curing agent with solvent dilution and formation group
Divide two.
15. the preparation method of hexagonal boron nitride epoxy composite anticorrosive paint according to claim 14, it is characterised in that:
In the hexagonal boron nitride dispersion liquid, the mass ratio of hexagonal boron nitride and polyaniline nano fiber is 1:10 ~ 10:1.
16. the coating that hexagonal boron nitride epoxy composite anticorrosive paint is formed as described in any one of claim 1-13.
17. a kind of preparation method of coating, characterized by comprising: by hexagonal boron nitride described in any one of claim 1-13
The component one of epoxy composite anticorrosive paint and component two carry out film process after evenly mixing, then through room temperature curing, described in formation
Coating.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN111154376A (en) * | 2020-01-16 | 2020-05-15 | 宁波宁静新材料科技有限公司 | Ag/BNNSs nano material modified epoxy resin composite coating |
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| CN111171667A (en) * | 2018-11-09 | 2020-05-19 | 江苏师范大学 | Preparation method of nano anticorrosive paint |
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