CN108178964A - A kind of graphene solvent free corrosion prevention coating and technology of preparing - Google Patents
A kind of graphene solvent free corrosion prevention coating and technology of preparing Download PDFInfo
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- CN108178964A CN108178964A CN201711074552.7A CN201711074552A CN108178964A CN 108178964 A CN108178964 A CN 108178964A CN 201711074552 A CN201711074552 A CN 201711074552A CN 108178964 A CN108178964 A CN 108178964A
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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Abstract
The invention belongs to a kind of graphene solvent free corrosion prevention coating, are widely used in the heavy antisepsis such as reservoir walls, shipbuilding industry, port and pier, buried pipeline field.It is characterized in that：Film forming matter is polymerized to by liquid-state epoxy resin, adds in the compositions such as graphene nano element, a variety of inorganic nano composite materials and its reactive diluent, auxiliary agent, filler, pigment and amine curing agent.Graphene (addition) of the present invention illustrates six point invention examples in modified coating aspect of performance on specification.Start to go out advantage and feature for the schemes show realized in following six kinds of non-solvent epoxies (weight) anticorrosive paints in Bai Shi high coating application processes at present；(seeing below 6 examples).Solvent free corrosion prevention coating is modified through graphene (addition), the Corrosion Protection for the coating that can improve a lot, meanwhile, coating is made to be provided with prominent green environmental protection.
Description
The invention belongs to a kind of graphene solvent free corrosion prevention coating, mainly construct in the environment of suitable for improper ventilation,
It can be used to load drinking water, food or other sensitive species.Graphene (addition) modified solvent free anticorrosive paint, makes to have more
Intensity is high, cure shrinkage is small, chemical resistance is excellent, alkali resistance is prominent, can 200~1000 μm of one-off construction, needleless
The advantages that hole, excellent antiseptic property, is widely used in the heavy antisepsis such as reservoir walls, shipbuilding industry, port and pier, buried pipeline neck
Domain becomes the essential coating variety in anticorrosive paint field.
The present invention relates to a kind of graphene solvent free corrosion prevention coating and technologies of preparing, it is characterised in that：By liquid epoxy tree
Fat is polymerized to film forming matter, add in graphene nano element, a variety of inorganic nano composite materials and its reactive diluent, auxiliary agent,
The compositions such as filler, pigment and amine curing agent.
It is a kind of coating of novel environmental close friend that graphene no-solvent type anti-corrosion, which looks askance at coating, generally refers to solid point after film forming
Content is close to or up to 100% coating, it be a kind of high-performance, high solid coating.Solventless coatings can claim activity again
Coatings volatile organic compounds, it is not to be entirely free of solvent, and refers to that solvent eventually becomes film component, during film-forming not to
Voc is discharged in air.
For no-solvent type coating, traditional defense coating is limited to own material property and technique, to metal
The corrosion protection effect of matrix is often not satisfactory, and the exsertile cost of individual is again very high, reduces the cost performance of coating, and
For quite a few coating because of the heavy metals such as leaded zinc or chromate or noxious material, there are certain risk of environmental pollution, also disappear
A large amount of non-renewable resources have been consumed, have been unfavorable for the sustainable development of social economy.Therefore, exploitation novel graphite alkene (addition) changes
Property solvent free corrosion prevention coating make long-acting environment friendly anticorrosive coating become new hot spot.
Graphene is a kind of two dimensional crystal material being made of sp2 hydbridized carbon atoms, has slightly wavy laminar knot
Structure, the conjugated structure of general graphene can cause its compatibility with water, organic solvent and polymer poor, thus increase
Its application difficulty in paint field.To solve the problems, such as this, can during graphene is prepared first by GO functional modifications,
It is restored on demand again.
Graphene (addition) modified solvent free anticorrosive paint of the present invention is generally bi-component, adds in addition before use sometimes
Agent common are epoxy resin, polyurethane resin, organic siliconresin, carbamide resin etc., rotproofness, weatherability, mechanical strength
Deng more prominent, one-pass film-forming, adhesive force is excellent, and the range of choice of raw material is wide, have pollution less, convenient construction, physical property
It is excellent, the features such as being widely used.
In the country uses at present graphene solventless coatings and binder, usage amount and use scope it is maximum be exactly ring
Oxygen resin contains in epoxy resin there are many group that different function effect can occur, such as epoxy group, ehter bond, hydroxyl and phenyl ring,
Epoxy group can crosslink the features such as reaction.
Graphene had both remained original property after functional modification, had also been attached to the reactivity of modified group, can have
Effect improves dispersibility of the graphene in coating system, compatibility or even can assign coating system certain specific function, therefore stone
The functional modification of black alkene is its essential important ring in paint field application.
Graphene coating is a kind of material, this containing graphene film diameter material, can be coated with different construction technologies
In object surface, formed and adhered to securely, with some strength, continuous solid film.The film common name film formed in this way, also known as
Paint film or coating, the coating of graphene coating.
The super-hydrophobicity on flake graphite alkene surface and flake graphite alkene arranged in parallel to the iris action of corrosion factor,
Possibility is provided as anticorrosive paint for graphene, graphene is studied by major industrial country and application is promoted to strategic height
Degree.
Dispersion is the key technical problem of graphene filler, to the anti-corrosion of solvent-free/water-based anticorrosive paint and epoxy coating
Property influence it is huge.Since graphene itself is reunited, generally by chemically grafting and modifying, but process is cumbersome, of high cost, it is difficult to industry
Change, because of the invention, succinctly effective dispersing method is most important.
In general, solventless coatings, is not without solvent, but this solvent can be with dissolving resin, and has and live
Property can react with resin, become a part for film.It is very little to the pollution of environment, is current anticorrosive coating
One of important development direction.But such coating, since system viscosity is larger, working life is short, and appearance of film quality is not ideal enough,
And construction requirement is higher, thus price is also higher, there are no obtain large range of application.
The present inventor carries graphene application performance with scheme in graphene modified solvent free anticorrosive paint application process
Go out it is following some.
(1) graphene has high-specific surface area, Quick conductive, excellent chemical stability, the mechanical property of protrusion, height
The performances such as thermal conductivity make its modification be widely used in solvent free corrosion prevention coating.
(2) graphene can greatly improve nothing in the coating systems such as modified anti-corrosive coating, conductive coating, anti-flaming dope
The comprehensive performance of coatings volatile organic compounds such as reduces coating layer thickness, increases the adhesive force to base material, promotes solvent free corrosion prevention material wearability,
And make coating that there is green environmental protection.Especially water-based anticorrosive paint, epoxy zinc-enriched paint, conductive coating, in have it is prominent
Performance.
(3) graphene passes through as a kind of novel anti-corrosion reinforcing material on the basis of common corrosion-resistant epoxy paint
Adding new coating prepared by graphene not only has the shielding of cathodic protection effect, glass-flake coating of epoxy zinc-enriched paint
Effect has the characteristics that good toughness, strong adhesive force, water-tolerant, hardness are high, and antiseptic property is applied more than existing heavy antisepsis
Material.
1. without volatile organic solvent, solid part is up to 100%
2. stronger to 5-45 DEG C of paint film adhesion of room temperature curing using graphene modification, mechanical performance is more excellent, is more easy to construct.
3. graphene makes paint film water resistance more excellent, due to using graphene biomass special type curing agent, the paint film after curing
It is more nontoxic, not polluted drinking water and food.
(4) for the conjugated structure of graphene with very high electron mobility and excellent electric property, this is people
Highly desirable utilizable performance.Traditional conductive coating by add in conductive material be used as additive reach film conduction
Purpose, conductivity additive is usually metal or metal oxide particle (such as silver powder, copper powder, zinc oxide), with application compared with
For extensive silver powder, dosage, grain size and form all have a significant impact to the electric conductivity of coating.Compared to silver powder, graphite
Alkene is also equipped with excellent mechanical performance and hot property other than having good electric conductivity, is splendid conductive coating additive.
(5) the two-dimensional slice structure of graphene, makes it be layering in coating, can form fine and close physical isolation layer,
Play the role of prominent physical isolation, improve flame retardant property；Graphene with resin can also be crosslinked it is compound, in coating just
One layer of fine and close protective film can be further formed, plays the role of obstructing air, so as to play fire-retardant effect；And in height
Under temperature, graphite ene coatings can generate CO2And water, and finer and close continuous layer of charcoal is generated, further iris action is played, so as to
Improve the flame retardant property of solventless coatings.
(6) thermal conductivity factor of graphene is up to 5300W/mK, higher than carbon nanotube and diamond.Graphene is modified without molten
Agent heat radiation coating makes it have high thermal conductivity, meanwhile, the high-specific surface area of graphene makes it be sufficient filling in the coating, increase
Coating cooling surface area, can reduce body surface and internal temperature.Graphene is modified heat dissipation solventless coatings can be long-term
It working at high temperature, wear resistant and impact resistant is strong, has good weatherability, salt spray resistance aging, soda acid aging, illumination ageing etc.,
In the usable purpose of various extreme environments.
The graphene and (BSG-8001 graphenes slurry) of the homemade two layers of stripping of inventor, start in following Bai Shi at present
The technical solution realized in six kinds of non-solvent epoxy (weight) anticorrosive paints in high coating.1. graphene non-solvent epoxy heavy antisepsis
2. graphene thickness applies wear-resisting solventless epoxy anti-corrosive coating 3. graphene nano TiO2 solventless epoxy anti-corrosive coatings 4. stone to coating
Black alkene (bi-component) the solventless epoxy anti-corrosive coating 5. wear-resisting solventless epoxy anti-corrosive coatings of graphene nano SiO2 6. graphene
The solvent-free super thick film epoxy heavy-duty anticorrosive coating of two-component spraying type.
Graphene prepared by general chemistry oxidation-reduction method, the edge of lamella is still containing a small amount of hydroxyl not being reduced
Base, carboxyl, this causes graphene to be provided with certain physics, chemism, can assign composite material some good performances, such as
Dispersed (hydrogen bond action), adhesive force etc..Also have simultaneously and participate in chemical crosslinking, improve crosslink density, reinforcement film mechanical property
The effect of energy.Nonetheless, but when graphene dosage is excessive, itself can be generated and reunited, destroy uniformity, the densification of its dispersion
Property, (graphene is reunited, and is applied for electric conductivity (conductive network structural damage forms point contact or line contact), mechanical performance
Stress concentration is generated inside film), antiseptic property declines instead.
Graphene slurry of the present invention in itself have hydrophobic and lyophobic property, lamellar structure have " labyrinth " effect, can hinder water,
The infiltration to metal base such as corrosive ion, delays the corrosion rate of metal base, and then plays the role of corrosion-resistant to ground.
1. by nearly four year under severe conditions, graphene slurry is formulated situation about using on anticorrosive paint
Under, it was demonstrated that and with the long-effective corrosion service life, the anticorrosive paint is in chemical atmosphere and marine environment, mainly by detecting instrument with setting
Standby detection confirms (generally can be used 10 years or 15 years or more), even if in acid, alkali, salt and solvent medium, and in certain temperature
Under the conditions of, more than (could be used that 6-8).
2. slow 20 times of the naked nickel of etch ratio of the nickel of the graphite ene coatings of the homemade two layers of stripping of inventor, and band four
The naked nickel of etch ratio of the nickel of layer transfer graphite ene coatings wants slow four times.
3. the graphene of the homemade two layers of stripping of inventor possesses atom level reticular structure, 3,000,000 layer graphenes just only have
One millimeters thick.
4. show that graphene coating can effectively inhibit metal oxidation reaction and oxidation according to cyclic voltammetry measuring method
Reduction reaction can be found that graphene is in itself and undamaged by electrochemical impedance spectroscopy measuring method, and following metal crack
In then there is corrosion phenomenon.
Therefore, the anticorrosive paint of BSG-8001 graphenes slurry and the main distinction of conventional anticorrosive paint are to be its skill
Art content is high, and technical difficulty is big, the technological progress and research and development of products being related to, it has no longer excessively relied on the knowledge and warp of coating
Test, it depends on the multi-disciplinary knowledge such as electronics, physics, ecology, machinery, instrument and management and crosses, his Technology origin in
The synthesis of high resistance to resin, the application of dispersant with high efficiency and auxiliary rheological agents, the impervious pigment of Novel corrosion and filler are developed, are advanced
With the uses such as supplementary measures such as special test equipment.
Due to graphene excellent physical properties, heat conductivility is also higher than carbon nanotube and diamond, which is 5300W/
MK, its electron mobility is more than 15000cm2/vs under room temperature environment, more than carbon nanotubes or silicon crystal.Graphene is current
The best material of electric conductivity in known materials in the world, resistivity is only 10-8 Ω cm, less than copper or silver.
So general watersoluble plumbago alkene slurry is wider for anticorrosive paint application face.
BSG-8001 watersoluble plumbago alkene slurries are mainly made of high-quality graphene and deionized water, are had purity height, are divided
It dissipates that property is good, the features such as haveing excellent performance, is widely used, domestic antistatic/conductive coating, anti-corrosion/anticorrosive paint, heat dissipation can be met
Coating, the application demand for enhancing coating are that exploitation is filled out with high-performance, the ideal of multi-functional, characteristic of low cost new coating
Expect (being chatted after specific formula).
Graphene (addition) of the present invention is in the above-mentioned six kinds of non-solvent epoxies (weight) anticorrosive paint aspect of performance of modification in this theory
Six point invention examples are illustrated on bright book.
A kind of this graphene modified solvent free epoxy (weight) anticorrosive paint processing performance, which significantly improves, (to be seen below at 6 points to show
Example).Solvent free corrosion prevention coating is modified through graphene (addition), the Corrosion Protection for the coating that can improve a lot, meanwhile, make painting
Layer is provided with prominent green environmental protection.
The technology important research neck for having become graphene in the application of non-solvent epoxy (weight) anticorrosive paint domestic at present
Domain.Following detailed technology statement：
1st, Bai Shi high (BSG-831 graphenes solvent-free epoxy heavy-duty anticorrosive coating) is bi-component, is that inventor is autonomous
Research and development, this anticorrosive paint (heavy-dutycoating) refers generally to apply in relatively harsh corrosive environment, and have
A kind of anticorrosive paint of protection period longer than conventional anticorrosive paint can be reached by having.
According to Fick laws, the time that corrosive medium infiltration reaches coating-metal interface is directly proportional to coating layer thickness square,
It is inversely proportional with diffusion coefficient.Paint film is thicker, and anti-corrosion life is longer.Therefore, thick-film be anticorrosive paint important symbol it
One.
Due to the raising of environmental requirement, coating gradually develops to large arch dam, solvent-free and Water-borne modification.
The present invention is mainly that the preparation of graphene solvent-free epoxy heavy-duty anticorrosive coating is as follows：
1. prepared by colored paint component A
The dispensing of epoxy resin, graphene slurry, diluent, dispersant and antifoaming agent is stirred evenly in a reservoir, is added in
Thixotropic agent, sericite in powder, talcum powder, barium sulfate and iron oxide red high speed dispersion to fineness be less than 80 μm, be cooled to 50 DEG C hereinafter,
It adds in polar solvent middling speed to be uniformly dispersed, filter and package.
2. prepared by curing agent B component
Modified fatty amine, accelerating agent, antifoaming agent, dispersant dispensing are uniformly dispersed in a reservoir, add in thixotropic agent, mica
Powder and barium sulfate high speed dispersion to fineness are less than 80 μm, are cooled to 50 DEG C and are uniformly dispersed hereinafter, adding in polar solvent middling speed, filter
Packaging.
3. coating property and technical indicator
Model is prepared according to GB1727-1992 and carries out performance detection, and testing result reaches technical indicator.
2nd, Bai Shi high (BSG-832 graphenes thickness applies wear-resisting solventless epoxy anti-corrosive coating) is bi-component, for invention
People's independent research, this bi-component is base-material using low viscosity bisphenol F epoxy resin, adds high abrasion color stuffing and auxiliary agent etc.,
Using modified fatty amine as curing agent, develop it is a kind of have it is thick apply, curing rate is fast, excellent in abrasion resistance, strong adhesive force, salt spray resistance
The solventless epoxy anti-corrosive coating for the features such as property is excellent, the fissility of resistance to cathode is good.
The present invention is mainly that the wear-resisting solventless epoxy anti-corrosive coating preparation of graphene thickness painting is as follows：
1. the preparation of colored paint component A coating
Low-viscosity bisphenol F epoxy resin and toughener are mixed in proportion first, in the mistake of high speed dispersor stirring
Cheng Zhong sequentially adds titanium dioxide, silicon carbide, silica flour, sericite in powder, dispersant, silane coupling agent and gas phase two in proportion
Silica；After mixing, ground twice with cone mill；Under conditions of high speed dispersion, antifoaming agent is added in, high speed dispersion
30min is to get coating finished product.
2. the preparation of model and coupon
Prepared coating is uniformly mixed in proportion with curing agent, according to corresponding national standard and rower SY/T0315-2005
≤ steel pipe clinkery epoxy powder external coating technical standard >=prepares test plate (panel) and coupon.The coating one-pass film-forming thickness can reach
1mm。
3. graphene thickness applies wear-resisting solventless epoxy anti-corrosive coating film performance and technical indicator coating property and technology refers to
Mark
Model is prepared according to GB1727-1992 and carries out performance detection, and testing result reaches technical indicator.
3rd, Bai Shi high (BSG-833 graphene nano TiO2 solventless epoxy anti-corrosive coatings) is inventor's independent research.
Technology is expressed as follows：Since nano TiO 2 has bulk effect, skin effect, quantum size effect, macro quanta tunnel effect,
And the performances such as excellent power, light, magnetic, electricity is under certain process conditions, and it is compound with epoxy resin base-material using it, it can overcome
Traditional coating mechanical strength, the shortcomings of wearability and antiseptic property are poor, obtain the excellent nano TiO 2 modified solvent free of anti-corrosive properties
Corrosion-resistant epoxy paint.
(1) preparation of nano TiO 2 dispersion liquid
1. weighing a certain amount of TiO_2 nanoparticles dried, making medium with isopropanol is configured to suspension, at a high speed
(1000r/min) disperses 30min, then ultrasonic disperse 30min, moves into three-necked flask.
2. a certain amount of silane coupling agent is dissolved in isopropanol medium simultaneously, 1000r/min is stirred under room temperature (25 DEG C)
Mix 15min.Above-mentioned 2 kinds of solution is mixed, disperses 30min in ultrasonic field, then at a certain temperature in being stirred in thermostatical oil bath,
Make coupling reaction 2h, nano TiO 2 dispersion liquid is made with spare.
3. general analyzed with dynamic light scattering (DLS) it is found that average grain diameter is about in the nano TiO 2 dispersion liquid prepared
100nm, grain size is in normal distribution and stability is good, and secondary agglomeration does not occur.
(2) preparation of modified epoxy：
1. in mass ratio 9: 1 add in epoxy resin and nbr carboxyl terminal in three-necked flask, blender is started
(800r/min), oil bath heating are reacted to 110~120 DEG C.
2. according to GB/T1677-2008《The measure of plasticizer epoxide number》Standard, the epoxide number of METHOD FOR CONTINUOUS DETERMINATION reaction system,
Until the epoxide number of system is stablized relatively, reaction reaches terminal.
3. being cooled to room temperature, nbr carboxyl terminal modified epoxy is obtained.
(3) preparation of nanometer corrosion-resistant epoxy paint：
1. weighing a certain amount of above-mentioned modified epoxy prepared, cashew nut oil modified epoxide resin reactive dilution is added in
Agent, at a high speed (800r/min) stir certain time to being uniformly dispersed.
2. adding in the nano TiO 2 dispersion liquid of above-mentioned preparation, pigment, filler and related auxiliaries are eventually adding, continue to stir
Nano TiO 2 solventless epoxy coating is made in ultrasonic disperse 2h after uniformly, discharging.
(4) graphene nano TiO2 modified solvent frees corrosion-resistant epoxy paint performance and technical indicator
Model is prepared according to GB1727-1992 and carries out performance detection, and testing result reaches technical indicator.
4th, Bai Shi high (BSG-834 graphenes (bi-component) solventless epoxy anti-corrosive coating) is the skill of inventor's independent research
Art is expressed as follows：In general, one kind using low-viscosity bisphenol A type epoxy resin as base-material, adds the strong laminal filter of barrier property
With each analog assistant, and using modified by cardanol amine as the solventless epoxy anti-corrosive coating of curing agent.This paint viscosity is low, during curing
Between it is short, easy for construction, good leveling property, coating machinery and adhesive force are excellent, and with good corrosion resistance.
(1) using the diluent compound system of single, double functional group, good diluting effect, Er Qieke can not only be played
The flexibility of film is improved, and will not significantly weaken the crosslinking degree of film.
(2) epoxy resin and the curing mainly epoxy group of modified by cardanol amine and reacting for amido.
(3) bond strength that the additive amount of silane coupling agent can promote film 0.3%, while it is resistance to enhance its
Corrosive nature.
(4) graphene (bi-component) solventless epoxy anti-corrosive coating film performance and technical indicator
According to corresponding national standard, basic performance detection is carried out to coating and coating, testing result reaches technical indicator.
5th, Bai Shi high (the wear-resisting solventless epoxy anti-corrosive coatings of BSG-835 graphene nanos SiO2), it is autonomous by inventor
The technology of research and development is expressed as follows：
The wear-resisting solventless epoxy anti-corrosive coatings of single-component nanometer SiO2 of this development, have that curing rate is fast, wearability is excellent
Different, strong adhesive force, salt fog resistance are excellent and the characteristics of antikathode fissility is good.
Common solvent class anticorrosive paint, since the volatilization of solvent easily forms the disadvantages such as pin hole, shrinkage cavity, makes in film forming procedure
Water, oxygen and corrosive medium generate infiltration and cause underfilm corrosion.Corrosion product expansion makes coating breaks down, medium along coating around
Diffusion, causes coating fall in flakes, and coating loses corrosion-resistant effect.
Solvent-free anticorrosive paint can eliminate coating pin hole because of solvent-free volatilization, improve permeability resistance and corrosion resistance,
The wasting of resources caused by avoiding solvent volatilization, reduces the destruction to environment.
Non-solvent epoxy and modified anticorrosive coating are with solid content is high, one-pass film-forming is thick, adhesive force is excellent, impervious
Can the corrosion such as good, acid and alkali-resistance salting liquid, water-fast, resistance to crude oil, diesel oil, gasoline, solvent the features such as.
(1) selection of film forming matter resin raw material
In the coating system, the main film forming matter bisphenol F epoxy resin of selection remove with bisphenol A epoxide resin all are excellent
Outside good characteristic, viscosity is far below bisphenol A epoxide resin, therefore does not need to add in solvent or reactive diluent in use,
More convenient operation, the mechanical property after cured paint film more preferably, have better solvent resistance, avoid due to adding in solvent or dilute
Agent is released, and paint film is made the disadvantages such as pin hole, brittleness is big occur.
Since bisphenol F epoxy resin price is higher than bisphenol A epoxide resin, in the base for considering coating Cost And Performance
On plinth, when determining that resin content accounts for the 35%~50% of total amount through overtesting, cost performance highest.
(2) the component selection of curing agent
Curing agent has length with the coating after resin Composition film forming used in the two-component coating requirement of solventless epoxy coating system
Phase resists the superperformance of external mechanical abrasion and chemical attack, and therefore, curing agent and crosslinking curing effect are to determine coating
The key of energy.The repaired mouth coating and bend pipe anticorrosive paint of long-distance transport pipes are required on the basis of antiseptic property is ensured, do solid work the time
It is short, generally it is less than 5h.
According to above-mentioned requirements, Ancamine modified fatty amines are selected, which has that room temperature viscosity is low, rate of drying
Soon, good dispersibility, hardness rise the characteristics of fast in the coating, generation amino first is reacted in reduction with Carbon Dioxide in Air
The chance of hydrochlorate, so as to avoid mist of oil face；Paint film intensity height after curing, flexibility are good, good chemical resistance.According to experiment
As a result think, it is only 3h which, which does solid work the time,.
(3) composition of color stuffing
The kind and dosage of color stuffing have the stability of coating, the corrosion resistance of coating and physical mechanical property very big
Influence, reasonably select color stuffing, be the important link of high-performance anticorrosion Design of Coatings Formulation.
Pigment used in high-performance, high abrasion anticorrosive coating and filler must have excellent anti-corrosion in various corrosive mediums
Performance.The transmission of the corrosion factors such as flakey filler energy shield water, oxygen, ion cuts off the pore in paint film.Friendship parallel to each other
Folded scale plays labyrinth effect in paint film, extends the approach that corrosion factor penetrates into paint film, improves the anti-corrosion capability of coating.
Therefore Scale filler plays key effect for increasing substantially the corrosion resisting property of heavy-duty anticorrosive coating.
Based on mentioned above principle, the fillers such as addition silica flour, silicon carbide have been selected, have greatly improved the chemical resistance of paint film
And abrasion resistance, wearability (knockout method) reach 4L/ μm；The sericite in powder of addition have big, the excellent insulating properties of radius-thickness ratio,
Wearability and toughness, it is completely inert in various chemical attack media, while the high-gravity fillers such as silica flour in coating can be prevented
Sedimentation and the sagging in coating process, the film of formation there is excellent salt fog resistance and antikathode to remove.
(4) selection of toughening/thickener
Toughener action principle is that interaction between toughening agent molecule and epoxy molecule is used to divide instead of epoxy resin
The intersegmental interaction of subchain, makes the glass transition temperature of coating reduce, and thus increases the toughness of high-molecular compound, improves coating
Brittleness.
In order to meet resistance to bend(ing) and impact resistance of the coating under thick coating (thickness of dry film is more than 1mm) state, and not
The antikathode fissility of coating can be impacted, by Experimental Comparison, Bai Shi high companies have been selected certainly in the coating thickener
The BSG- nanostructured rheological thickeners of system；Toughener has selected the cashew nut oil modified epoxy resin roughening of Ka Delai companies
Agent.
Not only with the excellent long aliphatic chain of hydrophobicity but also containing resistant to chemical etching on the molecular structure of the general toughener
Unsaturated double-bond on benzene ring structure and long aliphatic chain, such a construction ensures tough in effectively reduction system viscosity, increase system
Property while, and can remain unchanged other physicochemical properties of coating, and therefore will not reduce the corrosion resistance of paint film.
In the coating system of development, dosage is more suitable at 5% or so.
(5) selection of coupling agent
The fillers such as silica flour, sericite in powder are the key that influence paint film corrosion resistance, bonding with resin in order to increase
Ability should use coupling agent treatment, chemical bond or Hydrogenbond are formed between resin and scale, reach shielding and inhibit rotten
Lose the purpose of factor migration.In this study, silane coupling agent has been selected, the fillers such as sheet sericite in powder has been improved and is glued with resin
Performance is connect, so as to improve the anti-permeability performance of coating and corrosion resistance.
(6) selection of thixotropic agent
The solvent free corrosion prevention erosion coating category high build paint newly developed, coating due to once brushing formation it is thicker (1mm with
On), sagging is serious before curing for coating, therefore, it is necessary to suitable thixotropic agent be added, to improve the stream of the sedimentation of coating and coating
It hangs.
Common thixotropic agent has rilanit special, organobentonite and aerosil etc..The addition of thixotropic agent must
Must be just right, appropriate levelling can be given in low-viscosity in this way, but the time is not again long and avoid generating sagging, is originally grinding
In studying carefully, by experiment, using the homemade anti-settling stabilizer of BSG- nanostructureds of about 1.5% Bai Shi high companies as thixotropic agent,
And sludge proof can be played the role of, increase bin stability.
(7) selection of other auxiliary agents
Since the coating is high build paint, it is difficult to certainly into the bubble of coating system in production or coating whipping process
Row effusion, therefore antifoaming agent must be added.Antifoaming agent must have the ability for weakening and eliminating foam stabilization factor, improper use meeting
Side effect is generated, in addition to shrinkage cavity is caused, can also cause the disadvantages such as adhesive force reduction, coating film gloss decline.Pass through experiment, selection
The antifoaming agent of BYK companies, such antifoaming agent have the characteristics that additive amount is small, defoaming effect is apparent.Dispersant is can to improve painting
Expect the interface active agent of dispersion stability, can adsorb on the surface of pigment, prevent dispersed color stuffing particle once again
Harmful flocculation is formed, therefore the dispersant of BYK companies has been selected in the coating system, is worked well, there is coating good
Bin stability.
(8) the wear-resisting solventless epoxy anti-corrosive coating film performances of graphene nano SiO2 and technical indicator
According to corresponding national standard, basic performance detection is carried out to coating and coating, testing result reaches technical indicator.
6th, Bai Shi high (the solvent-free super thick film epoxy heavy-duty anticorrosive coating of BSG-836 graphene two-component spraying types), by sending out
The technology of person of good sense's independent research is expressed as follows：The solvent-free super thick film epoxy heavy-duty anticorrosive coating antiseptic property of spary coating type is splendid, construction
Performance energy is high, security performance is excellent, has very wide application prospect in coating heavy antisepsis field.
It is a kind of anticorrosive paint since the coating is the solvent-free super thick film corrosion-resistant epoxy paint of spary coating type, suitable for divulging information not
It constructs under good environment, can be used to load drinking water, food or other sensitive species.
(1) general product key property：
1. without volatile organic solvent, solid part is up to 100%
2. 545 DEG C of paint film adhesions of room temperature curing are strong, mechanical performance is excellent, easily constructs.
3. paint film water resistance is excellent, since using extraordinary curing agent, the paint film after curing is nontoxic, not polluted drinking water and food
Product.
(2) basic performance of the solvent-free super thick film epoxy heavy-duty anticorrosive coating of two-component spraying type：
Present invention design and the production technology and its recipe presentation researched and developed are as follows：
Example 1, Bai Shi high (BSG- graphenes solvent-free epoxy heavy-duty anticorrosive coating), by the raw material system of following parts by weight
Into：Component A-colored paint formulation：
Liquid-state epoxy resin 36~52, diluent 6~12, BSG-810 graphenes powder 1.0~3.5, dispersant 0.4~
0.8th, antifoaming agent 0.5~1, thixotropic agent 1~3, polar solvent 1~3, sericite in powder 6~8, talcum powder 10~12, barium sulfate 16~
28th, iron oxide red 1~3, summation 100.
B component-hardener formula：
Modified fatty amine 40~50, accelerating agent 0~4, dispersant 0~0.5, antifoaming agent 0~0.5, polar solvent 0.5~
1.5th, thixotropic agent 0~3, mica powder 5~10, barium sulfate 32~38, summation 100.
Example 2, Bai Shi high (BSG- graphenes thickness applies wear-resisting solventless epoxy anti-corrosive coating), by following parts by weight
Raw material is made：1.0~3.5m/g of homemade two layers of stripping graphene BSG-810 graphene powders, bisphenol F epoxy resin 36~
52m/g, 6~8m/g of toughener, 3~5m/g of titanium dioxide, 6~12m/g of silicon carbide, 6~12m/g of silica flour, sericite in powder 10
~13m/g, 1~2m/g of silane coupling agent, 1~2m/g of aerosil, 0.5~1m/g of dispersant, 0.5~1m/g of antifoaming agent
Deng composition.
Example 3, Bai Shi high (BSG- graphene nano TiO2 solventless epoxy anti-corrosive coatings), by following parts by weight
Raw material is made：Component A-epoxy resin E-51 5%, nbr carboxyl terminal 45%, cashew nut oil modified epoxide resin reactive are dilute
Release agent 2%, BSG-810 graphenes powder 1.0~3.5%, silane coupling agent (KH-550) 1.5~2%, nano TiO 2 (＜
100nm) 10~12%, isopropanol 0.8%, trbasic zinc phosphate 4.2%, iron oxide red (2 μm of ＜) 12%, talcum powder (680 mesh) 18%,
Nano kaoline (2 μm of ＜) 5.8%, wetting dispersing agent (BYK-163) 0.5%, antifoaming agent (BYK-066N) 0.5%
B component-it is cashew nut oil modified phenolic aldehyde amine epoxy curing agent：Curing agent (MD2008)
Example 4, Bai Shi high (BSG- graphenes (bi-component) solventless epoxy anti-corrosive coating), as shared by following each component
Total weight percent is：Homemade two layers of stripping BSG-810 graphenes powder 1.0~3.5%；Bisphenol A type epoxy resin E-51,
E-44, E-20, E-12, E-06, Ba Ling petrochemical industry；Reactive diluent 660 (butyl glycidyl ether), 207 (polypropylene glycol shrink it is sweet
Oily ether), modified by cardanol amine, polyamide curing agent；Sericite in powder (I types：800 mesh；II types：1000 mesh)；Levelling agent, wetting,
The auxiliary agents such as silane coupling agent.The present invention has the characteristics that anti-corrosion conducts electricity very well.
Example 5, Bai Shi high (the wear-resisting solventless epoxy anti-corrosive coatings of BSG- graphene nanos SiO2), by following parts by weight
Several raw materials are made：Bisphenol F epoxy resin 48%, BSG-810 graphenes powder 1.0~3.5, toughener 10~12%, thickening
Agent 0.6~0.8%, modified fatty amine curing agent 2%, nano-titanium dioxide 3%, silicon carbide 8%, silica flour 7%, sericite in powder
12%th, the groups such as silane coupling agent 1.6%, antifoaming agent 0.6%, dispersant 0.8%, nano silicon dioxide 5%, thixotropic agent 1.5%
Into.
Example 6, Bai Shi high (the solvent-free super thick film epoxy heavy-duty anticorrosive coating of BSG- graphene two-component spraying types), by with
The raw material of lower parts by weight is made：Thixotropy slurry：Epoxy resin 50~52, reactive diluent 8~10, plasticizer 10~12,
Thixotropic agent 15,
First component (colored paint component)：Epoxy resin 20, reactive diluent 3, BSG-810 graphenes powder 3.0~5.5%；
Plasticizer 2, inhibition filler 20, prevents cracking filler 20, thixotropy slurry 7 at auxiliary agent 2
Second component (curing agent component)：Epoxy resin 30, nano fumed silica 10, curing accelerator 2, thixotropic agent 2,
Wear-resisting pigment 40
Due to the addition of graphene nano material, increase substantially the performances such as adhesive force, consistency, intensity.It is main
Feature is：High temperature resistant anticorrosion, is not burnt, acid and alkali-resistance, salt spray resistance, waterproof.For the place more than soda acid, erosion.
Claims (3)
1. a kind of graphene solvent free corrosion prevention coating, and in particular to using a kind of graphene solvent free corrosion prevention coating and prepare skill
Art is polymerized to film forming matter by liquid-state epoxy resin, adds in graphene nano element, a variety of inorganic nano composite materials and its work
The compositions such as property diluent, auxiliary agent, filler, pigment and amine curing agent.Be widely used in reservoir walls, shipbuilding industry, port and pier,
The heavy antisepsis such as buried pipeline field becomes the essential coating variety in anticorrosive paint field.
2. its feature is with feature：Film forming matter is polymerized to by liquid-state epoxy resin, graphene nano element, a variety of inorganic is received
The materials such as nano composite material have the characteristics that a kind of graphene solvent-free epoxy heavy-duty anticorrosive coating.
3. according to claims 1：A kind of solvent free corrosion prevention coating and following six examples of technology of preparing claim etc..
Example 1, Bai Shi high (BSG- graphenes solvent-free epoxy heavy-duty anticorrosive coating), are prepared from the following raw materials in parts by weight：A
Component-colored paint formulation：
Liquid-state epoxy resin 36~52, diluent 6~12, BSG-810 graphenes powder 1.0~3.5, dispersant 0.4~0.8,
Antifoaming agent 0.5~1, thixotropic agent 1~3, polar solvent 1~3, sericite in powder 6~8, talcum powder 10~12, barium sulfate 16~28,
Iron oxide red 1~3, summation 100.
B component-hardener formula：
Modified fatty amine 40~50, dispersant 0~0.5, antifoaming agent 0~0.5, polar solvent 0.5~1.5, touches accelerating agent 0~4
Become agent 0~3, mica powder 5~10, barium sulfate 32~38, summation 100.
Example 2, Bai Shi high (BSG- graphenes thickness applies wear-resisting solventless epoxy anti-corrosive coating), by the raw material of following parts by weight
It is made：Homemade two layers of stripping graphene BSG-810 graphene powders 1.0~3.5m/g, 36~52m/g of bisphenol F epoxy resin,
6~8m/g of toughener, 3~5m/g of titanium dioxide, 6~12m/g of silicon carbide, 6~12m/g of silica flour, 10~13m/ of sericite in powder
G, the groups such as 1~2m/g of silane coupling agent, 1~2m/g of aerosil, 0.5~1m/g of dispersant, 0.5~1m/g of antifoaming agent
Into.
Example 3, Bai Shi high (BSG- graphene nano TiO2 solventless epoxy anti-corrosive coatings), by the raw material of following parts by weight
It is made：Component A-epoxy resin E-51 5%, nbr carboxyl terminal 45%, cashew nut oil modified epoxide resin reactive diluent
2%th, BSG-810 graphenes powder 1.0~3.5%, silane coupling agent (KH-550) 1.5~2%, nano TiO 2 (＜ 100nm)
10~12%, isopropanol 0.8%, trbasic zinc phosphate 4.2%, iron oxide red (2 μm of ＜) 12%, talcum powder (680 mesh) 18%, nanometer are high
Ridge soil (2 μm of ＜) 5.8%, wetting dispersing agent (BYK-163) 0.5%, antifoaming agent (BYK-066N) 0.5%
B component-it is cashew nut oil modified phenolic aldehyde amine epoxy curing agent：Curing agent (MD2008)
Example 4, Bai Shi high (BSG- graphenes (bi-component) solventless epoxy anti-corrosive coating), the gross weight as shared by following each component
Measuring percentage is：Homemade two layers of stripping BSG-810 graphenes powder 1.0~3.5%；Bisphenol A type epoxy resin E-51, E-
44th, E-20, E-12, E-06, Ba Ling petrochemical industry；Reactive diluent 660 (butyl glycidyl ether), 207 (polypropylene glycol glycidols
Ether), modified by cardanol amine, polyamide curing agent；Sericite in powder (I types：800 mesh；II types：1 000 mesh)；Levelling agent, wetting, silicon
The auxiliary agents such as alkane coupling agent.The present invention has the characteristics that anti-corrosion conducts electricity very well.
Example 5, Bai Shi high (the wear-resisting solventless epoxy anti-corrosive coatings of BSG- graphene nanos SiO2), by following parts by weight
Raw material is made：Bisphenol F epoxy resin 48%, BSG-810 graphenes powder 1.0~3.5, toughener 10~12%, thickener 0.6
~0.8%, modified fatty amine curing agent 2%, nano-titanium dioxide 3%, silicon carbide 8%, silica flour 7%, sericite in powder 12%,
The compositions such as silane coupling agent 1.6%, antifoaming agent 0.6%, dispersant 0.8%, nano silicon dioxide 5%, thixotropic agent 1.5%.
Example 6, Bai Shi high (the solvent-free super thick film epoxy heavy-duty anticorrosive coating of BSG- graphene two-component spraying types), by following heavy
The raw material of amount number is made：Thixotropy slurry：Epoxy resin 50~52, reactive diluent 8~10, plasticizer 10~12, thixotroping
Agent 15,
First component (colored paint component)：Epoxy resin 20, reactive diluent 3, BSG-810 graphenes powder 3.0~5.5%；Plasticising
Agent 2, inhibition filler 20, prevents cracking filler 20, thixotropy slurry 7 at auxiliary agent 2
Second component (curing agent component)：It is epoxy resin 30, nano fumed silica 10, curing accelerator 2, thixotropic agent 2, wear-resisting
Pigment 40
Due to the addition of graphene nano material, increase substantially the performances such as adhesive force, consistency, intensity.Its main feature
It is：High temperature resistant anticorrosion, is not burnt, acid and alkali-resistance, salt spray resistance, waterproof.For the place more than soda acid, erosion.
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|---|---|---|---|
| CN201711074552.7A CN108178964A (en) | 2017-11-01 | 2017-11-01 | A kind of graphene solvent free corrosion prevention coating and technology of preparing |
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| CN109135503A (en) * | 2018-07-12 | 2019-01-04 | 山东联星能源集团有限公司 | A kind of stone protectant of containing graphene and tourmaline |
| CN109439184A (en) * | 2018-11-05 | 2019-03-08 | 中北大学 | A kind of Metal surface anti-corrosion coating and its preparation and coating method |
| CN109575747A (en) * | 2018-11-16 | 2019-04-05 | 上海博歌建材有限公司 | A kind of solvent-free antistatic Self-leveling finishing coat of anti-corrosion type and preparation method thereof |
| CN109943190A (en) * | 2019-01-31 | 2019-06-28 | 北京化工大学 | A kind of static electricity conductive anticorrosive function and service coating material, preparation method and application |
| CN109957309A (en) * | 2019-04-02 | 2019-07-02 | 河南城建学院 | A kind of graphene modified epoxy anticorrosive paint and preparation method thereof |
| CN110358407A (en) * | 2019-07-26 | 2019-10-22 | 四川漆胜科技有限公司 | A kind of environment-friendly solvent-free graphene anticorrosive paint and preparation method thereof |
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| CN110982389A (en) * | 2019-11-26 | 2020-04-10 | 厦门双瑞船舶涂料有限公司 | High-solid-content heavy-duty anticorrosive paint and preparation method thereof |
| CN110982385A (en) * | 2019-12-25 | 2020-04-10 | 上海中如智慧能源集团有限公司 | Special temperature-resistant coating for corrosion prevention in heat storage tank |
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| CN110982385B (en) * | 2019-12-25 | 2021-11-16 | 上海中如智慧能源集团有限公司 | Special temperature-resistant coating for corrosion prevention in heat storage tank |
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| CN112680034A (en) * | 2020-12-25 | 2021-04-20 | 韩克军 | Anticorrosive heat-insulating coating and preparation method thereof |
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| CN114381182A (en) * | 2022-01-20 | 2022-04-22 | 陕西燕园众欣石墨烯科技有限公司 | Graphene type low-viscosity thin-coating high-hardness super-wear-resistant solvent-free epoxy coating and preparation method thereof |
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| CN116396645A (en) * | 2023-04-03 | 2023-07-07 | 广东新力通实业有限公司 | Corrosion-resistant and wear-resistant plastic-coated steel pipe and manufacturing process thereof |
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| CN116426195A (en) * | 2023-04-04 | 2023-07-14 | 哈尔滨工业大学（威海） | Graphene solvent-free epoxy heavy-duty anticorrosive paint |
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