阅读说明：本技术 一种复合材料、水性防腐涂料及其制备方法 (A kind of composite material, water-based anticorrosive paint and preparation method thereof ) 是由 肖凤娟 钱程 闫鑫蕊 李红丽 康泽坤 韩金言 顾文秀 杨宏郁 于 2019-09-06 设计创作，主要内容包括：本发明涉及防腐技术领域,具体公开一种复合材料、水性防腐涂料及其制备方法。所述复合材料由质量比为1:0.5-10的g-C<Sub>3</Sub>N<Sub>4</Sub>与海泡石制得。所述水性防腐涂料,包括A组分和B组分,其中A组分包括：所述复合材料、固化剂、防沉触变剂、防闪锈剂、去离子水；B组分包括：水性环氧丙烯酸树脂、消泡剂、润湿分散剂、流平剂、附着力促进剂、固化剂。本发明以g-C<Sub>3</Sub>N<Sub>4</Sub>与改性海泡石为防腐组分制备的防腐涂料具有优异的耐盐雾性能。(The present invention relates to technical field of anticorrosion, specifically disclose a kind of composite material, water-based anticorrosive paint and preparation method thereof.The g-C that the composite material is 1:0.5-10 by mass ratio 3 N 4 It is made with sepiolite.The water-based anticorrosive paint, including component A and B component, wherein component A includes: the composite material, curing agent, anti-settling thixotropic agent, anti-flash rusting agent, deionized water；B component includes: water-based epoxy acrylic resin, defoaming agent, wetting dispersing agent, levelling agent, adhesion promoter, curing agent.The present invention is with g-C 3 N 4 It is that anticorrosive paint prepared by antiseptic ingredient has excellent salt spray resistance with modified meerschaum.)

1. a kind of composite material, it is characterised in that: the g-C for being 1:0.5-10 by mass ratio₃N₄It is made with sepiolite.

2. composite material as described in claim 1, it is characterised in that: the sepiolite is modified meerschaum, preparation method Are as follows: sepiolite stock dispersion is obtained into sepiolite dispersion liquid in organic solvent, ionic surfactant is then added, is flowed back Reaction, obtained solid drying, ball milling sieving, obtains the modified meerschaum.

3. composite material as claimed in claim 2, it is characterised in that: the concentration of the sepiolite dispersion liquid is 3-7wt%； And/or:

The mass ratio of the sepiolite and the ionic surfactant is 0.8-1.2:1.8-2.2；And/or

The organic solvent is methanol, ethyl alcohol, propyl alcohol, butanol or acetone；And/or

The ionic surfactant is cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, dodecyl Benzene sulfonic acid sodium salt or lauryl sodium sulfate；And/or

The temperature of the drying is 35-45 DEG C；And/or

The fineness of the ball milling sieving is 200-300 mesh；And/or

The temperature of the back flow reaction is 60-70 DEG C, time 4-8h.

4. composite material as described in any one of claims 1-3, it is characterised in that: be prepared by following methods:

Step a, by g-C₃N₄It is dissolved in organic solvent, compound concentration is the g-C of 0.1-0.65mg/mL₃N₄Dispersion liquid；

Step b, the sepiolite and ionic surfactant are added to the g-C₃N₄It in dispersion liquid, stirs, is centrifuged, it will Centrifugation obtained solid is scattered in deionized water and reacts at 100-120 DEG C, and reaction terminates be centrifuged, wash, being dried to obtain institute State composite material.

5. composite material as claimed in claim 4, it is characterised in that: the ionic surfactant is cetyl front three Base ammonium bromide, Cetyltrimethylammonium bromide, neopelex or lauryl sodium sulfate；And/or

The organic solvent is methanol, ethyl alcohol, propyl alcohol, butanol or acetone；And/or

In step b, the mass ratio of the sepiolite and the ionic surfactant is 5:0.1-0.5；And/or

In step b, the detergent used that washs is the mixed liquor of the mass ratio ethyl alcohol for being 1:1-3 and deionized water；And/or

In step b, the drying temperature is 40-60 DEG C；And/or

In step b, the mixing time is 0.5-1h；And/or

In step b, the mass ratio of the solid and deionized water is 1:20-40；And/or

In step b, the time of the reaction is 12-15h.

6. application of the composite material in anticorrosive paint as described in claim any one of 1-5.

7. a kind of water-based anticorrosive paint including composite material as described in any one in claim 1-5, it is characterised in that: including Mass ratio is the component A and B component of 1:8-16, and wherein component A includes the component of following parts by weight: composite material: 5-15 parts, Gu Agent: 5-10 parts, anti-settling thixotropic agent: 0.1-2 parts, anti-flash rusting agent: 1-5 parts, deionized water: 10-30 parts；B component includes as follows The component of parts by weight: water-based epoxy acrylic resin: 40-60 parts, defoaming agent: 0.1-1 parts, wetting dispersing agent: 0.1-3 parts, stream Flat agent: 0.1-1 parts, adhesion promoter: 1-5 parts, curing agent: 5-10 parts.

8. water-based anticorrosive paint as claimed in claim 7, it is characterised in that: the solid content of the water-based epoxy acrylic resin For 68-78%.

9. water-based anticorrosive paint as claimed in claim 7, it is characterised in that: the curing agent is water-based isocyanate；And/or

The anti-settling thixotropic agent is at least one of organobentonite and fumed silica；And/or

The anti-flash rusting agent is the anti-flash rusting agent of borate ester；And/or

The defoaming agent is at least one of organic silicon defoamer, polyether-modified silicon defoaming agent；And/or

The wetting dispersing agent is polysiloxane copolymer；And/or

The levelling agent is acrylate leveling agent；And/or

The adhesion promoter is at least one of silane coupling agent or adenosine diphosphate (ADP).

10. a kind of preparation method of water-based anticorrosive paint, it is characterised in that: at least include the following steps:

Step a, each component is weighed according to the described in any item raw material proportionings of such as claim 7~9；

Step b, the composite material, curing agent, anti-settling thixotropic agent, anti-flash rusting agent and deionized water are subjected to mixing treatment, obtained To component A；

Step c, by the water-based epoxy acrylic resin, defoaming agent, wetting dispersing agent, levelling agent, adhesion promoter and consolidate Agent carries out mixing treatment and obtains B component；

Step d, the component A and B component are subjected to mixing treatment, obtain the water-based anticorrosive paint.

Technical field

The present invention relates to technical field of anticorrosion more particularly to a kind of composite material, water-based anticorrosive paint and preparation method thereof.

Background technique

In fields such as mechanical equipment, rail traffic, architectural engineerings, aqueous industrial coating is due to being free of volatile organic solvent (VOC), meet national green environmental requirement, comply with epoch sustainable development idea and obtain great development opportunity, become industry The hot spot of anticorrosive paint field concern.

Graphene is a kind of up-and-coming antiseptic ingredient, at the same introduce in graphene conducting polymer etc. other at Part, the oxidation rate of metal can be reduced and form passivation layer in metal surface, slow down corrosion of metal.With polyaniline and stone The antiseptic property of water paint can be improved as anti-corrosion composition for black alkene, however polyaniline/graphene anticorrosive paint still has During some problems, such as graphene long service, due to the appearance of coating hole and defect, corrosive medium enters, and makes stone Galvanic corrosion is generated between black alkene and steel plate, so that graphene is made to become a kind of corrosion accelerator and lose anti-corrosion ability, this resistance Its large-scale application in water-based anticorrosive paint is hindered.The different redox state of polyaniline influences very anti-corrosion effect Greatly, the polyaniline of different dopant states or different redox states causes the antiseptic property difference of coating huge, but regulates and controls poly- Doped with Aniline state and its redox state are complex, and routine prepares polyaniline and generally uses in hydrochloric acid medium Polymerization can introduce corrosivity very strong Cl when cleaning incomplete^-Ion accelerates the corrosion failure of coating.Therefore, prevent The performance of rotten component becomes an important factor for restricting anticorrosive paint large-scale promotion.So being badly in need of studying a kind of with excellent anti- Rotten performance, preparation method be simple, easily controlled antiseptic ingredient.

Summary of the invention

It is poor for existing anti-corrosion material antiseptic property, do not allow the problems such as easy-regulating, the present invention provides a kind of composite material.

And application of the above-mentioned composite material in anticorrosive paint.

And a kind of water-based anticorrosive paint.

And a kind of preparation method of water-based anticorrosive paint.

To achieve the above object of the invention, the embodiment of the present invention uses the following technical solution:

A kind of composite material, the g-C for being 1:0.5-10 by mass ratio₃N₄It is made with sepiolite.

Compared with the existing technology, composite material provided by the invention has the advantage that

The application is to have the g-C of the planar lamellar structure of approximate graphene₃N₄For effective component, with excellent Physical barrier performance, H can be prevented₂O、O₂With the infiltration of electrolyte, g-C₃N₄Due to the presence of N atom, its conductance is reduced Rate, electron transfer rate weaken, and reduce the thermocouple corrosiveness with metallic substrates, and with large specific surface area and adsorption capacity Strong sepiolite can adsorb in the network structure formed as anticorrosive packing and wrap up g-C₃N₄, not only improve g-C₃N₄'s Dispersibility reduces g-C₃N₄Point thermogalvanic corrision between metallic matrix, moreover it is possible to improve g-C₃N₄Isolated Shield effect and impermeabilisation Property, guarantee g-C₃N₄The stability being on active service for a long time in preservation process.

Preferably, the sepiolite is modified meerschaum, preparation method are as follows: the sepiolite is modified meerschaum, The preparation method comprises the following steps: sepiolite stock dispersion is obtained sepiolite dispersion liquid in organic solvent, it is living that ionic surface is then added Property agent, back flow reaction, obtained solid drying, ball milling sieving, obtain the modified meerschaum.

The present invention is modified sepiolite with ionic surfactant, and hydrophobic grouping is connected with sepiolite, parent Aqueous group is exposed to surface, and hydrophobic grouping also plays buffer action to sepiolite molecule, and it is fully dispersed to be conducive to sepiolite In organic solvent, the hydrophily of sepiolite is finally improved.

Preferably, the concentration of the sepiolite dispersion liquid is 3-7wt%.

Preferably, the mass ratio of the sepiolite and the ionic surfactant is 0.8-1.2:1.8-2.2.

It is preferred that the ratio of regulation sepiolite and the ionic surfactant, both can guarantee sepiolite in organic solvent Can be fully dispersed, its hydrophily is improved, and avoid ionic surfactant concentration too high and assemble and form micella, leads to Hai Pao Stone is fully wrapped around by micella.

Preferably, the ionic surfactant is cetyl trimethylammonium bromide, octadecyl trimethyl bromination Ammonium, neopelex or lauryl sodium sulfate.

Preferably, the temperature of the drying is 35-45 DEG C.

Preferably, the fineness of the ball milling sieving is 200-300 mesh.

It is preferred that controlling its fineness, modified meerschaum is thinner, and specific surface area is bigger, and it can be improved in g-C₃N₄Dispersion liquid In dispersibility, be conducive to g-C₃N₄It loads in sepiolite.

Preferably, the temperature of the back flow reaction is 60-70 DEG C, time 4-8h.

Preferably, the g-C₃N₄/ sepiolite composite material is prepared by following methods:

Step a, by g-C₃N₄It is dissolved in organic solvent, compound concentration is the g-C of 0.1-0.65mg/mL₃N₄Dispersion liquid；

Step b, the sepiolite and ionic surfactant are added to the g-C₃N₄In dispersion liquid, stirring, from The heart disperses centrifugation obtained solid in deionized water and reacts at 100-120 DEG C, and reaction terminates centrifugation, washing, dry To the g-C₃N₄/ sepiolite composite material.

The present invention is using sepiolite as anticorrosive packing, with g-C₃N₄By hydro-thermal reaction, by g-C₃N₄It is adsorbed on the net of sepiolite In network structure, the hydrophily and dispersibility of anti-corrosion material are improved, and then mentions the g-C₃N₄The barrier property of/sepiolite composite material Energy and antiseptic property.

Preferably, the ionic surfactant is cetyl trimethylammonium bromide, octadecyl trimethyl bromination Ammonium, neopelex or lauryl sodium sulfate.

Preferably, the organic solvent is methanol, ethyl alcohol, propyl alcohol, butanol or acetone.

Preferably, in step b, the mass ratio of the sepiolite and the ionic surfactant is 5:0.1-0.5.

It is preferred that controlling its ratio, enable sepiolite fully dispersed to g-C₃N₄In dispersion liquid, it is also beneficial to g-C₃N₄With sea Afrodite comes into full contact with, and is g-C₃N₄Basis is provided with sepiolite is loaded to.

Preferably, in step b, it is described wash the detergent that uses for mass ratio be 1:1-3 ethyl alcohol and deionized water Mixed liquor.

Preferably, in step b, the drying temperature is 40-60 DEG C.

Preferably, in step b, the mixing time is 0.5-1h.

Preferably, in step b, the mass ratio of the solid and deionized water is 1:20-40.

Preferably, in step b, the time of the reaction is 12-15h.

The application under conditions of controlled at 100-120 DEG C, sufficiently unfold by the structure for being conducive to modified meerschaum, and By g-C₃N₄It loads on the reticular structure of sepiolite.

It is further preferred that the reaction using autoclave as reaction vessels, is in inside it higher than atmospheric pressure Pressure is more advantageous to g-C₃N₄It loads on the reticular structure of sepiolite.

Further, the application the present invention also provides the composite material in anticorrosive paint field.

Further, the present invention also provides a kind of water-based anticorrosive paints including above-mentioned composite material, including mass ratio is The component A and B component of 1:8-16, wherein component A includes the component of following parts by weight: composite material: 5-15 parts, curing agent: 5- 10 parts, anti-settling thixotropic agent: 0.1-2 parts, anti-flash rusting agent: 1-5 parts, deionized water: 10-30 parts；B component includes following parts by weight Component: water-based epoxy acrylic resin: 40-60 parts, defoaming agent: 0.1-1 parts, wetting dispersing agent: 0.1-3 parts, levelling agent: 0.1- 1 part, adhesion promoter: 1-5 parts, curing agent: 5-10 parts.

Compared with the existing technology, water-based anticorrosive paint provided by the invention has the advantage that

The application forms spacial framework after being crosslinked with curing agent using water-based epoxy acrylic resin as film forming matter, With g-C₃N₄The anti-corrosion material of/sepiolite composite material, is punctured into its structure, forms fine and close paint film, and utilize g-C₃N₄Solely Special two-dimensional slice structure, can care for and resist corrosive medium O₂、H₂O、Cl^-Deng intrusion, increase corrosive medium diffusion in the coating Path significantly increases the shielding properties of coating, to have stronger antiseptic property；And utilize easily diffusion, adsorption energy in water The strong sepiolite of power, so that in g-C₃N₄Fine dispersion in coating, and further suppress g-C₃N₄The ability of electronics is transmitted, is improved The antiseptic property of coating.

Preferably, the solid content of the water-based epoxy acrylic resin is 68-78%.

The application, so that the compactness of paint film is good, is not easy using the Epocryl of high solids content as film forming matter Coating hole and phenomenon of osmosis are generated, the corrosion resistance for improving paint film is conducive to.

Preferably, the water-based epoxy acrylic resin is prepared by following methods:

Step a, by 13-15 parts of epoxy resin, 1-1.5 parts of α-methacrylic acids, 6-8 parts of methyl methacrylates, 9.5- 10.5 parts of butyl acrylates, 5-6 parts of styrene, 1.1-1.3 parts of silane coupling agents and 0.2-0.5 parts of acrylamides are uniformly mixed, Obtain mix monomer；

Step b, 1-1.5 parts of OP-10,0.3-0.5 parts of dodecyl sodium sulfates and 0.2-0.3 parts of ammonium hydrogen carbonate are added to In 10-30 parts of deionized waters, compound emulsifying agent is obtained；

Step c, 0.5-0.8 parts of ammonium persulfates are dissolved in 5-10 parts of deionized waters, obtain initiator solution；

Step d, the 30-35wt% of the 40-60wt% of the compound emulsifying agent and the mix monomer is mixed, is warming up to The initiator solution of 40-60% is added after 50-55 DEG C, reaction to blue light occurs under conditions of 70-75 DEG C, then keeps the temperature 25-35min obtains first emulsion；

Step e, remaining mix monomer, remaining compound emulsifying agent and remaining initiation are added in Xiang Suoshu first emulsion Agent emulsion reacts 1-2h under conditions of 80-90 DEG C, sieves with 100 mesh sieve to obtain the water-based epoxy acrylic resin.

Preferably, the curing agent is water-based isocyanate.

Preferably, the anti-settling thixotropic agent is at least one of organobentonite and fumed silica.

Using the hydrogen bond action between organobentonite chip in coating system, so that unstable reticular structure is formed, Certain thixotropy is provided for coating system；Fumed silica has the characteristic of anti-settling, thickening and resist sagging in the coating, It can flow freely and agglomeration resistance, to provide certain thixotropy for coating system, and there is scratch resistance and wearability, increase The corrosion resistance of strong coating.

Preferably, the anti-flash rusting agent is the anti-flash rusting agent of borate ester.

Since the covalency and valence electron number of boron atom are less than the feature of virtual orbital number, cause each boron in borate former Son belongs to electron deficient state, is easy that complexation reaction occurs with the hydrogen bond of Epocryl or other organic substances, improves The crosslink density of figure layer, and then corrosion-resistant effect is realized by the effect of the physical shielding of high density cross-linked coating.

The anti-flash rusting agent of borate ester simultaneously and coating good compatibility, improve the adhesive force of coating, can effectively inhibit irony bottom The flash rusting phenomenon that water paint on material occurs in the drying process can securely be adsorbed on substrate in a short time and form one layer Protective film is conducive to the rustless property and salt spray resistance that improve coating dry film.

Preferably, the defoaming agent is at least one of organic silicon defoamer, polyether-modified silicon defoaming agent.

It is preferred that the type of defoaming agent and coating system have good compatibility, each raw material in coating system is made With dispersion.

Preferably, the wetting dispersing agent is polysiloxane copolymer.

The organosilicon preferably contained in wetting dispersing agent can effective pigment is mixed and the loose colour that generates, also help In preventing Bei Nade whirlpool and striped, promotes surface slip, levelling agent can be promoted to orient, while Gao Yan can also be significantly reduced The viscosity of material and filler filling system, improves the mobility of coating system.

Preferably, the levelling agent is acrylate leveling agent.

Preferably using acrylate as levelling agent, can care for reduces reduction system surface tension, profit of the enhancing system to substrate Moist, levelability.

Preferably, the adhesion promoter is at least one of silane coupling agent or adenosine diphosphate (ADP).

Preferably adhesion promoter can by coating system organic polymer and inorganic filler be coupled, improve Or enhance its caking property, promote the ductility and impact resistance of paint film, the final adhesive force for improving paint film.

Preferably adenosine diphosphate (ADP) ADP can also improve the water resistance and salt spray resistance of paint film.

Further, the present invention also provides the preparation methods of the water-based anticorrosive paint.The preparation method, include at least with Lower step

Step a, each component is weighed according to above-mentioned raw material proportioning；

Step b, the composite material, curing agent, anti-settling thixotropic agent, anti-flash rusting agent and deionized water are carried out at mixing Reason, obtains component A；

Step c, by the water-based epoxy acrylic resin, defoaming agent, wetting dispersing agent, levelling agent, adhesion promoter Mixing treatment, which is carried out, with curing agent obtains B component；

Step d, the component A and B component are subjected to mixing treatment, obtain the water-based anticorrosive paint.

The preparation method of water-based anticorrosive paint provided by the present application is simple, and process is easy to control, and by A in the form of B component It saves, improves its service life, and be conducive to industrialization promotion.

Preferably, in step b, the condition of the mixing treatment are as follows: mixing speed 300-400rpm, mixing time 1- 2h。

Since system viscosity is larger, mixing speed preferably is not easy bubble stirring into system, if excessive velocities are held It is easily introduced bubble, when viscosity is big, bubble is not easy to be precipitated, and will affect filming performance.

Preferably, in step c, the condition of the mixing treatment are as follows: mixing speed 500-600rpm, mixing time are 50-80min。

Contain film forming matter in system, it is therefore preferable that mixing speed can make system reach uniform effect, if speed Too fast influence system performance.

Preferably, in step d, the condition of the mixing treatment are as follows: mixing speed 800-1000rpm, mixing time are 25-35min。

Preferably high-speed stirring facilitates each component and is uniformly dispersed.

Detailed description of the invention

It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached Figure.

Fig. 1 is the modulus of impedance spirogram for the coating that the embodiment of the present invention and comparative example provide；

Fig. 2 is the coating corrosion potential diagram that the embodiment of the present invention and comparative example provide.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.