CN110655071A - Sulfonic group modified graphene, preparation method thereof and application of sulfonic group modified graphene in water-based epoxy coating - Google Patents
Sulfonic group modified graphene, preparation method thereof and application of sulfonic group modified graphene in water-based epoxy coating Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- 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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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention belongs to the technical field of water-based paint, and particularly relates to sulfonic group modified graphene, a preparation method thereof and application thereof in water-based epoxy paint. The sheet diameter of the sulfonic group modified graphene is 5-10 mu m, and the sheet thickness is less than 5 nm; the preparation method of the sulfonic group modified graphene is also included. The water-based epoxy coating comprises a component A and a component B in a mass ratio of 100 (40-80), wherein the component A comprises: 10-20 parts of curing agent, 5-30 parts of solvent N, 40-80 parts of antirust filler, 10-40 parts of functional filler, 1-10 parts of cosolvent, 1-10 parts of auxiliary agent, and 0-1 part of sulfonic group modified graphene powder according to claim 7; the component B is water-based epoxy emulsion. The water-based epoxy coating can effectively prevent the coating from cracking and has excellent salt spray resistance and corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to sulfonic group modified graphene, a preparation method thereof and application thereof in water-based epoxy paint.
Background
Metal corrosion causes huge economic losses each year. According to survey, the direct economic loss caused by corrosion in China accounts for about 4% of the total economic value of the nation each year, and the loss exceeds the sum of the losses caused by fire, wind and earthquake. Meanwhile, metal corrosion can cause serious injuries and deaths, environmental pollution and other hazards. Currently, surface coating technology is the most effective prevention and approach to solve this problem. China is the first country of paint production and use in the world, but the existing anticorrosive paint is solvent-based, so that the VOC content is high, and the environment and the human body health are seriously polluted. The water-based anticorrosive paint has low VOC content, small environmental pollution and safe storage, becomes a green industrial anticorrosive paint which can be generally popularized at present, and is also an inevitable trend of paint development
Graphene is expected to be the most promising new material in the 21 st century in the field of anticorrosive coatings. The graphene has a special lamellar structure, and can be applied to the anticorrosive paint as fillers like flaky mica powder, aluminum powder, glass flakes and the like. The lamellar structure of the graphene has a good physical shielding effect on the diffusion of water, oxygen and ions, and can increase the permeation path of a corrosive medium in a coating, so that the corrosion prevention function of a metal material is achieved, and the process is called as a labyrinth effect of the graphene; meanwhile, due to the lubricating effect of the graphene, the friction coefficient of the surface layer of the coating is reduced, and the wear rate is reduced. However, the aggregation of graphene due to pi-pi conjugation and van der waals adsorption is difficult to disperse in the coating slurry, which limits the application of graphene in the coating field.
Chinese patent application No. 201611219416.8 discloses a graphene modified waterborne epoxy zinc-rich coating and a preparation method and application thereof. The graphene is obtained by a preparation method disclosed in Chinese patent with application number 201310508801.4. The sulfur trioxide and the concentrated sulfuric acid are needed in the graphene preparation process of the patent as media, wherein the concentrated sulfuric acid easily destroys the structure of the graphene, and the danger coefficient is large.
The application number CN201810487106.7 Chinese patent discloses a method for preparing an epoxy resin anticorrosive coating by doping functionalized graphene, the functionalized graphene prepared by the method needs flammable and explosive substances such as hydrazine hydrate to reduce graphene oxide, the inherent structure of graphene is damaged, more defects can be introduced, the obtained graphene only has good dispersibility in solvent-based coatings, and the application of the functionalized graphene in the coating field is greatly limited along with the water-based coating.
Disclosure of Invention
In order to solve the defect of poor dispersibility of graphene in a water-based paint in the prior art, the invention provides a sulfonic group modified graphene, a preparation method thereof and a water-based epoxy paint.
The invention is realized by the following technical scheme:
a preparation method of sulfonic group modified graphene comprises the following steps:
(1) uniformly mixing a graphite raw material and a sulfonic acid grinding aid, adding a solvent M, and mechanically stirring to obtain a dispersion liquid;
(2) pouring the dispersion liquid obtained in the step (1) into a ball milling tank, adding grinding balls, and carrying out ball milling to obtain sulfonic group modified graphene slurry;
(3) concentrating, ultrasonically dispersing, filtering and drying the sulfonic group modified graphene slurry obtained in the step (2) to obtain sulfonic group modified graphene powder.
Preferably, the graphite raw material is one or more of natural crystalline flake graphite, expanded graphite, expandable graphite and graphite powder; the solvent M is one or more of water, ethanol, acetone, ethylene glycol, glycerol and ethyl acetate.
Preferably, the sulfonic acid grinding aid is a mixture of one or more of sodium styrene sulfonate, alpha-sodium alkenyl sulfonate, sodium dodecyl benzene sulfonate, 2-acrylamide-2-methylpropanesulfonic acid, sodium lignosulfonate, polyoxyethylene ether sulfonate and sodium alkyl benzene sulfonate and one or more of sodium sulfate, sodium carbonate, sodium bicarbonate, urea, polyvinylpyrrolidone, sodium chloride and calcium carbonate.
Preferably, the mass ratio of the graphite raw material to the sulfonic acid-based grinding aid to the solvent is 1: (5-50): (10-80).
Preferably, the rotation speed of the ball milling in the step (2) is 150-; the grinding balls are made of stainless steel or zirconia, and the mass ratio of the grinding balls to the dispersion liquid is 1 (5-40); the grinding balls are obtained by mixing large grinding balls with the diameter of 20mm, medium grinding balls with the diameter of 10mm and small grinding balls with the diameter of 6mm according to the mass ratio of 3:4: 4.
Preferably, the ultrasonic dispersion in the step (3) is to disperse the concentrated sulfonic group modified graphene slurry in deionized water to be uniformly dispersed; the filtration mode is centrifugation, filter pressing or nanofiltration; the drying mode is one or more of spray drying, vacuum drying and freeze drying.
The invention also aims to provide the sulfonic group modified graphene prepared by the method, the sheet diameter is 5-10 mu m, and the sheet thickness is less than 5 nm.
The invention also aims to provide an application of the sulfonic acid group modified graphene in a water-based epoxy coating, wherein the sulfonic acid group modified graphene comprises a component A and a component B in a mass ratio of 100 (40-80), wherein:
the component A comprises the following components in parts by weight: 10-20 parts of curing agent, 5-30 parts of solvent N, 40-80 parts of antirust filler, 10-40 parts of functional filler, 1-10 parts of cosolvent, 1-10 parts of auxiliary agent, and 0-1 part of sulfonic group modified graphene powder according to claim 7;
the component B is water-based epoxy emulsion.
Preferably, the solvent N in component a is water; the antirust filler is any one or more of aluminum hydroxide, zinc phosphate, mica powder, iron oxide red and zinc oxide; the functional filler is one or more of talcum powder, titanium dioxide, silica powder, quartz powder, bentonite and precipitated barium sulfate; the cosolvent is one or more of propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol ethyl ether, ethylene glycol butyl ether and ethanol; the auxiliary agent is any one or more of a dispersing agent, a defoaming agent, a thickening agent, a coupling agent, a wetting agent, a flatting agent, a pH regulator and an anti-flash rust agent.
Preferably, the aqueous epoxy emulsion is prepared by using epoxy resin through a conventional method, wherein the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydroxymethyl bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin and nylon modified epoxy resin.
Compared with the prior art, the invention has the beneficial effects that:
(1) the sulfonic group modified graphene prepared by the ball milling method has the inherent structure of graphene, and has few defects; the sulfonic group is grafted on the edge of the graphene sheet, so that the graphene is easy to wet by water, and meanwhile, the sulfonic group enables the graphene sheet to carry negative charges, so that the electrostatic repulsion among the graphene sheets is increased, the dispersibility and stability of the sulfonic group modified graphene in the water-based paint are improved, and the storage performance is good; and the preparation waste liquid can be used as a cement raw material for recycling, has no pollution to the environment, is simple and safe in preparation process, and is suitable for large-scale industrial production.
(2) The existence of the graphene has a good physical shielding effect on the diffusion of water, oxygen and ions, and the permeation path of a corrosive medium in a coating can be increased, so that the anticorrosion function of a metal material is achieved, and the process is generally called as a labyrinth effect of the graphene; meanwhile, due to the lubricating effect of the graphene, the friction coefficient of the surface layer of the coating is reduced, and the wear rate is reduced; the epoxy resin can not prevent cracks from generating and plastic deformation of the epoxy resin to cause the coating to be easy to form cracks, the existence of the sulfonic group modified graphene can change the fracture mode of the resin, the cracking tendency is inhibited, the coating can be matched with various intermediate paints and finish paints for use, and the salt spray resistance and the corrosion resistance are excellent.
(3) According to the water-based epoxy coating, water is used as a solvent, so that the discharge of VOCs in the production and use processes of the coating can be effectively reduced, the national green and environmental protection policy is met, and the transportation safety and the production and storage stability can be obviously improved.
(4) The method comprises the steps of performing wet ball milling by using a common ball milling principle, and adding sulfonic acid substances into a ball milling system in view of the secondary agglomeration phenomenon possibly occurring in graphene during grinding, so that excessive impact damage of grinding balls is avoided, the structure of the graphene is protected, and under the mechanical force chemical action, a conjugated plane structure inside the graphene and the sulfonic acid substances are subjected to pi-pi conjugation, part of sulfonic acid substances are adsorbed on the surface of the graphene, and meanwhile, sulfonic acid groups are successfully grafted on the edge of the graphene to prepare the sulfonic acid group modified graphene. The structure of the graphene is protected and is modified synchronously with the sulfonic acid group, so that the modified graphene material has good dispersion stability in a coating system.
Drawings
FIG. 1 is an SEM image of a water-based epoxy paint coating obtained in comparative example 1;
FIG. 2 is an SEM photograph of the water-borne epoxy paint coating obtained in example 1;
FIG. 3 is a photograph of the water-based epoxy coating obtained in comparative example 1 as a primer in a salt spray resistance test for 100 hours;
FIG. 4 is a photograph of the water-borne epoxy coating obtained in example 1 as a primer in a salt spray resistance test for 600 h.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples, but is not limited thereto.
Example 1
(1) Preparation of sulfonic group modified graphene
(1-1) mixing graphite raw materials: natural flake graphite and sulfonic acid grinding aid: placing sodium lignosulfonate and sodium carbonate in a beaker, and stirring to enable the materials to be in a uniform state to obtain a mixed material; wherein the mass ratio of the sodium lignosulphonate to the sodium carbonate is 2: 1;
(1-2) adding a solvent N: ethanol, mechanically stirring to obtain a dispersion liquid;
(1-3) pouring the dispersion liquid into a ball milling tank, adding grinding balls, stirring to be in a uniform state, then placing the ball milling tank on a planetary ball mill, and carrying out ball milling for 12 hours at a rotating speed of 200rpm to obtain sulfonic group modified graphene slurry;
(1-4) concentrating the sulfonic group modified graphene slurry through a rotary evaporator, removing a solvent N, dispersing into deionized water, and performing ultrasonic dispersion, filtration and freeze drying to obtain sulfonic group modified graphene powder;
the mass ratio of the graphite raw material to the sulfonic acid-based grinding aid to the solvent is 1: 20: 50; the mass ratio of the grinding balls to the dispersion liquid is 1: 20; the grinding balls are obtained by mixing large grinding balls with the diameter of 20mm, medium grinding balls with the diameter of 10mm and small grinding balls with the diameter of 6mm according to the mass ratio of 3:4: 4.
(2) Water-based epoxy paint: the component A and the component B are mixed according to the mass ratio of 100:60 to obtain the composite material.
The components and the formula of the component A are shown in the table 1:
TABLE 1
Component a was prepared as follows:
a. adding 200 parts by weight of water, a dispersing agent, a neutralizing agent and a wetting agent into a dispersing barrel in sequence, and stirring and dispersing for 5 minutes at 500 r/min;
b. adding 20g of antirust filler, and stirring and dispersing for 5 minutes at 500 r/min;
c. adding the sulfonic group modified graphene into the materials, and dispersing at a high speed of 1500r/min for 30 minutes;
d. functional filler is sequentially and slowly added to prevent splashing, the dispersion is carried out at 1500r/min, 30g of water is added in the middle to ensure the dispersion effect, and the dispersion is carried out until the fineness is below 30 mu m;
e. adding a defoaming agent at 500r/min, and stirring and dispersing for 5 minutes;
f. adding a curing agent, and dispersing for 30 minutes at 1500 r/min;
g. dispersing for 10 minutes at a low rotating speed of 500r/min to remove bubbles;
h. diluting the thickening agent with a cosolvent, and adding the diluted thickening agent into the materials at 500 r/min;
i. obtaining the component A, and packaging and storing.
Component B is finished epoxy emulsion BANCO 2056, purchased from Union chemistry group.
Example 2
(1) Preparation of sulfonic group modified graphene
The preparation method is the same as that of example 1, except that: the mass ratio of the graphite raw material to the sulfonic acid grinding aid to the solvent is 1: 5: 10, the mass ratio of the grinding balls to the dispersion liquid is 1: 5.
(2) Water-based epoxy paint: the component A and the component B are mixed according to the mass ratio of 100:40 to obtain the composite material.
The components and the formula of the component A are shown in the table 2:
TABLE 2
The preparation of component A was carried out as in example 1.
Component B is finished epoxy emulsion BANCO 2056, purchased from Union chemistry group.
Example 3
(1) Preparation of sulfonic group modified graphene
The preparation method is the same as that of example 1, except that: the mass ratio of the graphite raw material to the sulfonic acid grinding aid to the solvent is 1: 50: 80, the mass ratio of the grinding balls to the dispersion liquid is 1: 35.
(2) Water-based epoxy paint: the component A and the component B are mixed according to the mass ratio of 100:80 to obtain the composite material.
The components and the formula of the component A are shown in the table 3:
TABLE 3
The preparation of component A was carried out as in example 1.
Component B is finished epoxy emulsion BANCO 2056, purchased from Union chemistry group.
Comparative example 1
(1) Water-based epoxy coating
The formulation is substantially the same as in example 1, except that no sulfonic acid group was added to the modified graphene in component a.
The preparation method is the same as example 1.
SEM images of the water-based epoxy coatings formed by coating the water-based epoxy paints prepared in comparative example 1 and example 1 under the same conditions are shown in fig. 1 and fig. 2, respectively, and it can be seen that the coating in fig. 1 has many ravines on the surface, is rough and uneven, and has a few cracks; fig. 2 is a water-based epoxy coating with sulfonic acid group-modified graphene, which is uniform and flat, has no cracks or ravines, and the sulfonic acid group-modified graphene is uniformly distributed in the coating.
Salt spray resistance test:
the water-based epoxy coatings obtained in comparative example 1 and example 1 are tested according to the salt spray resistance test method of GB/T1771-2007, and the results are respectively shown in FIG. 3 and FIG. 4, FIG. 3 is a photo of the water-based epoxy coating obtained in comparative example 1 as a primer for a salt spray resistance test of 100h, FIG. 4 is a photo of the water-based epoxy coating obtained in example 1 as a primer for a salt spray resistance test of 600h, and it can be seen that the water-based epoxy coating obtained in example 1 of the present invention has more excellent salt spray resistance and corrosion resistance.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of sulfonic group modified graphene is characterized by comprising the following steps:
(1) uniformly mixing a graphite raw material and a sulfonic acid grinding aid, adding a solvent M, and mechanically stirring to obtain a dispersion liquid;
(2) pouring the dispersion liquid obtained in the step (1) into a ball milling tank, adding grinding balls, and carrying out ball milling to obtain sulfonic group modified graphene slurry;
(3) concentrating, ultrasonically dispersing, filtering and drying the sulfonic group modified graphene slurry obtained in the step (2) to obtain sulfonic group modified graphene powder.
2. The preparation method of sulfonic acid group modified graphene according to claim 1, wherein the graphite raw material is one or more of natural crystalline flake graphite, expanded graphite, expandable graphite and graphite powder; the solvent M is one or more of water, ethanol, acetone, ethylene glycol, glycerol and ethyl acetate.
3. The preparation method of the sulfonic acid group modified graphene according to claim 1, wherein the sulfonic acid group grinding aid is a mixture of one or more of sodium styrene sulfonate, sodium alpha-olefin sulfonate, sodium dodecyl benzene sulfonate, 2-acrylamide-2-methylpropanesulfonic acid, sodium lignin sulfonate, polyoxyethylene ether sulfonate and sodium alkyl benzene sulfonate and one or more of sodium sulfate, sodium carbonate, sodium bicarbonate, urea, polyvinylpyrrolidone, sodium chloride and calcium carbonate.
4. The preparation method of sulfonic acid group modified graphene according to any one of claims 1 to 3, wherein the mass ratio of the graphite raw material, the sulfonic acid group grinding aid and the solvent is 1: (5-50): (10-80).
5. The preparation method of sulfonic acid group modified graphene as claimed in claim 1, wherein the rotation speed of the ball milling in step (2) is 150-; the grinding balls are made of stainless steel or zirconia, and the mass ratio of the grinding balls to the dispersion liquid is 1 (5-40); the grinding balls are obtained by mixing large grinding balls with the diameter of 20mm, medium grinding balls with the diameter of 10mm and small grinding balls with the diameter of 6mm according to the mass ratio of 3:4: 4.
6. The preparation method of sulfonic acid group modified graphene according to claim 1, wherein the ultrasonic dispersion in step (3) is to disperse the concentrated sulfonic acid group modified graphene slurry in deionized water to be uniform; the filtration mode is centrifugation, filter pressing or nanofiltration; the drying mode is one or more of spray drying, vacuum drying and freeze drying.
7. The sulfonic acid group modified graphene prepared by the method of any one of claims 1 to 6, wherein the sheet diameter is 5-10 μm, and the sheet thickness is less than 5 nm.
8. The application of the sulfonic acid group modified graphene in a water-based epoxy coating, which is characterized in that the water-based epoxy coating comprises a component A and a component B in a mass ratio of 100 (40-80), wherein:
the component A comprises the following components in parts by weight: 10-20 parts of curing agent, 5-30 parts of solvent N, 40-80 parts of antirust filler, 10-40 parts of functional filler, 1-10 parts of cosolvent, 1-10 parts of auxiliary agent, and 0-1 part of sulfonic group modified graphene powder according to claim 7;
the component B is water-based epoxy emulsion.
9. The use according to claim 8, wherein the solvent N in component A is water; the antirust filler is any one or more of aluminum hydroxide, zinc phosphate, mica powder, iron oxide red and zinc oxide; the functional filler is one or more of talcum powder, titanium dioxide, silica powder, quartz powder, bentonite and precipitated barium sulfate; the cosolvent is one or more of propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol ethyl ether, ethylene glycol butyl ether and ethanol; the auxiliary agent is any one or more of a dispersing agent, a defoaming agent, a thickening agent, a coupling agent, a wetting agent, a flatting agent, a pH regulator and an anti-flash rust agent.
10. The use according to claim 8, wherein the aqueous epoxy emulsion is prepared by a conventional method by using an epoxy resin, and the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydroxymethyl bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin and nylon modified epoxy resin.
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