CN114907710B - Rust-proof pigment, preparation method thereof, paint and application thereof - Google Patents
Rust-proof pigment, preparation method thereof, paint and application thereof Download PDFInfo
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- CN114907710B CN114907710B CN202110172861.8A CN202110172861A CN114907710B CN 114907710 B CN114907710 B CN 114907710B CN 202110172861 A CN202110172861 A CN 202110172861A CN 114907710 B CN114907710 B CN 114907710B
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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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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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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- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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Abstract
The application provides an anti-rust pigment, a preparation method thereof, a coating and application thereof, wherein the anti-rust pigment comprises a flaky zinc chelate/graphite alkyne oxide/graphene microchip composite material, and in the flaky zinc chelate/graphite alkyne oxide/graphene microchip composite material, the graphite alkyne oxide is adsorbed between the flaky zinc chelate and the graphene microchip; the zinc chelate includes at least one of zinc phosphate, zinc molybdate, and zinc tungstate. The anti-corrosion pigment containing the flaky zinc chelate/graphite oxide alkyne/graphene microchip compound can be applied to a coating to remarkably improve the anti-corrosion performance of the coating by utilizing the good stability and the good physical barrier effect, the chemical passivation effect and the long-term effective anti-corrosion performance of the flaky zinc chelate/graphite oxide alkyne/graphene microchip compound.
Description
Technical Field
The application relates to the technical field of coatings, in particular to an antirust pigment, a preparation method thereof, a coating and application thereof.
Background
In recent years, as natural environments continue to deteriorate, human awareness of environmental protection has gradually increased. In the paint industry, the rust-proof pigment containing heavy metals such as lead, chromium and the like has excellent corrosion resistance, but has great toxicity and causes great influence on human health and environment, so the production and the use of the pigment are gradually eliminated by the market. The development of low-toxicity or non-toxic rust inhibitive pigments has attracted considerable social interest. Among them, there are new environmental protection pigments such as phosphate, aluminate, borate, tungstate, metal oxide, metal powder, etc., which have been developed and developed, but the above pigments have limited rust preventing effect and cannot meet the requirement of long-term corrosion preventing property.
Disclosure of Invention
In view of the above, the present application has an object to provide an anticorrosive pigment, a method for preparing the same, a paint and an application thereof, which can remarkably improve the anticorrosive performance of the paint by applying the anticorrosive pigment comprising the flaky zinc chelate/graphite alkyne oxide/graphene microchip composite to the paint by utilizing good stability and good physical barrier effect, chemical passivation effect and long-term effective anticorrosive performance of the flaky zinc chelate/graphite alkyne oxide/graphene microchip composite.
In order to achieve the above object, the present application provides the following technical solutions:
an anti-rust pigment comprises a flaky zinc chelate/graphite alkyne oxide/graphene microchip compound, wherein the graphite alkyne oxide is adsorbed between the flaky zinc chelate and the graphene microchip in the flaky zinc chelate/graphite alkyne oxide/graphene microchip compound.
The zinc chelate includes at least one of zinc phosphate, zinc molybdate, and zinc tungstate.
In a possible embodiment, the sheet diameter of the sheet zinc chelate is 1 μm to 15 μm.
In one possible embodiment, the graphene nanoplatelets have a thickness of 5nm or less.
In one possible embodiment, the number of layers of the graphene microchip is less than or equal to 10.
In one possible embodiment, the graphene nanoplatelets have a carbon content of 90wt% to 99wt%.
In one possible embodiment, the graphite alkyne oxide has an oxygen content of from 20wt% to 60wt%.
In one possible embodiment, the graphene nanoplatelets have a sheet diameter of 5 μm to 15 μm.
In one possible embodiment, the particle size of the graphite alkyne oxide is from 1nm to 20nm.
A preparation method of an anti-rust pigment, wherein the anti-rust pigment is the anti-rust pigment; the preparation method comprises the following steps:
providing a dispersion comprising a graphite alkyne oxide/graphene microchip complex;
and mixing the dispersion liquid with zinc salt and chelate in turn for reaction, and then carrying out solid-liquid separation, wherein the solid is the antirust pigment.
In one possible embodiment, the dispersion is obtained by mixing and dispersing graphene nanoplatelets, graphite alkyne oxide, and a solvent.
In one possible embodiment, the solvent includes at least one of water, ethanol, ethylene glycol, and diethyl ether.
In one possible embodiment, the dispersion is obtained by mixing and dispersing graphene microplates with an aqueous solution of graphite alkyne oxide.
In a possible embodiment, the concentration of the aqueous solution of graphite alkyne oxide is from 0.1g/L to 10g/L.
In one possible embodiment, the dispersing means includes one or more of ultrasonic, ball milling, shearing and homogenizing.
In a possible embodiment, the solid-liquid separation is preceded by mixing the mixture after the mixing reaction with the solvent.
In one possible embodiment, the mass ratio of graphene microplates to graphite alkyne oxide is 1: (0.05-1).
In one possible embodiment, the mass ratio of the graphene nanoplatelets to the zinc salt is 1: (1-9).
In one possible embodiment, the zinc salt comprises one or more of zinc chloride, zinc acetate, zinc sulfate and zinc nitrate.
In one possible embodiment, the chelate is a chelated salt aqueous solution.
In one possible embodiment, the chelating salt comprises one or more of sodium phosphate, ammonium phosphate, sodium dihydrogen phosphate, ammonium molybdate, sodium molybdate, and sodium tungstate.
In a possible embodiment, the reaction time of the dispersion with the zinc salt is from 5min to 30min.
In a possible embodiment, the ratio of the amount of zinc salt to the amount of chelating salt species is 1: (0.1-2).
In one possible embodiment, the graphene nanoplatelets have a thickness of 5nm or less.
In one possible embodiment, the number of layers of the graphene microchip is less than or equal to 10.
In one possible embodiment, the graphene nanoplatelets have a sheet diameter of 5 μm to 15 μm.
In one possible embodiment, the graphene nanoplatelets have a carbon content of 90wt% to 99wt%.
In one possible embodiment, the graphite alkyne oxide has an oxygen content of from 20wt% to 60wt%.
In a possible embodiment, the reaction time of the dispersion with the zinc salt is from 5min to 30min.
In one possible embodiment, the solid-liquid separation comprises at least one of centrifugation and filtration.
In one possible embodiment, the filtration employs membrane filtration; more preferably, the membrane filtration employs a polytetrafluoroethylene membrane having a membrane pore size of 0.1 μm to 1 μm.
In a possible embodiment, the solid-liquid separation further comprises drying the solid obtained by the solid-liquid separation.
In one possible embodiment, the drying temperature is 150 ℃ to 300 ℃.
A coating comprising the rust inhibitive pigment.
The application of the coating in engineering machinery products.
The beneficial effects of this application:
(1) The rust-proof pigment comprises a flaky zinc chelate/graphite alkyne oxide/graphene microchip compound, wherein graphite alkyne oxide is positioned between the flaky zinc chelate and the graphene microchip and respectively plays an adsorption role on the flaky zinc chelate and the graphene microchip, so that the flaky zinc chelate/graphite alkyne oxide/graphene microchip compound has good stability, good physical barrier effect, chemical passivation effect and long-term effective anti-corrosion performance; the anti-rust pigment can be applied to the paint to obviously improve the anti-corrosion performance of the paint.
(2) According to the preparation method of the antirust pigment, on one hand, graphene microplates are used as templates, graphite alkyne oxide is firmly adsorbed on the surfaces of the graphene microplates through pi bonds on the basal planes of the graphene microplates to serve as a cross-linking agent, so that the intrinsic characteristics of the graphene microplates are not damaged, and the dispersion stability of the graphene microplates in a solvent can be improved; on the other hand, the functional group with negative electricity on the edge of the graphite alkyne oxide is utilized to carry out charge adsorption with the zinc ion with positive electricity, and then the functional group is combined with the chelate in a reaction way, so that a product zinc chelate combined with the zinc ion grows into a flaky two-dimensional structure on the surface of the graphene microchip, and the product zinc chelate is firmly adsorbed on the surface of the graphene microchip through the graphite alkyne oxide to obtain a flaky zinc chelate/graphite alkyne oxide/graphene microchip compound with a sandwich structure.
(3) The preparation method is simple, has simple requirements on operation conditions, uses wide sources of raw materials, is green and pollution-free, has high cost performance, is suitable for large-scale production, and has wide market application prospect.
In order to make the above objects, features and advantages of the present application more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic diagram of a front side structure of the zinc phosphate/graphite alkyne oxide/graphene microchip composite rust inhibitive pigment obtained in example 1;
FIG. 2 is a schematic side view of the zinc phosphate/graphite alkyne oxide/graphene microchip composite rust inhibitive pigment obtained in example 1;
FIG. 3 is an AFM topography of a dispersion of graphite alkyne oxide/graphene platelet composites in example 1;
fig. 4 is an SEM morphology image of the zinc phosphate/graphite alkyne oxide/graphene microchip composite rust inhibitive pigment obtained in example 1 at 10000 times magnification.
Detailed Description
In order to facilitate an understanding of the present application, a technical solution of the present application is described in detail below in conjunction with examples, and numerous specific details are set forth in the following description in order to provide a thorough understanding of the present application.
This application is, however, susceptible of embodiment in many other ways than those herein described and similar modifications can be made by those skilled in the art without departing from the spirit of the application, and therefore the application is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification, definitions, will control.
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The application provides an anti-rust pigment, which comprises a flaky zinc chelate/graphite alkyne oxide/graphene microchip compound, wherein graphite alkyne oxide is adsorbed between the flaky zinc chelate and the graphene microchip in the flaky zinc chelate/graphite alkyne oxide/graphene microchip compound.
The zinc chelate includes at least one of zinc phosphate, zinc molybdate and zinc tungstate.
In some embodiments, the sheet zinc chelate complex has a sheet diameter of 1 μm to 15 μm.
In some embodiments, the graphene nanoplatelets have a thickness of 5nm or less.
In some embodiments, the number of layers of the graphene nanoplatelets is less than or equal to 10.
In some embodiments, the graphene nanoplatelets have a carbon content of 90wt% to 99wt%.
In some embodiments, the graphite alkyne oxide has an oxygen content of 20wt% to 60wt%.
In some embodiments, the graphene microplates have a plate diameter of 5 μm to 15 μm.
In some embodiments, the particle size of the graphite alkyne oxide is from 1nm to 20nm.
The application also provides a preparation method of the rust-proof pigment, which comprises the following steps:
s100, providing a dispersion liquid, wherein the dispersion liquid comprises graphite alkyne oxide/graphene microchip compound.
The dispersion liquid is obtained by mixing and dispersing graphene microplates, graphite alkyne oxide and a solvent.
In some embodiments, the above solvent includes at least one of water, ethanol, ethylene glycol, and diethyl ether, and preferably water or a mixed solution of water and at least one of the above organic solvents (ethanol, ethylene glycol, and diethyl ether) is used as the solvent.
In some embodiments, the dispersion is obtained by mixing and dispersing graphene microplates with an aqueous solution of graphite alkyne oxide; the concentration of the aqueous solution of the graphite alkyne oxide is 0.1g/L to 10g/L.
In some embodiments, the above-described manner of dispersing includes one or more of sonication, ball milling, shearing, and homogenization.
And S200, mixing the dispersion liquid with zinc salt and chelate in sequence for reaction, and then carrying out solid-liquid separation, wherein the solid is the rust-proof pigment.
In some embodiments, the zinc salt may be one or more of zinc chloride, zinc acetate, zinc sulfate, and zinc nitrate. The chelate is a chelate salt water solution; the chelate salt may be one or more of sodium phosphate, ammonium phosphate, sodium dihydrogen phosphate, ammonium molybdate, sodium molybdate and sodium tungstate.
In some embodiments, the mass ratio of the graphene microplates to the graphite alkyne oxide is 1: (0.05-1); the mass ratio of the graphene microchip to the zinc salt is 1: (1-9); the ratio of the amount of zinc salt to the amount of chelating salt material is 1: (0.1-2).
The graphene microchip is used as a template, so that the graphite alkyne oxide is adsorbed on the surface of the graphene microchip through pi bonds of a basal plane of the graphene microchip to obtain a graphite alkyne oxide/graphene microchip compound, the intrinsic characteristics of the graphene microchip are not damaged, and the dispersion stability of the graphene microchip in a solvent can be improved; the zinc ion is uniformly adsorbed on the surface of the graphene microchip by utilizing the negatively charged functional groups (such as hydroxyl, carboxyl and the like) at the edge of the graphite alkyne oxide and positively charged zinc ion, and then the zinc ion is combined with the chelate in a reaction way, so that a product zinc chelate combined with the zinc ion grows in an extending way by taking the adsorption site as the center, a large-size flaky two-dimensional structure is grown, and the flaky zinc chelate/graphite alkyne oxide/graphene microchip compound with a sandwich structure is obtained by firmly adsorbing the graphite alkyne oxide on the surface of the graphene microchip (as shown in figures 1 and 2); the structure is stable and not easy to be separated by mechanical acting force, can better exert the intrinsic electron conductivity of the graphene microchip and the chemical passivation and barrier capacities of the graphene microchip and the flaky zinc chelate, can effectively exert the physical labyrinth effect of the flaky material, and meanwhile, the graphite alkyne oxide serving as a nanometer-sized flaky material is uniformly distributed between the graphene microchip and the flaky zinc chelate, so that the activity of catalyzing the flaky zinc chelate is facilitated, the composite acting force of the graphene microchip and the flaky zinc chelate is enhanced, and the corrosion resistance of the graphene microchip and the flaky zinc chelate in the paint is remarkably improved.
Therefore, the anti-rust pigment with the sandwich structure has good physical barrier effect, chemical passivation effect and long-term effective anti-corrosion performance, and can obviously improve the anti-corrosion performance of the paint when applied to the paint.
In some embodiments, the zinc salt is added to the dispersion liquid in a mode of slowly adding the zinc salt while stirring, so that the reaction rate is effectively controlled, and zinc ions are fully adsorbed to the surface of the graphene microchip. It is to be noted that the zinc salt may be prepared as an aqueous zinc salt solution and then added dropwise to the dispersion with stirring.
In some embodiments, the thickness of the graphene microplates is less than or equal to 5nm, the plate diameter of the graphene microplates is 5-15 μm, and the particle diameter of the graphite alkyne oxide is 1-20 nm; the method is more favorable for combining graphite alkyne oxide with graphene microplates and generating a large-size two-dimensional lamellar structure on the surface of the graphene microplates by zinc chelate which is a product of combining zinc ions with chelate.
In some embodiments, the number of layers of graphene nanoplatelets is less than or equal to 10.
In some embodiments, the graphene nanoplatelets have a carbon content of 90wt% to 99wt%; the oxygen content of the graphite alkyne oxide is 20-60 wt%.
In some embodiments, the reaction time of the dispersion with the zinc salt is 5min-30min, so that zinc ions can be completely adsorbed on the surface of the graphene microchip.
The solid-liquid separation includes at least one of centrifugation and filtration.
In some embodiments, the filtration described above employs membrane filtration; more preferably, the membrane filtration employs a polytetrafluoroethylene membrane having a membrane pore size of 0.1 μm to 1 μm.
Further, the mixture after the above mixing reaction is mixed with the above solvent, preferably water, and then subjected to solid-liquid separation, and this step can be repeated to thoroughly remove unreacted zinc salts and chelate salts.
In some embodiments, the solid-liquid separation further comprises drying the solid obtained by the solid-liquid separation.
The drying mode can adopt a common oven for drying, and the drying temperature is preferably 150-300 ℃; of course, vacuum drying may also be employed.
The application also provides a coating, which comprises the antirust pigment.
The application also provides application of the coating on engineering machinery products such as ships, wind power equipment, marine pipe fittings and the like, for example, a paint film is formed on the surface of a ship shell by using the coating, so that the ship shell has strong corrosion resistance, and the service life of the ship is prolonged.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Weighing graphene microplates with the mass of 5.0g, the plate diameter range of 5 mu m-10 mu m and the carbon content of 90wt%, adding the graphene microplates into an aqueous solution of graphite alkyne oxide with the volume of 1.0L, the concentration of 5.0g/L, the particle size range of 1nm-10nm and the oxygen content of 20wt%, and performing ultrasonic dispersion for 30min under the ultrasonic condition with the power of 1000W to obtain a dispersion liquid of a graphite alkyne oxide/graphene microplate compound; then weighing 5.0g of zinc nitrate, slowly adding the zinc nitrate into the dispersion liquid while stirring, and continuously stirring and reacting for 30min to obtain a mixed liquid A; and then according to the mass ratio of zinc nitrate to sodium phosphate as 1:2, weighing 5.6g of sodium phosphate, dispersing in 100mL of deionized water to obtain a sodium phosphate aqueous solution, slowly adding the sodium phosphate aqueous solution into the mixed solution A until the reaction is complete to obtain a mixed solution B; and finally adding deionized water into the mixed solution B, filtering, adding deionized water into the solid obtained by filtering, continuously filtering, repeating the step for 3 times, collecting the final solid, and drying in an oven at 150 ℃ for 3 hours to obtain the zinc phosphate/graphite alkyne oxide/graphene microchip compound antirust pigment.
Example 2
Weighing graphene microplates with the mass of 5.0g, the plate diameter range of 10-15 mu m and the carbon content of 99wt%, adding the graphene microplates into an aqueous solution of graphite alkyne oxide with the volume of 1.0L, the concentration of 0.25g/L, the particle size range of 10-20 nm and the oxygen content of 60wt%, and carrying out high-pressure homogenization and dispersion for 2 times under the pressure of 1500bar to obtain a dispersion liquid of the graphite alkyne oxide/graphene microplate compound; then weighing 45.0g of zinc nitrate, slowly adding the zinc nitrate into the dispersion liquid while stirring, and continuously stirring and reacting for 5min to obtain a mixed liquid A; and then according to the mass ratio of zinc nitrate to sodium phosphate as 1: under the condition of 0.1, 4.2g of sodium phosphate is weighed and dispersed in 300mL of deionized water to obtain a sodium phosphate aqueous solution, and the sodium phosphate aqueous solution is slowly added into the mixed solution A until the reaction is completed to obtain a mixed solution B; and finally adding deionized water into the mixed solution B, filtering, adding deionized water into the solid obtained by filtering, continuously filtering, repeating the step for 3 times, collecting the final solid, and drying in an oven at 300 ℃ for 1h to obtain the zinc phosphate/graphite alkyne oxide/graphene microchip compound antirust pigment.
Example 3
Weighing 5.0g of graphene microplates with the plate diameter ranging from 8 mu m to 12 mu m and the carbon content of 95wt%, adding the graphene microplates into an aqueous solution of graphite alkyne oxide with the volume of 1.0L, the concentration of 4.0g/L, the particle size ranging from 5nm to 15nm and the oxygen content of 40wt%, and dispersing the graphite alkyne oxide in the aqueous solution for 10min under the high shearing condition of 3000rpm to obtain a dispersion liquid of a graphite alkyne oxide/graphene microplate compound; then weighing 25.0g of zinc sulfate, slowly adding the zinc sulfate into the dispersion liquid while stirring, and continuing stirring reaction for 15min to obtain a mixed liquid A; and then the ratio of the zinc sulfate to the sodium dihydrogen phosphate is 1:1, 1.5g of sodium dihydrogen phosphate is weighed and dispersed in 100mL of deionized water to obtain sodium dihydrogen phosphate aqueous solution, and the sodium dihydrogen phosphate aqueous solution is slowly added into the mixed solution A until the reaction is complete to obtain mixed solution B; and finally adding deionized water into the mixed solution B, filtering, adding deionized water into the solid obtained by filtering, continuously filtering, repeating the step for 3 times, collecting the final solid, and drying in a drying oven at 200 ℃ for 1.5 hours to obtain the zinc phosphate/graphite alkyne oxide/graphene microchip compound antirust pigment.
Example 4
Weighing 5.0g of graphene microplates with the plate diameter ranging from 5 mu m to 8 mu m and the carbon content of 99wt%, adding the graphene microplates into an aqueous solution of graphite oxide alkyne with the volume of 1.0L, the concentration of 5.0g/L, the particle size ranging from 12nm to 20nm and the oxygen content of 20wt%, and dispersing the graphite oxide alkyne in a ball milling condition of 400rpm for 30min to obtain a dispersion liquid of a graphite oxide alkyne/graphene microplate compound; then weighing 45.0g of zinc chloride, slowly adding the zinc chloride into the dispersion liquid while stirring, and continuously stirring and reacting for 30min to obtain a mixed liquid A; and then the ratio of the zinc chloride to the sodium phosphate is 1:2, weighing 108.2g of sodium phosphate, dispersing in 500mL of deionized water to obtain a sodium phosphate aqueous solution, slowly adding the sodium phosphate aqueous solution into the mixed solution A until the reaction is complete to obtain a mixed solution B; and finally adding deionized water into the mixed solution B, filtering, adding deionized water into the solid obtained by filtering, continuously filtering, repeating the step for 3 times, collecting the final solid, and drying in an oven at 150 ℃ for 5 hours to obtain the zinc phosphate/graphite alkyne oxide/graphene microchip compound antirust pigment.
Example 5
Weighing graphene microplates with the mass of 10.0g, the plate diameter range of 6-10 mu m and the carbon content of 96wt%, adding the graphene microplates into an aqueous solution of graphite alkyne oxide with the volume of 1.0L, the concentration of 10.0g/L, the particle size range of 8-12 nm and the oxygen content of 45wt%, and dispersing the aqueous solution for 15min under the high shearing condition of 3000rpm to obtain a dispersion liquid of the graphite alkyne oxide/graphene microplate compound; then weighing 10.0g of zinc sulfate, slowly adding the zinc sulfate into the dispersion liquid while stirring, and continuously stirring and reacting for 15min to obtain a mixed liquid A; and then the ratio of the amount of zinc sulfate to the amount of ammonium molybdate is 1:1, weighing 12.2g of ammonium molybdate, dispersing the ammonium molybdate in 100mL of deionized water to obtain an ammonium molybdate aqueous solution, and slowly adding the ammonium molybdate aqueous solution into the mixed solution A until the reaction is complete to obtain a mixed solution B; and finally adding deionized water into the mixed solution B, filtering, adding deionized water into the solid obtained by filtering, continuously filtering, repeating the step for 3 times, collecting the final solid, and drying in an oven at 200 ℃ for 2 hours to obtain the zinc molybdate/graphite alkyne oxide/graphene microchip compound antirust pigment.
Example 6
2.0g of graphene microplates with the diameter ranging from 10 mu m to 15 mu m and the carbon content of 99wt% are weighed and added into an aqueous solution of graphite oxide alkyne with the volume of 1.0L, the concentration of 0.1g/L, the particle size ranging from 8nm to 12nm and the oxygen content of 55wt%, and the mixture is dispersed for 20min under the high shearing condition of 3000rpm to obtain a dispersion liquid of the graphite oxide alkyne/graphene microplate compound; then weighing 10.0g of zinc chloride, slowly adding the zinc chloride into the dispersion liquid while stirring, and continuously stirring and reacting for 15min to obtain a mixed liquid A; and then the ratio of the zinc chloride to sodium tungstate is 1:1, 21.6g of sodium tungstate is weighed and dispersed in 200mL of deionized water to obtain sodium tungstate aqueous solution, and the sodium tungstate aqueous solution is slowly added into the mixed solution A until the reaction is complete to obtain mixed solution B; and finally adding deionized water into the mixed solution B, filtering, adding deionized water into the solid obtained by filtering, continuously filtering, repeating the step for 3 times, collecting the final solid, and drying in an oven at 200 ℃ for 2 hours to obtain the zinc tungstate/graphite alkyne oxide/graphene microchip compound antirust pigment.
Example 7
This embodiment differs from embodiment 1 in that: the procedure of example 1 was repeated except that the aqueous solution of graphite alkyne oxide was replaced with an aqueous solution of 80% by mass of ethanol.
Example 8
This embodiment differs from embodiment 1 in that: the procedure of example 1 was repeated except that the aqueous solution of graphite-alkyne oxide was replaced with an aqueous solution of diethyl ether having a mass fraction of 70%.
Comparative example 1
The difference between this comparative example and example 3 is that: the graphene microchip composite antirust pigment is obtained by replacing graphite alkyne oxide with a titanate coupling agent TMC-201 and performing the same operation as in example 3.
Comparative example 2
The difference between this comparative example and example 3 is that: the graphene microchip composite rust-preventing pigment is obtained by replacing graphite alkyne oxide with an aluminate coupling agent DL-411 and otherwise carrying out the same procedure as in example 3.
Comparative example 3
Adding 4g of 3-aminopropyl triethoxysilane, 6g of gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, 4g of OP-10 and 1g of sodium dodecyl benzene sulfonate into 80g of deionized water under stirring, uniformly stirring to form mixed slurry, slowly adding 3g of conductive graphene and 1g of reduced graphene oxide into the mixed slurry under stirring, and uniformly stirring at a low speed for reacting for 5 hours at 90 ℃ to form graphene slurry; adding 100g of the graphene slurry into a dispersing feed cylinder, stirring at a rotating speed of 500r/min, slowly adding 12g of zinc oxide with purity of more than 99.5%, uniformly stirring, transferring into a sand mill, and grinding for 2.5h to form grinding slurry; diluting 5g of industrial phosphoric acid with the concentration of 85wt% to 25wt%, heating to 35 ℃ in a reaction kettle, slowly adding the grinding slurry into the reaction kettle, heating to 55 ℃, reacting for 4 hours, and centrifugally filtering and washing the obtained precipitate; and drying the graphene composite antirust pigment obtained by filtering at 120 ℃ in a pneumatic drying mode for 0.5h, and then crushing to 5-10 mu m to obtain the graphene composite antirust pigment.
Comparative example 4
Weighing 2.0g of graphene oxide microplates with the mass of 2.0g, the sheet diameter range of 5-10 mu m and the oxygen content of 30wt%, adding the graphene oxide microplates into 500mL of aqueous solution, and dispersing for 20min under the high shearing condition of 3000rpm to obtain graphene oxide dispersion liquid; then weighing 5.0g of zinc sulfate, slowly adding the zinc sulfate into the dispersion liquid while stirring, and continuously stirring and reacting for 30min to obtain a mixed liquid A; and then the ratio of the amount of zinc sulfate to the amount of ammonium phosphate is 1:1, weighing 4.6g of ammonium phosphate, dispersing in 100mL of deionized water to obtain an ammonium phosphate aqueous solution, slowly adding the ammonium phosphate solution into the mixed solution A until the reaction is complete to obtain a mixed solution B; and finally adding deionized water into the mixed solution B, filtering, adding deionized water into the solid obtained by filtering, continuously filtering, repeating the step for 3 times, collecting the final solid, and drying in an oven at 120 ℃ for 1h to obtain the zinc phosphate/graphene oxide compound antirust pigment.
1. Performing morphology analysis on the dispersion liquid of the graphite oxide alkyne/graphene microchip compound in the embodiment 1 and the obtained zinc phosphate/graphite oxide alkyne/graphene microchip compound antirust pigment; the test results are shown in fig. 3 and 4.
FIG. 3 is an AFM topography of a dispersion of graphite alkyne oxide/graphene platelet composites in example 1; fig. 4 is an SEM morphology diagram of the zinc phosphate/graphite alkyne oxide/graphene microchip composite rust-preventing pigment obtained in example 1 at 10000 times, and it can be seen from fig. 3 and 4 that the zinc phosphate in the obtained zinc phosphate/graphite alkyne oxide/graphene microchip composite rust-preventing pigment is a large-sized flake structure of micron order, and the flake zinc phosphate is tightly combined with the graphene microchip through graphite alkyne oxide.
The morphology of the rust inhibitive pigment obtained in examples 2 to 8 was the same as that of the zinc phosphate/graphite oxide alkyne/graphene microchip composite rust inhibitive pigment obtained in example 1.
2. The rust inhibitive pigments obtained in examples 1 to 8 and comparative examples 1 to 4 and commercial zinc phosphate were added to the paint, respectively, 13 groups of paint such as the rust inhibitive pigments obtained in examples 1 to 8 and comparative examples 1 to 4 and the commercial zinc phosphate were added to the paint, respectively, to prepare corresponding paint films, and the dry film thickness of each group of paint films was measured;
1. salt spray resistance tests were carried out on each group of paint films, and the salt spray resistance time of each group was recorded, and the results are shown in the following table 1;
2. the resistance values were tested after each group of paint films was immersed in a 3.5wt% sodium chloride solution for 72 hours, and the results are shown in table 1 below:
TABLE 1
From the results in table 1 above, it can be seen that: the resistance at 72 hours of the paint film made by adding the paint of the rust inhibitive pigment prepared by the present application is significantly higher than the resistance at 72 hours of the paint film made by adding the rust inhibitive pigments of comparative examples 1 to 4 and the paint of commercially available zinc phosphate; and the salt spray resistance time of a paint film prepared by adding the anti-rust pigment prepared by the method is obviously longer than that of a paint film prepared by adding the anti-rust pigments of comparative examples 1-4 and the paint of the commercial zinc phosphate.
In comparative example 3, graphene was chemically modified with a silane coupling agent, the modified graphene was milled and dispersed with high-purity zinc oxide, and reacted with low-concentration phosphoric acid by dipping, the phosphate group was adsorbed on the surface of graphene, and zinc oxide was continuously diffused as a zinc source to the surface of graphene and reacted with the phosphate group to produce nano-sized supported zinc phosphate. According to the method, nano zinc phosphate can be uniformly loaded on the surface of graphene, the flaky graphene can play a certain physical barrier role, but the corrosion resistance of the coating can be influenced by the silane coupling agent used when the silane coupling agent is doped into the coating system, and the nano zinc phosphate has high activity and high consumption and cannot meet the requirement of long-term corrosion resistance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (15)
1. The preparation method of the rust-proof pigment is characterized in that the rust-proof pigment comprises a flaky zinc chelate/graphite alkyne oxide/graphene microchip compound, wherein the graphite alkyne oxide is adsorbed between the flaky zinc chelate and the graphene microchip in the flaky zinc chelate/graphite alkyne oxide/graphene microchip compound;
the zinc chelate includes at least one of zinc phosphate, zinc molybdate and zinc tungstate;
the preparation method comprises the following steps:
providing a dispersion comprising a graphite alkyne oxide/graphene microchip complex;
mixing the dispersion liquid with zinc salt and chelate in sequence for reaction, and then carrying out solid-liquid separation to obtain the antirust pigment;
the chelate is a chelate salt aqueous solution, and the chelate salt comprises at least one of sodium phosphate, ammonium phosphate, sodium dihydrogen phosphate, ammonium molybdate, sodium molybdate and sodium tungstate;
the zinc salt comprises one or more of zinc chloride, zinc acetate, zinc sulfate and zinc nitrate.
2. The method for producing a rust inhibitive pigment according to claim 1, wherein the sheet diameter of the sheet-like zinc chelate compound is 1 μm to 15 μm;
and/or the thickness of the graphene microchip is less than or equal to 5nm;
and/or the number of layers of the graphene microchip is less than or equal to 10;
and/or the carbon content of the graphene microplatelets is 90-99 wt%;
and/or, the oxygen content of the graphite alkyne oxide is 20-60 wt%;
and/or the diameter of the graphene micro-plate is 5-15 μm;
and/or the particle size of the graphite alkyne oxide is 1nm-20nm.
3. The method for producing a rust inhibitive pigment according to claim 1, wherein the dispersion liquid is obtained by mixing and dispersing graphene microplates, graphite alkyne oxide and a solvent.
4. The method for preparing a rust inhibitive pigment according to claim 3, wherein the solvent comprises at least one of water, ethanol, ethylene glycol and diethyl ether.
5. The method for producing a rust inhibitive pigment according to claim 3, wherein said step of mixing said mixture after the mixing reaction with said solvent is further included before said solid-liquid separation.
6. The method for producing a rust inhibitive pigment according to claim 1, wherein the dispersion liquid is obtained by mixing and dispersing graphene microplates with an aqueous solution of graphite alkyne oxide.
7. The method for producing a rust inhibitive pigment according to claim 6, wherein the concentration of said aqueous solution of graphite alkyne oxide is 0.1g/L to 10g/L.
8. The method for preparing a rust inhibitive pigment according to any one of claims 3 to 7, wherein the dispersing means comprises one or more of ultrasonic, ball milling, shearing and homogenizing.
9. The method for preparing the rust inhibitive pigment according to claim 1, wherein the mass ratio of the graphene microplates to the graphite alkyne oxide is 1: (0.05-1);
and/or the mass ratio of the graphene microchip to the zinc salt is 1: (1-9).
10. The method for preparing a rust inhibitive pigment according to claim 1, wherein the reaction time of the dispersion with the zinc salt is 5min to 30min;
and/or the ratio of the amount of zinc salt to the amount of chelating salt is 1: (0.1-2).
11. The method for producing a rust inhibitive pigment according to claim 1, wherein said solid-liquid separation comprises at least one of centrifugal separation and filtration.
12. The method for preparing a rust inhibitive pigment according to claim 11, wherein the filtration is membrane filtration;
the membrane filter adopts a polytetrafluoroethylene membrane with the membrane pore diameter of 0.1-1 μm.
13. The method for producing a rust inhibitive pigment according to claim 1, wherein said solid-liquid separation further comprises drying the solid obtained by said solid-liquid separation;
the drying temperature is 150-300 ℃.
14. A paint comprising the rust inhibitive pigment produced by the production method according to any one of claims 1 to 13.
15. Use of the coating of claim 14 in a work machine product.
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| GB2572764B (en) * | 2018-04-09 | 2023-06-07 | Applied Graphene Mat Uk Ltd | Corrosion protection for metallic substrates |
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