WO2017036085A2 - Graphene heavy-duty anti-corrosion environmentally friendly hard repair coating and preparation method therefor - Google Patents

Graphene heavy-duty anti-corrosion environmentally friendly hard repair coating and preparation method therefor Download PDF

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WO2017036085A2
WO2017036085A2 PCT/CN2016/072300 CN2016072300W WO2017036085A2 WO 2017036085 A2 WO2017036085 A2 WO 2017036085A2 CN 2016072300 W CN2016072300 W CN 2016072300W WO 2017036085 A2 WO2017036085 A2 WO 2017036085A2
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powder
graphene
component
carboxymethyl
methylpyrrole
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PCT/CN2016/072300
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French (fr)
Chinese (zh)
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赖晓明
邵聪
王金娥
张航
郑华伟
孙志伟
张晓辉
谭海丰
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中兴通讯股份有限公司
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Publication of WO2017036085A2 publication Critical patent/WO2017036085A2/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02Polyureas
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/082Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084Inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to a graphene heavy anti-corrosion coating, in particular to a graphene heavy anti-corrosion environmental protection hard repair coating, belonging to the field of organic coatings.
  • Primers on the surface of outdoor metal substrates are usually repaired with paints.
  • Primers and primers are usually used for repairing paints.
  • Primers are usually solvent-based epoxy coatings.
  • Topcoats are generally aliphatic acrylic polyurethane coatings. Primer is guaranteed. The adhesion and corrosion resistance of the metal substrate, the topcoat provides appearance and weather resistance, but the substrate needs to be strictly treated during the repair, the primer is applied first, the topcoat is applied after the surface is dried, and the repair cycle is long, generally requires at least 2 Sub-coating, with at least tens of minutes of primer drying time in the middle, is not suitable for the quickness of field repair; and it is a dangerous chemical, which is difficult to transport and costly in the international scope.
  • water-based paints are more environmentally friendly, existing water-based paints generally require higher environmental humidity on the surface of metal substrates, environmental relative humidity requirements of not more than 80%, and inability to dry or film normally in environments below 10 ° C or It takes several hours to completely dry, and the water-resistant paint has poor water resistance, damp heat resistance and salt spray resistance, which seriously affects the promotion and use of water-based repair paint in the field of heavy-duty anti-corrosion of outdoor equipment.
  • polyurea elastic coatings have developed rapidly in the fields of anti-corrosion, wear-resisting, waterproof, etc., and have been widely used. Although they have superior performance, there are many problems in the field as repair coatings, such as too fast reaction time. Only a few seconds to a dozen seconds, the wettability to the metal substrate is not good, the adhesion is very poor, and special spraying equipment is needed. For small areas or irregular surfaces that need to be manually brushed, it is impossible to construct, even if it is The polyaspartic acid ester polyurea elastic coating called the third generation polyurea has excellent adhesion to the metal substrate and in-situ coating of the outdoor equipment of galvanized steel sheet.
  • graphene demonstrate its enormous potential in the field of corrosion protection of metallic materials.
  • the stable sp2 hybrid structure of graphene makes it possible to form a physical barrier between the metal and the active medium to prevent diffusion and penetration.
  • graphene has good thermal and chemical stability, both at high temperatures. Under conditions (up to 1500 ° C), it can remain stable in corrosive or oxidizing gases and liquids.
  • the good electrical and thermal conductivity of graphene provides favorable conditions for the service environment of metals in corrosive environments. Therefore, the repair coating prepared by using the graphene composite material can greatly improve the corrosion resistance of the coating.
  • the embodiment of the present invention provides a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating which is convenient for repairing and corrosion of a metal substrate surface coating in a field repairing device, and the graphene heavy weight of the embodiment of the present invention.
  • Anti-corrosion and environmental protection hard repair coating does not contain organic volatile solvent, almost odorless, non-hazardous chemicals, achieve primer and topcoat in one, no need to brush primer, excellent anti-corrosion and weather resistance, pencil hardness of more than 3H, attached Excellent impact resistance, normal construction above -10 °C, rapid drying, simple construction; not only strong adhesion to galvanized steel substrate, but also suitable for repair of cold-rolled steel, aluminum alloy, magnesium alloy and other metal substrates Single layer heavy anti-corrosion hard repair coating.
  • an embodiment of the present invention provides a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating, wherein the first component and the second component are formed;
  • the first component comprises: polyaspartate resin, N-carboxymethyl N-methylpyrrole and graphene powder;
  • the second component is an HDI trimer curing agent
  • the mass ratio of the first component to the second component is 3-4:1.
  • the first component further comprises: an anti-rust pigment, a coloring pigment, a molecular sieve activated powder, an organic digestive powder, a rheological additive and other auxiliary agents.
  • the mass ratio of the anti-rust pigment, the coloring pigment, the molecular sieve activated powder, the organic digestive powder, the rheological additive and other auxiliary agents is 10-20:3-15:2-5:0-15: 0.2-0.6: 0.4-0.8.
  • the graphene powder is a graphene sheet powder composed of a plurality of layers of single-layer graphene, and the graphene powder of the embodiment of the invention is uniformly dispersed in the base resin and other additives, and can be improved. Repair the environmental stability and comprehensive corrosion resistance of the coating.
  • the number of layers of the graphene sheet powder is 1-10 layers.
  • the graphene powder is activated by an ethanol solution of a surfactant before use, and is used to prepare the graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating.
  • the mass fraction of the surfactant ethanol solution for treating the graphene powder is 1%.
  • the surfactant is one or more of sodium alkylbenzenesulfonate, sodium polyacrylate, sodium alginate and sodium stearate, used for surface modification of graphene, changing graphene Surface energy, increasing its dispersion properties.
  • the anti-rust pigment is zinc phosphate and/or modified aluminum tripolyphosphate, and the anti-rust pigment can not only improve the adhesion of the repair coating to the galvanized steel sheet, but also increase the comprehensive anti-corrosion ability of the repair coating.
  • the coloring pigment is a high weathering inorganic pigment or organic pigment, including but not limited to: rutile titanium dioxide, high pigment carbon black, iron oxide red, iron oxide yellow, chrome yellow, phthalocyanine blue, lanthanum Cyanine green, permanent red, permanent yellow, permanent solid purple, etc., used to obtain the appearance color required for repair.
  • the molecular sieve activated powder is one or more of 3A, 4A, 5A molecular sieve activated powder, and the addition of the molecular sieve activated powder can remove the moisture in the coating system and improve the coating quality. Avoid foaming and save curing time.
  • the organic digestive powder is a modified urea polymer powder, and the addition of the organic digestive powder can reduce the gloss and make the coating closer to the standard template.
  • the rheology aid is an organosilicone modified fumed silica, which has the functions of anti-precipitation and discharge.
  • the other auxiliary agent includes a dispersing agent, an antifoaming agent and a leveling agent.
  • the mass ratio of the dispersant, the antifoaming agent and the leveling agent is 1:1:1.
  • the dispersing agent the main chemical component is a prepolymer of a long-chain polycarboxylic acid and a polyhydric alcohol, and functions to improve the dispersibility and stability of the pigment.
  • the antifoaming agent component is a modified polydimethylsiloxane, which functions to eliminate bubbles in the production process of the coating.
  • the leveling agent is a polyether modified polydimethylsiloxane, which functions to reduce the surface tension of the coating, avoid shrinkage, and improve the flatness of the coating.
  • the mass percentage of other auxiliary agents are: 45-55% of polyaspartic acid ester resin; 2-4% of N-carboxymethyl-N-methylpyrrole; 0.2-1% of graphene powder; antirust pigment 10 -20%; coloring pigment 3-15%; molecular sieve activated powder 2-5%; organic digestive powder 0-15%; rheological additive 0.2-0.6%; other additives 0.4-0.8%.
  • the polyaspartic acid ester resin and the HDI trimer curing agent are film-forming substances of the repair coating, and the two can be crosslinked at room temperature to form a coating film having excellent toughness and weather resistance
  • N-carboxymethyl N- Methylpyrrole is a multifunctional additive that has a toughening effect and also dissolves metal oxides that disperse the steel surface to improve the adhesion of the coating to the metal substrate.
  • Another aspect of the present invention provides a method for preparing a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating, comprising:
  • the raw material comprising polyaspartic acid ester resin, N-carboxymethyl N-methylpyrrole and graphene powder is mixed and stirred to obtain a first component;
  • An HDI trimer curing agent as a second component is added to the first component, and the mixture is uniformly stirred.
  • the mass ratio of the first component to the second component is 3-4:1.
  • the raw material comprising the polyaspartic acid ester resin, the N-carboxymethyl N-methylpyrrole and the graphene powder is mixed and stirred to obtain the first component comprising:
  • the graphene powder is added to the surfactant ethanol solution, stirred and sonicated, filtered and dried to obtain an activated graphene powder;
  • the activated graphene powder is uniformly stirred with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole and other auxiliary agents to prepare a preliminary material of the graphene liquid raw material mixture;
  • the coloring pigment, the rust preventive pigment, the molecular sieve activated powder, the organic digestive powder and the rheological assistant are added to the preliminary material of the graphene liquid raw material mixture, stirred and uniformly mixed to obtain a first component.
  • the mass fraction of the surfactant ethanol solution is 1%.
  • the ratio of the weight of the graphene powder to the volume of the surfactant ethanol solution is 1-2 g: 50-100 ml.
  • the stirring time of the graphene powder and the surfactant ethanol solution is 20-30 min, and the stirring speed is 200-600 r/min.
  • the treatment time for sonicating the graphene powder and the surfactant is 20-30 min.
  • the stirring time of the preliminary material of the graphene liquid raw material mixture is 20-30 min, and the stirring speed is 800-1500 r/min.
  • the coloring pigment, the rust preventive pigment and the molecular sieve activated powder are first added to the preliminary material of the graphene liquid raw material mixture, stirred for 20-30 min and ground to uniformly disperse.
  • the organic digestive powder and the rheological assistant are further added thereto, stirred at a stirring speed of 800 to 1500 r/min for 20 to 30 minutes, and uniformly mixed to obtain the first component.
  • the HDI trimer curing agent is added to the first component which has been uniformly mixed, and the mixture is uniformly stirred to obtain a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating.
  • the mass percentage of other auxiliary agents are: 45-55% of polyaspartic acid ester resin; 2-4% of N-carboxymethyl-N-methylpyrrole; 0.2-1% of graphene powder; antirust pigment 10 -20%; coloring pigment 3-15%; molecular sieve activated powder 2-5%; organic digestive powder 0-15%; rheological additive 0.2-0.6%; other additives 0.4-0.8%.
  • the graphene powder is a graphene sheet powder composed of a plurality of layers of single-layer graphene, and the graphene powder of the embodiment of the invention is uniformly dispersed in the base resin and other additives, and the repair coating can be improved. Environmental stability and comprehensive corrosion resistance.
  • the number of layers of the graphene sheet powder is 1-10 layers.
  • the surfactant is one or more of sodium alkylbenzenesulfonate, sodium polyacrylate, sodium alginate and sodium stearate, used for surface modification of graphene, changing graphene Surface energy, increasing its dispersion properties.
  • the anti-rust pigment is zinc phosphate and/or modified aluminum tripolyphosphate, and the anti-rust pigment can not only improve the adhesion of the repair coating to the galvanized steel sheet, but also increase the comprehensive anti-corrosion ability of the repair coating.
  • the coloring pigment is a high weathering inorganic pigment or organic pigment, including but not limited to: rutile titanium dioxide, high pigment carbon black, iron oxide red, iron oxide yellow, chrome yellow, phthalocyanine blue, lanthanum Cyanine green, permanent red, permanent yellow, permanent solid purple, etc., used to obtain the appearance color required for repair.
  • the molecular sieve activated powder is a kind of 3A, 4A, 5A molecular sieve activated powder. Or several kinds of molecular sieve activated powder can remove the moisture in the coating system, improve the coating quality, avoid foaming, and save curing time.
  • the organic digestive powder is a modified urea polymer powder, and the addition of the organic digestive powder can reduce the gloss and make the coating closer to the standard template.
  • the rheology aid is an organosilicone modified fumed silica, which has the functions of anti-precipitation and discharge.
  • the other auxiliary agent includes a dispersing agent, an antifoaming agent and a leveling agent.
  • the mass ratio of the dispersant, the antifoaming agent and the leveling agent is 1:1:1.
  • the dispersing agent the main chemical component is a prepolymer of a long-chain polycarboxylic acid and a polyhydric alcohol, and functions to improve the dispersibility and stability of the pigment.
  • the antifoaming agent component is a modified polydimethylsiloxane, which functions to eliminate bubbles in the production process of the coating.
  • the leveling agent is a polyether modified polydimethylsiloxane, which functions to reduce the surface tension of the coating, avoid shrinkage, and improve the flatness of the coating.
  • polyaspartate and HDI trimer curing agent are film-forming materials for refinishing coatings, which can be crosslinked at room temperature to form a coating film with excellent toughness and weather resistance, N-carboxymethyl N-A
  • the pyrrole is a multifunctional additive that has a toughening effect and also dissolves metal oxides that disperse the steel surface to improve the adhesion of the coating to the metal substrate.
  • the graphene heavy-duty anti-corrosion environmentally-friendly hard repairing coating of the embodiment of the invention does not contain organic volatile solvent, is almost odorless, and is non-hazardous chemical, and is very suitable for repairing rusted parts or damaged coatings of outdoor equipment.
  • the preparation method of the graphene heavy-duty anti-corrosion environmental protection hard repairing coating of the embodiment of the invention is simple and quick, and the first component and the second component can be uniformly mixed, and the curing is not required for a long time, which is very suitable for designing into a small package. Carrying and construction of common items.
  • the graphene heavy anti-corrosion environmental protection hard repair paint primer and top coat are combined into one, no need to apply primer, excellent anti-corrosion and weather resistance, pencil hardness of more than 3H, excellent adhesion and impact resistance. It can be normally constructed above -10 °C, which can repair the damaged coating or rusted area of metal directly and quickly. It can be dried quickly, and the surface is completely dry within 1h, and the performance is excellent.
  • the graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating of the embodiment of the invention can not only repair the original coating of the metal substrate such as galvanized sheet, cold-rolled steel sheet or aluminum alloy sheet, including: outdoor powder coating and amino baking coating. Layer, polyurethane coating, etc.; can also directly brush the metal substrate, adhesion to galvanized steel substrate, and excellent adhesion to cold-rolled steel, aluminum alloy, magnesium alloy and other metal substrates. ,Wide range of applications.
  • the graphene heavy-duty anti-corrosion environmental protection hard repair coating of the embodiment of the invention has the adhesion, water resistance, acid resistance, alkali resistance, sulfur dioxide resistance, salt spray resistance and aging resistance of the xenon lamp on the surface of the hot-dip galvanized steel sheet equipment. Excellent performance.
  • the polyaspartic acid ester resin used in the examples of the present invention is one or a mixture of Bayer Desmophen 1420, Desmophen 1520, Desmophen 1220, Zhuhai Feiyang Chemical F420, F520, F530, F220; molecular sieve activated powder It is 3A, 4A, 5A molecular sieve activated powder; organic digestive powder is Shengyuan Chemical E-7; rheological additive is fumed silica Cabot TS-720; dispersing agent is BYK108 of German BYK; defoaming agent is Degao Company TEGO N; leveling agent is Shanghai Tyco Polymer Company TECH-284; HDI trimer curing agent is Bayer Desmodur N3600.
  • Polyaspartate resin 50% (Desmophen 142025%, Desmophen 152025%); N-carboxymethyl-N-methylpyrrole 3%; graphene powder 0.8%; zinc phosphate 16%; rutile titanium dioxide 13 %; molecular sieve activated powder 3.5%; organic matting powder 12.8%; fumed silica 0.3%; dispersant 0.2%; defoamer 0.2%; leveling agent 0.2%.
  • the graphene powder is added to a sodium benzene sulfonate ethanol solution having a mass fraction of 1%, wherein the ratio of the weight of the graphene powder to the volume of the 1% sodium alkylbenzene sulfonate solution is 1.5.
  • g 60 ml, stirred at a stirring speed of 300 r / min for 25 min, and sonicated for 25 min, to obtain activated graphene powder;
  • the activated graphene powder is mixed with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole, dispersant, antifoaming agent and leveling agent, and stirred at a stirring speed of 1200 r/min. After processing for 25 minutes, a preliminary material of the graphene liquid raw material mixture is obtained;
  • the rutile type titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the starting material of the graphene liquid raw material mixture, stirred for 25 minutes and ground to be uniformly dispersed, and then the organic digestive powder and fumed silica are added thereto at 1000 r/ The mixture was stirred for 25 min at a stirring speed of min, and uniformly mixed to obtain a first component.
  • the graphene heavy anti-corrosion and environmentally-friendly hard repair coating can be obtained, wherein the first component and the second component are obtained.
  • the mass ratio is 3.3:1.
  • the prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating was manually brushed on the surface of the hot-dip galvanized steel sheet, and the thickness of the coating was 200-380 ⁇ m after manual brushing.
  • the test results were as follows:
  • Table 1 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 1 was manually brushed on the surface of the hot-dip galvanized steel sheet.
  • Polyaspartate resin 53% (F53027%, Desmophen 152026%); N-carboxymethyl-N-methylpyrrole 2.5%; graphene powder 0.5%; zinc phosphate 10%; rutile titanium dioxide 14.75% Molecular sieve activated powder 4%; organic digestive powder 14%; fumed silica 0.5%; dispersant 0.25%; defoamer 0.25%; leveling agent 0.25%.
  • the graphene powder is added to a 1% sodium polyacrylate ethanol solution, wherein the ratio of the weight of the graphene powder to the volume of the 1% sodium polyacrylate solution is 2 g: 60 ml, stirring at 400 r/min. Stirring at a speed of 20 min, and sonicating for 20 min, to obtain activated graphene powder;
  • the rutile type titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the starting material of the graphene liquid raw material mixture, stirred for 20 min and ground to make it evenly dispersed, and then the organic digestive powder and fumed silica are added thereto at 1200 r/ The mixture was stirred for 20 min at a stirring speed of min, and uniformly mixed to obtain a first component.
  • the graphene heavy anti-corrosion and environmentally-friendly hard repair coating can be obtained, wherein the first component and the second component are obtained.
  • the mass ratio is 3.5:1.
  • the prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating was manually brushed on the surface of the hot-dip galvanized steel sheet, and the thickness of the coating after manual brushing was 220-350 ⁇ m.
  • the test results were as follows:
  • Polyaspartate resin 50% (Desmophen 1420 or F420); N-carboxymethyl-N-methylpyrrole 3.5%; graphene powder 0.6%; modified aluminum tripolyphosphate 18%; rutile titanium dioxide 9.9%; phthalocyanine green 3%; molecular sieve activated powder 2%; organic digestive powder 12%; fumed silica 0.4%; dispersant 0.2%; defoamer 0.2%; leveling agent 0.2%.
  • the activated graphene powder is mixed with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole, dispersant, antifoaming agent and leveling agent, and stirred at a stirring speed of 800 r/min. After processing for 30 minutes, a preliminary material of the graphene liquid raw material mixture is obtained;
  • the rutile type titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the starting material of the graphene liquid raw material mixture, stirred for 30 min and ground to make it evenly dispersed, and then the organic digestive powder and fumed silica are added thereto at 900 r/ After stirring at a stirring speed of min for 30 min, the mixture was uniformly mixed to obtain a first component.
  • the graphene heavy anti-corrosion and environmentally-friendly hard repair coating can be obtained, wherein the first component and the second component are obtained.
  • the mass ratio is 3.8:1.
  • the prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating is hand-made on the surface of the hot-dip galvanized steel sheet. After brushing and coating, the thickness of the coating after hand brushing is 200-350 ⁇ m.
  • the test results are as follows:
  • Table 3 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 3 was manually brushed on the surface of the hot-dip galvanized steel sheet.
  • Polyaspartate resin 55% (Desmophen 1220 or F220); N-carboxymethyl-N-methylpyrrole 4%; graphene powder 1%; modified aluminum tripolyphosphate 16.4%; rutile titanium dioxide 2%; iron oxide yellow 1%; molecular sieve activated powder 5%; organic digestive powder 15%; fumed silica 0.2%; dispersant 0.13%; defoamer 0.13%; leveling agent 0.13%.
  • the activated graphene powder is mixed with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole, dispersant, antifoaming agent and leveling agent, and stirred at a stirring speed of 1500 r/min. After processing for 20 minutes, a preliminary material of the graphene liquid raw material mixture is obtained;
  • the rutile type titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the starting material of the graphene liquid raw material mixture, stirred for 20 min and ground to make it evenly dispersed, and then the organic digestive powder and fumed silica are added thereto at 1500 r/ The mixture was stirred for 20 min at a stirring speed of min, and uniformly mixed to obtain a first component.
  • the graphene heavy anti-corrosion and environmentally-friendly hard repair coating can be obtained, wherein the first component and the second component are obtained.
  • the quality ratio is 4:1.
  • the prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating was hand-brushed on the surface of the hot-dip galvanized steel sheet, and the thickness of the coating after manual brushing was 220-380 ⁇ m.
  • the test results were as follows:
  • Table 4 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 4 was manually brushed on the surface of the hot-dip galvanized steel sheet.
  • Polyaspartate resin 40% (Desmophen 1520 or F520); N-carboxymethyl-N-methylpyrrole 4%; graphene powder 0.2%; modified aluminum tripolyphosphate 20%; rutile titanium dioxide 5%; permanent solid red 5%; permanent solid yellow 5%; organic matting powder 15%; molecular sieve activated powder 4.4%; fumed silica 0.6%; dispersant 0.27%; defoamer 0.27%; leveling agent 0.27% .
  • the activated graphene powder is mixed with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole, dispersant, antifoaming agent and leveling agent, and stirred at a stirring speed of 900 r/min. After processing for 30 minutes, a preliminary material of the graphene liquid raw material mixture is obtained;
  • the rutile titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the preliminary material of the graphene liquid raw material mixture, stirred for 30 min and ground to make it evenly dispersed, and then the organic digestive powder and fumed silica are added thereto at 800 r/ After stirring at a stirring speed of min for 30 min, the mixture was uniformly mixed to obtain a first component.
  • the prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating was hand-brushed on the surface of the hot-dip galvanized steel sheet, and the thickness of the coating after manual brushing was 220-380 ⁇ m.
  • the test results were as follows:
  • Table 5 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 5 was manually brushed on the surface of the hot-dip galvanized steel sheet.
  • the graphene heavy anti-corrosion environmental protection hard repairing coating of the embodiment of the invention does not contain organic volatile solvent, almost odorless, non-hazardous chemicals, primer and topcoat are combined into one, no need to apply primer, and excellent anti-corrosion and weather resistance performance.
  • Pencil hardness of more than 3H, excellent adhesion and impact resistance can be normally constructed above -10 °C, dry quickly, easy to construct; not only strong adhesion to galvanized steel substrate, but also It is suitable for single-layer heavy-duty anti-corrosion hard repair coating for repairing metal substrates such as cold-rolled steel sheets, aluminum alloys and magnesium alloys.

Description

一种石墨烯重防腐环保硬质修补涂料及其制备方法Graphene heavy anti-corrosion environmental protection hard repair coating and preparation method thereof 技术领域Technical field
本发明涉及一种石墨烯重防腐涂料,尤其涉及一种石墨烯重防腐环保硬质修补涂料,属于有机涂料领域。The invention relates to a graphene heavy anti-corrosion coating, in particular to a graphene heavy anti-corrosion environmental protection hard repair coating, belonging to the field of organic coatings.
背景技术Background technique
户外金属基材表面的重防腐涂层修补通常会采用修补油漆,修补油漆一般包括底漆和面漆,底漆通常为溶剂型环氧涂料,面漆一般为脂肪族丙烯酸聚氨酯涂料,底漆保证与金属底材的附着力和防腐蚀性,面漆提供外观和耐候性,但修补时需严格处理基材,先涂底漆,表干后再涂面漆,修补周期长,一般需要至少2次涂覆,中间还有至少几十分钟的底漆表干等待时间,不太适合野外修补的快捷性要求;而且属于危险化学品,国际范围内运输难度大、成本高。Heavy-duty anti-corrosion coatings on the surface of outdoor metal substrates are usually repaired with paints. Primers and primers are usually used for repairing paints. Primers are usually solvent-based epoxy coatings. Topcoats are generally aliphatic acrylic polyurethane coatings. Primer is guaranteed. The adhesion and corrosion resistance of the metal substrate, the topcoat provides appearance and weather resistance, but the substrate needs to be strictly treated during the repair, the primer is applied first, the topcoat is applied after the surface is dried, and the repair cycle is long, generally requires at least 2 Sub-coating, with at least tens of minutes of primer drying time in the middle, is not suitable for the quickness of field repair; and it is a dangerous chemical, which is difficult to transport and costly in the international scope.
虽然水性油漆更加环保,但是现有的水性修补油漆通常对金属基材表面的环境湿度要求较高,环境相对湿度要求不高于80%且无法在低于10℃的环境中正常干燥成膜或需要几个小时的时间才能完全干燥,同时水性油漆的耐水性、耐湿热、耐盐雾性能较差,严重影响了水性修补油漆在户外设备重防腐领域的推广和使用。Although water-based paints are more environmentally friendly, existing water-based paints generally require higher environmental humidity on the surface of metal substrates, environmental relative humidity requirements of not more than 80%, and inability to dry or film normally in environments below 10 ° C or It takes several hours to completely dry, and the water-resistant paint has poor water resistance, damp heat resistance and salt spray resistance, which seriously affects the promotion and use of water-based repair paint in the field of heavy-duty anti-corrosion of outdoor equipment.
近年来,聚脲弹性涂料在防腐、耐磨、防水等领域发展迅速并得到广泛应用,虽然表现出优越的性能,但在野外作为修补涂料使用存在不少问题,例如反应速度过快凝胶时间只有几秒到十几秒,对金属基材的浸润性不好,附着力极差,还需要专门的喷涂设备,对于小面积或不规则需要手工刷涂的表面无法施工等不足,即便是被称为第三代聚脲的聚天门冬氨酸酯聚脲弹性涂料,对镀锌钢板户外设备金属基材及原位涂层的附着力也极 差,需要与底漆配套使用,由于镀锌板存在氧化锌、氢氧化锌,常规聚天门冬氨酸酯聚脲涂料附着力极差,无法保证镀锌钢板户外设备的修补效果。In recent years, polyurea elastic coatings have developed rapidly in the fields of anti-corrosion, wear-resisting, waterproof, etc., and have been widely used. Although they have superior performance, there are many problems in the field as repair coatings, such as too fast reaction time. Only a few seconds to a dozen seconds, the wettability to the metal substrate is not good, the adhesion is very poor, and special spraying equipment is needed. For small areas or irregular surfaces that need to be manually brushed, it is impossible to construct, even if it is The polyaspartic acid ester polyurea elastic coating called the third generation polyurea has excellent adhesion to the metal substrate and in-situ coating of the outdoor equipment of galvanized steel sheet. Poor, need to be used with the primer, due to the presence of zinc oxide and zinc hydroxide in the galvanized sheet, the adhesion of the conventional polyaspartic acid polyurea coating is extremely poor, and the repairing effect of the outdoor equipment of the galvanized steel sheet cannot be guaranteed.
石墨烯独特的性能展现了其在金属材料防腐领域的巨大潜力。首先,石墨烯稳定的sp2杂化结构使其能在金属与活性介质间形成物理阻隔层,阻止扩散渗透的进行;其次,石墨烯具有很好的热稳定性和化学稳定性,不论是在高温条件下(可高达1500℃),还是在具有腐蚀或氧化性的气体、液体环境中均能保持稳定。另外,石墨烯良好的导电、导热性能对金属在腐蚀环境下的服役的环境提供了有利条件。因此,利用石墨烯复合材料制备的修补涂料能够极大提升涂料的防腐能力。The unique properties of graphene demonstrate its enormous potential in the field of corrosion protection of metallic materials. First, the stable sp2 hybrid structure of graphene makes it possible to form a physical barrier between the metal and the active medium to prevent diffusion and penetration. Secondly, graphene has good thermal and chemical stability, both at high temperatures. Under conditions (up to 1500 ° C), it can remain stable in corrosive or oxidizing gases and liquids. In addition, the good electrical and thermal conductivity of graphene provides favorable conditions for the service environment of metals in corrosive environments. Therefore, the repair coating prepared by using the graphene composite material can greatly improve the corrosion resistance of the coating.
发明内容Summary of the invention
本发明实施例针对现有修补涂料技术的不足,提供一种方便野外作业快捷修复设备金属基材表面涂层损伤或腐蚀的石墨烯重防腐环保硬质修补涂料,本发明实施例的石墨烯重防腐环保硬质修补涂料不含有机挥发溶剂,几乎无气味,非危险化学品,实现底漆、面漆合二为一,无需刷涂底漆,防腐耐候性能优异,铅笔硬度达3H以上,附着力耐冲击性能优异,可在-10℃以上正常施工,干燥迅速,施工简便;不仅对镀锌钢板基材附着力强,还适用于冷轧钢板、铝合金、镁合金等金属基材修补的单层重防腐硬质修补涂料。The embodiment of the present invention provides a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating which is convenient for repairing and corrosion of a metal substrate surface coating in a field repairing device, and the graphene heavy weight of the embodiment of the present invention. Anti-corrosion and environmental protection hard repair coating does not contain organic volatile solvent, almost odorless, non-hazardous chemicals, achieve primer and topcoat in one, no need to brush primer, excellent anti-corrosion and weather resistance, pencil hardness of more than 3H, attached Excellent impact resistance, normal construction above -10 °C, rapid drying, simple construction; not only strong adhesion to galvanized steel substrate, but also suitable for repair of cold-rolled steel, aluminum alloy, magnesium alloy and other metal substrates Single layer heavy anti-corrosion hard repair coating.
为达到上述目的,本发明实施例一方面提供一种石墨烯重防腐环保硬质修补涂料,其中,由第一组分和第二组分构成;In order to achieve the above object, an embodiment of the present invention provides a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating, wherein the first component and the second component are formed;
所述第一组分包括:聚天门冬氨酸酯树脂、N-羧甲基N-甲基吡咯以及石墨烯粉体;The first component comprises: polyaspartate resin, N-carboxymethyl N-methylpyrrole and graphene powder;
所述第二组分为HDI三聚体固化剂;The second component is an HDI trimer curing agent;
其中,所述第一组分和第二组分的质量之比为3-4:1。Wherein the mass ratio of the first component to the second component is 3-4:1.
上述方案中,所述聚天门冬氨酸酯树脂、N-羧甲基N-甲基吡咯以及石 墨烯粉体的质量之比为45-55:2-4:0.2-1。In the above scheme, the polyaspartate resin, N-carboxymethyl N-methylpyrrole and stone The mass ratio of the ocene powder is 45-55: 2-4: 0.2-1.
上述方案中,所述第一组分还包括:防锈颜料、着色颜料、分子筛活化粉、有机消化粉、流变助剂和其它助剂。In the above solution, the first component further comprises: an anti-rust pigment, a coloring pigment, a molecular sieve activated powder, an organic digestive powder, a rheological additive and other auxiliary agents.
上述方案中,所述防锈颜料、着色颜料、分子筛活化粉、有机消化粉、流变助剂和其它助剂的质量之比为10-20:3-15:2-5:0-15:0.2-0.6:0.4-0.8。In the above solution, the mass ratio of the anti-rust pigment, the coloring pigment, the molecular sieve activated powder, the organic digestive powder, the rheological additive and other auxiliary agents is 10-20:3-15:2-5:0-15: 0.2-0.6: 0.4-0.8.
上述方案中,所述石墨烯粉体为由多层单层石墨烯构成的石墨烯片层粉体,本发明实施例的石墨烯粉体均匀的分散在基础树脂和其它助剂当中,可以提升修补涂料的环境稳定性和综合防腐能力。In the above solution, the graphene powder is a graphene sheet powder composed of a plurality of layers of single-layer graphene, and the graphene powder of the embodiment of the invention is uniformly dispersed in the base resin and other additives, and can be improved. Repair the environmental stability and comprehensive corrosion resistance of the coating.
上述方案中,所述石墨烯片层粉体的层数为1-10层。In the above aspect, the number of layers of the graphene sheet powder is 1-10 layers.
上述方案中,所述石墨烯粉体在使用前先经表面活性剂的乙醇溶液活化处理,再用于制备所述石墨烯重防腐环保硬质修补涂料。In the above solution, the graphene powder is activated by an ethanol solution of a surfactant before use, and is used to prepare the graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating.
上述方案中,所述用于处理石墨烯粉体的表面活性剂乙醇溶液的质量分数为1%。In the above embodiment, the mass fraction of the surfactant ethanol solution for treating the graphene powder is 1%.
上述方案中,所述表面活性剂为烷基苯磺酸钠、聚丙烯酸钠、海藻酸钠和硬脂酸钠中的一种或几种,用于对石墨烯的表面改性,改变石墨烯的表面能、增加其分散性能。In the above solution, the surfactant is one or more of sodium alkylbenzenesulfonate, sodium polyacrylate, sodium alginate and sodium stearate, used for surface modification of graphene, changing graphene Surface energy, increasing its dispersion properties.
上述方案中,所述防锈颜料为磷酸锌和/或改性三聚磷酸铝,防锈颜料不仅可以提高修补涂料对镀锌钢板的附着力,还可以增加修补涂料的综合防腐能力。In the above solution, the anti-rust pigment is zinc phosphate and/or modified aluminum tripolyphosphate, and the anti-rust pigment can not only improve the adhesion of the repair coating to the galvanized steel sheet, but also increase the comprehensive anti-corrosion ability of the repair coating.
上述方案中,所述着色颜料为高耐候性的无机颜料或有机颜料,包括但不限于:金红石型钛白粉、高色素炭黑、氧化铁红、氧化铁黄、铬黄、酞菁蓝、酞菁绿、永固红、永固黄、永固紫等,用于获得修补所需的外观颜色。In the above solution, the coloring pigment is a high weathering inorganic pigment or organic pigment, including but not limited to: rutile titanium dioxide, high pigment carbon black, iron oxide red, iron oxide yellow, chrome yellow, phthalocyanine blue, lanthanum Cyanine green, permanent red, permanent yellow, permanent solid purple, etc., used to obtain the appearance color required for repair.
上述方案中,所述分子筛活化粉为3A、4A、5A分子筛活化粉的一种或几种,分子筛活化粉的加入可以除去涂料体系中的水分,提高涂层质量, 避免起泡,节约固化时间。In the above solution, the molecular sieve activated powder is one or more of 3A, 4A, 5A molecular sieve activated powder, and the addition of the molecular sieve activated powder can remove the moisture in the coating system and improve the coating quality. Avoid foaming and save curing time.
上述方案中,所述有机消化粉为改性脲聚合物粉末,有机消化粉的加入可以降低光泽度,使涂料与标准样板更接近。In the above solution, the organic digestive powder is a modified urea polymer powder, and the addition of the organic digestive powder can reduce the gloss and make the coating closer to the standard template.
上述方案中,所述流变助剂为有机硅酮改性的气相二氧化硅,具有防沉淀和放流挂的作用。In the above solution, the rheology aid is an organosilicone modified fumed silica, which has the functions of anti-precipitation and discharge.
上述方案中,所述其它助剂包括:分散剂、消泡剂和流平剂。In the above scheme, the other auxiliary agent includes a dispersing agent, an antifoaming agent and a leveling agent.
上述方案中,所述分散剂、消泡剂和流平剂的质量之比为1:1:1。In the above scheme, the mass ratio of the dispersant, the antifoaming agent and the leveling agent is 1:1:1.
上述方案中,所述分散剂,主要化学成分为长链多元羧酸和多元醇的预聚物,作用是提高颜料的分散性、稳定性。In the above solution, the dispersing agent, the main chemical component is a prepolymer of a long-chain polycarboxylic acid and a polyhydric alcohol, and functions to improve the dispersibility and stability of the pigment.
上述方案中,所述消泡剂成分为改性聚二甲基硅氧烷,作用是消除涂料生产过程中的气泡。In the above solution, the antifoaming agent component is a modified polydimethylsiloxane, which functions to eliminate bubbles in the production process of the coating.
上述方案中,所述流平剂为聚醚改性聚二甲基硅氧烷,作用是降低涂料表面张力,避免缩孔,提高涂层平整性。In the above solution, the leveling agent is a polyether modified polydimethylsiloxane, which functions to reduce the surface tension of the coating, avoid shrinkage, and improve the flatness of the coating.
上述方案中,所述聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯、石墨烯粉体、防锈颜料、着色颜料、分子筛活化粉、有机消化粉、流变助剂和其它助剂的质量百分比为:聚天门冬氨酸酯树脂45-55%;N-羧甲基-N-甲基吡咯2-4%;石墨烯粉体0.2-1%;防锈颜料10-20%;着色颜料3-15%;分子筛活化粉2-5%;有机消化粉0-15%;流变助剂0.2-0.6%;其它助剂0.4-0.8%。In the above scheme, the polyaspartate resin, N-carboxymethyl-N-methylpyrrole, graphene powder, anti-rust pigment, coloring pigment, molecular sieve activated powder, organic digestive powder, rheological additive And the mass percentage of other auxiliary agents are: 45-55% of polyaspartic acid ester resin; 2-4% of N-carboxymethyl-N-methylpyrrole; 0.2-1% of graphene powder; antirust pigment 10 -20%; coloring pigment 3-15%; molecular sieve activated powder 2-5%; organic digestive powder 0-15%; rheological additive 0.2-0.6%; other additives 0.4-0.8%.
上述配方中聚天门冬氨酸酯树脂和HDI三聚体固化剂是修补涂料的成膜物质,二者可以在室温下交联成坚韧、耐候性优越的涂膜,N-羧甲基N-甲基吡咯是多功能添加剂,有增韧效果,还可以溶解分散钢铁表面的金属氧化物,提高涂料在金属基材的附着力。In the above formula, the polyaspartic acid ester resin and the HDI trimer curing agent are film-forming substances of the repair coating, and the two can be crosslinked at room temperature to form a coating film having excellent toughness and weather resistance, N-carboxymethyl N- Methylpyrrole is a multifunctional additive that has a toughening effect and also dissolves metal oxides that disperse the steel surface to improve the adhesion of the coating to the metal substrate.
本发明实施例另一方面提供一种石墨烯重防腐环保硬质修补涂料的制备方法,包括: Another aspect of the present invention provides a method for preparing a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating, comprising:
将包含聚天门冬氨酸酯树脂、N-羧甲基N-甲基吡咯以及石墨烯粉体的原料混合搅拌处理,制得第一组分;The raw material comprising polyaspartic acid ester resin, N-carboxymethyl N-methylpyrrole and graphene powder is mixed and stirred to obtain a first component;
将作为第二组分的HDI三聚体固化剂加入到所述第一组分中,搅拌均匀,即得。An HDI trimer curing agent as a second component is added to the first component, and the mixture is uniformly stirred.
其中,所述第一组分和第二组分的质量之比为3-4:1。Wherein the mass ratio of the first component to the second component is 3-4:1.
上述方案中,所述的将包含聚天门冬氨酸酯树脂、N-羧甲基N-甲基吡咯以及石墨烯粉体的原料混合搅拌处理,制得第一组分包括:In the above aspect, the raw material comprising the polyaspartic acid ester resin, the N-carboxymethyl N-methylpyrrole and the graphene powder is mixed and stirred to obtain the first component comprising:
将石墨烯粉体加入到表面活性剂乙醇溶液中,对其进行搅拌及超声处理,抽滤、干燥后,制得活化后的石墨烯粉体;The graphene powder is added to the surfactant ethanol solution, stirred and sonicated, filtered and dried to obtain an activated graphene powder;
将所述活化后的石墨烯粉体与聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯和其它助剂搅拌均匀,制得石墨烯液体原料混合物初料;The activated graphene powder is uniformly stirred with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole and other auxiliary agents to prepare a preliminary material of the graphene liquid raw material mixture;
将着色颜料、防锈颜料、分子筛活化粉、有机消化粉和流变助剂加入所述石墨烯液体原料混合物初料中,边加边搅拌,使其混合均匀,制得第一组分。The coloring pigment, the rust preventive pigment, the molecular sieve activated powder, the organic digestive powder and the rheological assistant are added to the preliminary material of the graphene liquid raw material mixture, stirred and uniformly mixed to obtain a first component.
其中,所述表面活性剂乙醇溶液的质量分数为1%。Wherein, the mass fraction of the surfactant ethanol solution is 1%.
上述方案中,所述石墨烯粉体的重量和表面活性剂乙醇溶液的体积之比为1-2g:50-100ml。In the above embodiment, the ratio of the weight of the graphene powder to the volume of the surfactant ethanol solution is 1-2 g: 50-100 ml.
上述方案中,对所述石墨烯粉体和表面活性剂乙醇溶液进行搅拌处理的搅拌时间为20-30min,搅拌速度为200-600r/min。In the above embodiment, the stirring time of the graphene powder and the surfactant ethanol solution is 20-30 min, and the stirring speed is 200-600 r/min.
上述方案中,对所述石墨烯粉体和表面活性剂进行超声处理的处理时间为20-30min。In the above scheme, the treatment time for sonicating the graphene powder and the surfactant is 20-30 min.
上述方案中,制得石墨烯液体原料混合物初料的搅拌时间为20-30min,搅拌速度为800-1500r/min。In the above scheme, the stirring time of the preliminary material of the graphene liquid raw material mixture is 20-30 min, and the stirring speed is 800-1500 r/min.
上述方案中,先将所述着色颜料、防锈颜料和分子筛活化粉加入到所述石墨烯液体原料混合物初料中,搅拌20-30min并研磨,使其分散均匀, 再将所述有机消化粉和流变助剂加入其中,在800-1500r/min的搅拌速度下搅拌20-30min,使其混合均匀,制得所述第一组分。In the above solution, the coloring pigment, the rust preventive pigment and the molecular sieve activated powder are first added to the preliminary material of the graphene liquid raw material mixture, stirred for 20-30 min and ground to uniformly disperse. The organic digestive powder and the rheological assistant are further added thereto, stirred at a stirring speed of 800 to 1500 r/min for 20 to 30 minutes, and uniformly mixed to obtain the first component.
将HDI三聚体固化剂加入到已经混合均匀的第一组分中,搅拌混合均匀,即可制得石墨烯重防腐环保硬质修补涂料。The HDI trimer curing agent is added to the first component which has been uniformly mixed, and the mixture is uniformly stirred to obtain a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating.
上述方案中,所述聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯、石墨烯粉体、防锈颜料、着色颜料、分子筛活化粉、有机消化粉、流变助剂和其它助剂的质量百分比为:聚天门冬氨酸酯树脂45-55%;N-羧甲基-N-甲基吡咯2-4%;石墨烯粉体0.2-1%;防锈颜料10-20%;着色颜料3-15%;分子筛活化粉2-5%;有机消化粉0-15%;流变助剂0.2-0.6%;其它助剂0.4-0.8%。In the above scheme, the polyaspartate resin, N-carboxymethyl-N-methylpyrrole, graphene powder, anti-rust pigment, coloring pigment, molecular sieve activated powder, organic digestive powder, rheological additive And the mass percentage of other auxiliary agents are: 45-55% of polyaspartic acid ester resin; 2-4% of N-carboxymethyl-N-methylpyrrole; 0.2-1% of graphene powder; antirust pigment 10 -20%; coloring pigment 3-15%; molecular sieve activated powder 2-5%; organic digestive powder 0-15%; rheological additive 0.2-0.6%; other additives 0.4-0.8%.
其中,所述石墨烯粉体为由多层单层石墨烯构成的石墨烯片层粉体,本发明实施例的石墨烯粉体均匀的分散在基础树脂和其它助剂当中,可以提升修补涂料的环境稳定性和综合防腐能力。Wherein, the graphene powder is a graphene sheet powder composed of a plurality of layers of single-layer graphene, and the graphene powder of the embodiment of the invention is uniformly dispersed in the base resin and other additives, and the repair coating can be improved. Environmental stability and comprehensive corrosion resistance.
上述方案中,所述石墨烯片层粉体的层数为1-10层。In the above aspect, the number of layers of the graphene sheet powder is 1-10 layers.
上述方案中,所述表面活性剂为烷基苯磺酸钠、聚丙烯酸钠、海藻酸钠和硬脂酸钠中的一种或几种,用于对石墨烯的表面改性,改变石墨烯的表面能、增加其分散性能。In the above solution, the surfactant is one or more of sodium alkylbenzenesulfonate, sodium polyacrylate, sodium alginate and sodium stearate, used for surface modification of graphene, changing graphene Surface energy, increasing its dispersion properties.
上述方案中,所述防锈颜料为磷酸锌和/或改性三聚磷酸铝,防锈颜料不仅可以提高修补涂料对镀锌钢板的附着力,还可以增加修补涂料的综合防腐能力。In the above solution, the anti-rust pigment is zinc phosphate and/or modified aluminum tripolyphosphate, and the anti-rust pigment can not only improve the adhesion of the repair coating to the galvanized steel sheet, but also increase the comprehensive anti-corrosion ability of the repair coating.
上述方案中,所述着色颜料为高耐候性的无机颜料或有机颜料,包括但不限于:金红石型钛白粉、高色素炭黑、氧化铁红、氧化铁黄、铬黄、酞菁蓝、酞菁绿、永固红、永固黄、永固紫等,用于获得修补所需的外观颜色。In the above solution, the coloring pigment is a high weathering inorganic pigment or organic pigment, including but not limited to: rutile titanium dioxide, high pigment carbon black, iron oxide red, iron oxide yellow, chrome yellow, phthalocyanine blue, lanthanum Cyanine green, permanent red, permanent yellow, permanent solid purple, etc., used to obtain the appearance color required for repair.
上述方案中,所述分子筛活化粉为3A、4A、5A分子筛活化粉的一种 或几种,分子筛活化粉的加入可以除去涂料体系中的水分,提高涂层质量,避免起泡,节约固化时间。In the above solution, the molecular sieve activated powder is a kind of 3A, 4A, 5A molecular sieve activated powder. Or several kinds of molecular sieve activated powder can remove the moisture in the coating system, improve the coating quality, avoid foaming, and save curing time.
上述方案中,所述有机消化粉为为改性脲聚合物粉末,有机消化粉的加入可以降低光泽度,使涂料与标准样板更接近。In the above solution, the organic digestive powder is a modified urea polymer powder, and the addition of the organic digestive powder can reduce the gloss and make the coating closer to the standard template.
上述方案中,所述流变助剂为有机硅酮改性的气相二氧化硅,具有防沉淀和放流挂的作用。In the above solution, the rheology aid is an organosilicone modified fumed silica, which has the functions of anti-precipitation and discharge.
上述方案中,所述其它助剂包括:分散剂、消泡剂和流平剂。In the above scheme, the other auxiliary agent includes a dispersing agent, an antifoaming agent and a leveling agent.
上述方案中,所述分散剂、消泡剂和流平剂的质量之比为1:1:1。In the above scheme, the mass ratio of the dispersant, the antifoaming agent and the leveling agent is 1:1:1.
上述方案中,所述分散剂,主要化学成分为长链多元羧酸和多元醇的预聚物,作用是提高颜料的分散性、稳定性。In the above solution, the dispersing agent, the main chemical component is a prepolymer of a long-chain polycarboxylic acid and a polyhydric alcohol, and functions to improve the dispersibility and stability of the pigment.
上述方案中,所述消泡剂成分为为改性聚二甲基硅氧烷,作用是消除涂料生产过程中的气泡。In the above solution, the antifoaming agent component is a modified polydimethylsiloxane, which functions to eliminate bubbles in the production process of the coating.
上述方案中,所述流平剂为聚醚改性聚二甲基硅氧烷,作用是降低涂料表面张力,避免缩孔,提高涂层平整性。In the above solution, the leveling agent is a polyether modified polydimethylsiloxane, which functions to reduce the surface tension of the coating, avoid shrinkage, and improve the flatness of the coating.
上述配方中聚天门冬氨酸酯和HDI三聚体固化剂是修补涂料的成膜物质,二者可以在室温下交联成坚韧、耐候性优越的涂膜,N-羧甲基N-甲基吡咯是多功能添加剂,有增韧效果,还可以溶解分散钢铁表面的金属氧化物,提高涂料在金属基材的附着力。The above-mentioned formulas of polyaspartate and HDI trimer curing agent are film-forming materials for refinishing coatings, which can be crosslinked at room temperature to form a coating film with excellent toughness and weather resistance, N-carboxymethyl N-A The pyrrole is a multifunctional additive that has a toughening effect and also dissolves metal oxides that disperse the steel surface to improve the adhesion of the coating to the metal substrate.
本发明实施例的优点和有益技术效果如下:The advantages and beneficial technical effects of the embodiments of the present invention are as follows:
1、本发明实施例的石墨烯重防腐环保硬质修补涂料不含有机挥发溶剂,几乎无气味,非危险化学品,非常适合用于户外设备锈蚀部分或破损涂层的修补。1. The graphene heavy-duty anti-corrosion environmentally-friendly hard repairing coating of the embodiment of the invention does not contain organic volatile solvent, is almost odorless, and is non-hazardous chemical, and is very suitable for repairing rusted parts or damaged coatings of outdoor equipment.
2、本发明实施例石墨烯重防腐环保硬质修补涂料的制备方法简单快捷,第一组分和第二组分混合均匀即可制得,无需长时间的固化,非常适合设计成小包装按普通物品携带和施工。 2. The preparation method of the graphene heavy-duty anti-corrosion environmental protection hard repairing coating of the embodiment of the invention is simple and quick, and the first component and the second component can be uniformly mixed, and the curing is not required for a long time, which is very suitable for designing into a small package. Carrying and construction of common items.
3、本发明实施例的石墨烯重防腐环保硬质修补涂料底漆、面漆合二为一,无需刷涂底漆,防腐耐候性能优异,铅笔硬度达3H以上,附着力耐冲击性能优异,可在-10℃以上正常施工,可以方便快捷的修复金属原破损涂层或生锈区域,干燥迅速,1h之内即表干完全,性能优良。3. The graphene heavy anti-corrosion environmental protection hard repair paint primer and top coat are combined into one, no need to apply primer, excellent anti-corrosion and weather resistance, pencil hardness of more than 3H, excellent adhesion and impact resistance. It can be normally constructed above -10 °C, which can repair the damaged coating or rusted area of metal directly and quickly. It can be dried quickly, and the surface is completely dry within 1h, and the performance is excellent.
4、本发明实施例的石墨烯重防腐环保硬质修补涂料不仅可以修补镀锌板、冷轧钢板、铝合金板等金属基材原有涂层,包括:户外粉末涂层、氨基烘烤涂层、聚氨酯涂层等;还可以直接对金属基材进行手工刷涂,对镀锌钢板基材附着力强,对冷轧钢板、铝合金、镁合金等金属基材也表现出优异的附着力,适用范围广。4. The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating of the embodiment of the invention can not only repair the original coating of the metal substrate such as galvanized sheet, cold-rolled steel sheet or aluminum alloy sheet, including: outdoor powder coating and amino baking coating. Layer, polyurethane coating, etc.; can also directly brush the metal substrate, adhesion to galvanized steel substrate, and excellent adhesion to cold-rolled steel, aluminum alloy, magnesium alloy and other metal substrates. ,Wide range of applications.
5、本发明实施例的石墨烯重防腐环保硬质修补涂料在热镀锌钢板设备表面的附着力、耐水性、耐酸性、耐碱性、耐二氧化硫、耐盐雾、耐氙灯老化等性能也表现优异。5. The graphene heavy-duty anti-corrosion environmental protection hard repair coating of the embodiment of the invention has the adhesion, water resistance, acid resistance, alkali resistance, sulfur dioxide resistance, salt spray resistance and aging resistance of the xenon lamp on the surface of the hot-dip galvanized steel sheet equipment. Excellent performance.
具体实施方式detailed description
下面通过具体实施方式对本发明作进一步说明:The present invention is further described below by way of specific embodiments:
原料和试剂:本发明实施例中所用聚天门冬氨酸酯树脂为拜耳Desmophen 1420、Desmophen 1520,Desmophen 1220,珠海飞扬化工F420、F520、F530、F220中的一种或几种混合物;分子筛活化粉为3A、4A、5A分子筛活化粉;有机消化粉为圣源化工E-7;流变助剂为气相二氧化硅Cabot TS-720;分散剂为德国毕克公司BYK108;消泡剂为德高公司TEGO N;流平剂为上海泰科聚合物公司TECH-284;HDI三聚体固化剂为拜耳Desmodur N3600。Raw materials and reagents: The polyaspartic acid ester resin used in the examples of the present invention is one or a mixture of Bayer Desmophen 1420, Desmophen 1520, Desmophen 1220, Zhuhai Feiyang Chemical F420, F520, F530, F220; molecular sieve activated powder It is 3A, 4A, 5A molecular sieve activated powder; organic digestive powder is Shengyuan Chemical E-7; rheological additive is fumed silica Cabot TS-720; dispersing agent is BYK108 of German BYK; defoaming agent is Degao Company TEGO N; leveling agent is Shanghai Tyco Polymer Company TECH-284; HDI trimer curing agent is Bayer Desmodur N3600.
实施例1Example 1
制备一种石墨烯重防腐环保硬质修补涂料(浅灰)并对其涂刷结果进行测试: Prepare a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating (light gray) and test its coating results:
1、按照如下质量比备料:1. Prepare according to the following quality ratio:
聚天门冬氨酸酯树脂50%(Desmophen 142025%,Desmophen 152025%);N-羧甲基-N-甲基吡咯3%;石墨烯粉体0.8%;磷酸锌16%;金红石型钛白粉13%;分子筛活化粉3.5%;有机消光粉12.8%;气相二氧化硅0.3%;分散剂0.2%;消泡剂0.2%;流平剂0.2%。Polyaspartate resin 50% (Desmophen 142025%, Desmophen 152025%); N-carboxymethyl-N-methylpyrrole 3%; graphene powder 0.8%; zinc phosphate 16%; rutile titanium dioxide 13 %; molecular sieve activated powder 3.5%; organic matting powder 12.8%; fumed silica 0.3%; dispersant 0.2%; defoamer 0.2%; leveling agent 0.2%.
2、将石墨烯粉体加入到质量分数为1%的烷基苯磺酸钠乙醇溶液中,其中石墨烯粉体的重量和1%的烷基苯磺酸钠乙醇溶液的体积之比为1.5g:60ml,在300r/min的搅拌速度下搅拌25min,并超声处理25min,制得活化后的石墨烯粉体;2. The graphene powder is added to a sodium benzene sulfonate ethanol solution having a mass fraction of 1%, wherein the ratio of the weight of the graphene powder to the volume of the 1% sodium alkylbenzene sulfonate solution is 1.5. g: 60 ml, stirred at a stirring speed of 300 r / min for 25 min, and sonicated for 25 min, to obtain activated graphene powder;
将活化后的石墨烯粉体与聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯、分散剂、消泡剂和流平剂混合,在1200r/min的搅拌速度下搅拌处理25min,制得石墨烯液体原料混合物初料;The activated graphene powder is mixed with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole, dispersant, antifoaming agent and leveling agent, and stirred at a stirring speed of 1200 r/min. After processing for 25 minutes, a preliminary material of the graphene liquid raw material mixture is obtained;
先将金红石型钛白粉、磷酸锌和分子筛活化粉加入到石墨烯液体原料混合物初料中,搅拌25min并研磨,使其分散均匀,再将有机消化粉和气相二氧化硅加入其中,在1000r/min的搅拌速度下搅拌25min,使其混合均匀,制得第一组分。The rutile type titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the starting material of the graphene liquid raw material mixture, stirred for 25 minutes and ground to be uniformly dispersed, and then the organic digestive powder and fumed silica are added thereto at 1000 r/ The mixture was stirred for 25 min at a stirring speed of min, and uniformly mixed to obtain a first component.
3、将HDI三聚体固化剂加入到已经混合均匀的第一组分中,搅拌混合均匀,即可制得石墨烯重防腐环保硬质修补涂料,其中,第一组分与第二组分的质量之比为3.3:1。3. Adding the HDI trimer curing agent to the first component which has been uniformly mixed, and stirring and mixing uniformly, the graphene heavy anti-corrosion and environmentally-friendly hard repair coating can be obtained, wherein the first component and the second component are obtained. The mass ratio is 3.3:1.
将制得的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂制样,手工刷涂后涂层厚度为200-380μm,测试结果如下:The prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating was manually brushed on the surface of the hot-dip galvanized steel sheet, and the thickness of the coating was 200-380 μm after manual brushing. The test results were as follows:
表1 实施例1制备的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂测试结果Table 1 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 1 was manually brushed on the surface of the hot-dip galvanized steel sheet.
Figure PCTCN2016072300-appb-000001
Figure PCTCN2016072300-appb-000001
Figure PCTCN2016072300-appb-000002
Figure PCTCN2016072300-appb-000002
实施例2Example 2
制备一种石墨烯重防腐环保硬质修补涂料(浅灰)并对其涂刷结果进行测试:Prepare a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating (light gray) and test its coating results:
1、按照如下质量比备料:1. Prepare according to the following quality ratio:
聚天门冬氨酸酯树脂53%(F53027%,Desmophen 152026%);N-羧甲基-N-甲基吡咯2.5%;石墨烯粉体0.5%;磷酸锌10%;金红石型钛白粉14.75%;分子筛活化粉4%;有机消化粉14%;气相二氧化硅0.5%;分散剂0.25%;消泡剂0.25%;流平剂0.25%。Polyaspartate resin 53% (F53027%, Desmophen 152026%); N-carboxymethyl-N-methylpyrrole 2.5%; graphene powder 0.5%; zinc phosphate 10%; rutile titanium dioxide 14.75% Molecular sieve activated powder 4%; organic digestive powder 14%; fumed silica 0.5%; dispersant 0.25%; defoamer 0.25%; leveling agent 0.25%.
2、将石墨烯粉体加入到1%的聚丙烯酸钠乙醇溶液中,其中石墨烯粉体的重量和1%的聚丙烯酸钠的乙醇溶液体积之比为2g:60ml,在400r/min的搅拌速度下搅拌20min,并超声处理20min,制得活化后的石墨烯粉体;2. The graphene powder is added to a 1% sodium polyacrylate ethanol solution, wherein the ratio of the weight of the graphene powder to the volume of the 1% sodium polyacrylate solution is 2 g: 60 ml, stirring at 400 r/min. Stirring at a speed of 20 min, and sonicating for 20 min, to obtain activated graphene powder;
将活化后的石墨烯粉体与聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡 咯、分散剂、消泡剂和流平剂混合,在1000r/min的搅拌速度下搅拌处理20min,制得石墨烯液体原料混合物初料;Activated graphene powder with polyaspartate resin, N-carboxymethyl-N-methylpyridinium Mixing, dispersing agent, antifoaming agent and leveling agent, stirring and stirring at 1000r/min for 20min to prepare a preliminary material of the graphene liquid raw material mixture;
先将金红石型钛白粉、磷酸锌和分子筛活化粉加入到石墨烯液体原料混合物初料中,搅拌20min并研磨,使其分散均匀,再将有机消化粉和气相二氧化硅加入其中,在1200r/min的搅拌速度下搅拌20min,使其混合均匀,制得第一组分。The rutile type titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the starting material of the graphene liquid raw material mixture, stirred for 20 min and ground to make it evenly dispersed, and then the organic digestive powder and fumed silica are added thereto at 1200 r/ The mixture was stirred for 20 min at a stirring speed of min, and uniformly mixed to obtain a first component.
3、将HDI三聚体固化剂加入到已经混合均匀的第一组分中,搅拌混合均匀,即可制得石墨烯重防腐环保硬质修补涂料,其中,第一组分与第二组分的质量之比为3.5:1。3. Adding the HDI trimer curing agent to the first component which has been uniformly mixed, and stirring and mixing uniformly, the graphene heavy anti-corrosion and environmentally-friendly hard repair coating can be obtained, wherein the first component and the second component are obtained. The mass ratio is 3.5:1.
将制得的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂制样,手工刷涂后涂层厚度为220-350μm,测试结果如下:The prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating was manually brushed on the surface of the hot-dip galvanized steel sheet, and the thickness of the coating after manual brushing was 220-350 μm. The test results were as follows:
表2 实施例2制备的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂测试结果Table 2 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 2 was manually brushed on the surface of the hot-dip galvanized steel sheet.
Figure PCTCN2016072300-appb-000003
Figure PCTCN2016072300-appb-000003
Figure PCTCN2016072300-appb-000004
Figure PCTCN2016072300-appb-000004
实施例3Example 3
制备一种石墨烯重防腐环保硬质修补涂料(草绿色)并对其涂刷结果进行测试:Prepare a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating (grass green) and test its brushing results:
1、按照如下质量比备料:1. Prepare according to the following quality ratio:
聚天门冬氨酸酯树脂50%(Desmophen 1420或F420);N-羧甲基-N-甲基吡咯3.5%;石墨烯粉体0.6%;改性三聚磷酸铝18%;金红石型钛白粉9.9%;酞菁绿3%;分子筛活化粉2%;有机消化粉12%;气相二氧化硅0.4%;分散剂0.2%;消泡剂0.2%;流平剂0.2%。Polyaspartate resin 50% (Desmophen 1420 or F420); N-carboxymethyl-N-methylpyrrole 3.5%; graphene powder 0.6%; modified aluminum tripolyphosphate 18%; rutile titanium dioxide 9.9%; phthalocyanine green 3%; molecular sieve activated powder 2%; organic digestive powder 12%; fumed silica 0.4%; dispersant 0.2%; defoamer 0.2%; leveling agent 0.2%.
2、将石墨烯粉体加入到1%的海藻酸钠和硬质酸钠的乙醇溶液混合物中,其中石墨烯粉体的重量和1%的海藻酸钠和硬质酸钠的乙醇溶液体积之比为1g:80ml,在500r/min的搅拌速度下搅拌30min,并超声处理30min,制得活化后的石墨烯粉体;2. Add graphene powder to a mixture of 1% sodium alginate and sodium hard acid in ethanol solution, wherein the weight of the graphene powder and the volume of 1% sodium alginate and sodium hard acid in ethanol solution The ratio of 1g: 80ml, stirring at a stirring speed of 500r / min for 30min, and sonicating for 30min, to obtain activated graphene powder;
将活化后的石墨烯粉体与聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯、分散剂、消泡剂和流平剂混合,在800r/min的搅拌速度下搅拌处理30min,制得石墨烯液体原料混合物初料;The activated graphene powder is mixed with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole, dispersant, antifoaming agent and leveling agent, and stirred at a stirring speed of 800 r/min. After processing for 30 minutes, a preliminary material of the graphene liquid raw material mixture is obtained;
先将金红石型钛白粉、磷酸锌和分子筛活化粉加入到石墨烯液体原料混合物初料中,搅拌30min并研磨,使其分散均匀,再将有机消化粉和气相二氧化硅加入其中,在900r/min的搅拌速度下搅拌30min,使其混合均匀,制得第一组分。The rutile type titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the starting material of the graphene liquid raw material mixture, stirred for 30 min and ground to make it evenly dispersed, and then the organic digestive powder and fumed silica are added thereto at 900 r/ After stirring at a stirring speed of min for 30 min, the mixture was uniformly mixed to obtain a first component.
3、将HDI三聚体固化剂加入到已经混合均匀的第一组分中,搅拌混合均匀,即可制得石墨烯重防腐环保硬质修补涂料,其中,第一组分与第二组分的质量之比为3.8:1。3. Adding the HDI trimer curing agent to the first component which has been uniformly mixed, and stirring and mixing uniformly, the graphene heavy anti-corrosion and environmentally-friendly hard repair coating can be obtained, wherein the first component and the second component are obtained. The mass ratio is 3.8:1.
将制得的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工 刷涂制样,手工刷涂后涂层厚度为200-350μm,测试结果如下:The prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating is hand-made on the surface of the hot-dip galvanized steel sheet. After brushing and coating, the thickness of the coating after hand brushing is 200-350μm. The test results are as follows:
表3 实施例3制备的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂测试结果Table 3 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 3 was manually brushed on the surface of the hot-dip galvanized steel sheet.
Figure PCTCN2016072300-appb-000005
Figure PCTCN2016072300-appb-000005
实施例4Example 4
制备一种石墨烯重防腐环保硬质修补涂料(浅黄灰)并对其涂刷结果进行测试:Prepare a graphene heavy-duty anti-corrosion and environmentally-friendly hard repair coating (light yellow ash) and test its brushing results:
1、按照如下质量比备料:1. Prepare according to the following quality ratio:
聚天门冬氨酸酯树脂55%(Desmophen 1220或F220);N-羧甲基-N-甲基吡咯4%;石墨烯粉体1%;改性三聚磷酸铝16.4%;金红石型钛白粉2%;氧化铁黄1%;分子筛活化粉5%;有机消化粉15%;气相二氧化硅0.2%;分散剂0.13%;消泡剂0.13%;流平剂0.13%。Polyaspartate resin 55% (Desmophen 1220 or F220); N-carboxymethyl-N-methylpyrrole 4%; graphene powder 1%; modified aluminum tripolyphosphate 16.4%; rutile titanium dioxide 2%; iron oxide yellow 1%; molecular sieve activated powder 5%; organic digestive powder 15%; fumed silica 0.2%; dispersant 0.13%; defoamer 0.13%; leveling agent 0.13%.
2、将石墨烯粉体加入到1%的海藻酸钠和硬质酸钠的乙醇溶液中,其 中石墨烯粉体的重量和1%的海藻酸钠和硬质酸钠的乙醇溶液体积之比为2g:50ml,在600r/min的搅拌速度下搅拌20min,并超声处理20min,制得活化后的石墨烯粉体;2. Add graphene powder to 1% sodium alginate and sodium hard acid in ethanol solution, The ratio of the weight of the graphene powder to the volume of 1% sodium alginate and sodium carbonate in ethanol solution is 2g: 50ml, stirred at a stirring speed of 600r/min for 20min, and sonicated for 20min to obtain the activated Graphene powder;
将活化后的石墨烯粉体与聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯、分散剂、消泡剂和流平剂混合,在1500r/min的搅拌速度下搅拌处理20min,制得石墨烯液体原料混合物初料;The activated graphene powder is mixed with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole, dispersant, antifoaming agent and leveling agent, and stirred at a stirring speed of 1500 r/min. After processing for 20 minutes, a preliminary material of the graphene liquid raw material mixture is obtained;
先将金红石型钛白粉、磷酸锌和分子筛活化粉加入到石墨烯液体原料混合物初料中,搅拌20min并研磨,使其分散均匀,再将有机消化粉和气相二氧化硅加入其中,在1500r/min的搅拌速度下搅拌20min,使其混合均匀,制得第一组分。The rutile type titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the starting material of the graphene liquid raw material mixture, stirred for 20 min and ground to make it evenly dispersed, and then the organic digestive powder and fumed silica are added thereto at 1500 r/ The mixture was stirred for 20 min at a stirring speed of min, and uniformly mixed to obtain a first component.
3、将HDI三聚体固化剂加入到已经混合均匀的第一组分中,搅拌混合均匀,即可制得石墨烯重防腐环保硬质修补涂料,其中,第一组分与第二组分的质量之比为4:1。3. Adding the HDI trimer curing agent to the first component which has been uniformly mixed, and stirring and mixing uniformly, the graphene heavy anti-corrosion and environmentally-friendly hard repair coating can be obtained, wherein the first component and the second component are obtained. The quality ratio is 4:1.
将制得的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂制样,手工刷涂后涂层厚度为220-380μm,测试结果如下:The prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating was hand-brushed on the surface of the hot-dip galvanized steel sheet, and the thickness of the coating after manual brushing was 220-380 μm. The test results were as follows:
表4 实施例4制备的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂测试结果Table 4 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 4 was manually brushed on the surface of the hot-dip galvanized steel sheet.
Figure PCTCN2016072300-appb-000006
Figure PCTCN2016072300-appb-000006
Figure PCTCN2016072300-appb-000007
Figure PCTCN2016072300-appb-000007
实施例5Example 5
制备一种石墨烯重防腐环保硬质修补涂料(橙红色)并对其涂刷结果进行测试:Prepare a graphene heavy-duty anti-corrosion and environmentally-friendly hard repair coating (orange-red) and test its brushing results:
1、按照如下质量比备料:1. Prepare according to the following quality ratio:
聚天门冬氨酸酯树脂40%(Desmophen 1520或F520);N-羧甲基-N-甲基吡咯4%;石墨烯粉体0.2%;改性三聚磷酸铝20%;金红石型钛白粉5%;永固红5%;永固黄5%;有机消光粉15%;分子筛活化粉4.4%;气相二氧化硅0.6%;分散剂0.27%;消泡剂0.27%;流平剂0.27%。Polyaspartate resin 40% (Desmophen 1520 or F520); N-carboxymethyl-N-methylpyrrole 4%; graphene powder 0.2%; modified aluminum tripolyphosphate 20%; rutile titanium dioxide 5%; permanent solid red 5%; permanent solid yellow 5%; organic matting powder 15%; molecular sieve activated powder 4.4%; fumed silica 0.6%; dispersant 0.27%; defoamer 0.27%; leveling agent 0.27% .
2、将石墨烯粉体加入到1%的海藻酸钠和硬质酸钠的乙醇溶液中,其中石墨烯粉体的重量和1%的海藻酸钠和硬质酸钠的乙醇溶液体积之比为1g:100ml,在200r/min的搅拌速度下搅拌30min,并超声处理30min,制得活化后的石墨烯粉体;2. Add graphene powder to 1% sodium alginate and sodium hard acid in ethanol solution, wherein the weight of graphene powder and the ratio of 1% sodium alginate and sodium hard acid in ethanol solution 1 g: 100 ml, stirred at a stirring speed of 200 r / min for 30 min, and sonicated for 30 min, to obtain activated graphene powder;
将活化后的石墨烯粉体与聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯、分散剂、消泡剂和流平剂混合,在900r/min的搅拌速度下搅拌处理30min,制得石墨烯液体原料混合物初料;The activated graphene powder is mixed with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole, dispersant, antifoaming agent and leveling agent, and stirred at a stirring speed of 900 r/min. After processing for 30 minutes, a preliminary material of the graphene liquid raw material mixture is obtained;
先将金红石型钛白粉、磷酸锌和分子筛活化粉加入到石墨烯液体原料混合物初料中,搅拌30min并研磨,使其分散均匀,再将有机消化粉和气相二氧化硅加入其中,在800r/min的搅拌速度下搅拌30min,使其混合均匀,制得第一组分。The rutile titanium dioxide, zinc phosphate and molecular sieve activated powder are first added to the preliminary material of the graphene liquid raw material mixture, stirred for 30 min and ground to make it evenly dispersed, and then the organic digestive powder and fumed silica are added thereto at 800 r/ After stirring at a stirring speed of min for 30 min, the mixture was uniformly mixed to obtain a first component.
3、将HDI三聚体固化剂加入到已经混合均匀的第一组分中,搅拌混合 均匀,即可制得石墨烯重防腐环保硬质修补涂料,其中,第一组分与第二组分的质量之比为3:1。3. Add the HDI trimer curing agent to the first component that has been uniformly mixed, and mix and mix. Evenly, a graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating can be obtained, wherein the ratio of the mass of the first component to the second component is 3:1.
将制得的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂制样,手工刷涂后涂层厚度为220-380μm,测试结果如下:The prepared graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating was hand-brushed on the surface of the hot-dip galvanized steel sheet, and the thickness of the coating after manual brushing was 220-380 μm. The test results were as follows:
表5 实施例5制备的石墨烯重防腐环保硬质修补涂料在热镀锌钢板表面进行手工刷涂测试结果Table 5 The graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating prepared in Example 5 was manually brushed on the surface of the hot-dip galvanized steel sheet.
Figure PCTCN2016072300-appb-000008
Figure PCTCN2016072300-appb-000008
工业实用性Industrial applicability
本发明实施例的石墨烯重防腐环保硬质修补涂料不含有机挥发溶剂,几乎无气味,非危险化学品,底漆、面漆合二为一,无需刷涂底漆,防腐耐候性能优异,铅笔硬度达3H以上,附着力耐冲击性能优异,可在-10℃以上正常施工,干燥迅速,施工简便;不仅对镀锌钢板基材附着力强,还 适用于冷轧钢板、铝合金、镁合金等金属基材修补的单层重防腐硬质修补涂料。 The graphene heavy anti-corrosion environmental protection hard repairing coating of the embodiment of the invention does not contain organic volatile solvent, almost odorless, non-hazardous chemicals, primer and topcoat are combined into one, no need to apply primer, and excellent anti-corrosion and weather resistance performance. Pencil hardness of more than 3H, excellent adhesion and impact resistance, can be normally constructed above -10 °C, dry quickly, easy to construct; not only strong adhesion to galvanized steel substrate, but also It is suitable for single-layer heavy-duty anti-corrosion hard repair coating for repairing metal substrates such as cold-rolled steel sheets, aluminum alloys and magnesium alloys.

Claims (10)

  1. 一种石墨烯重防腐环保硬质修补涂料,由第一组分和第二组分构成:A graphene heavy-duty anti-corrosion environmentally-friendly hard repair coating consisting of a first component and a second component:
    所述第一组分包括:聚天门冬氨酸酯树脂、N-羧甲基N-甲基吡咯以及石墨烯粉体;The first component comprises: polyaspartate resin, N-carboxymethyl N-methylpyrrole and graphene powder;
    所述第二组分为HDI三聚体固化剂;The second component is an HDI trimer curing agent;
    其中,所述第一组分和第二组分的质量之比为3-4:1。Wherein the mass ratio of the first component to the second component is 3-4:1.
  2. 如权利要求1所述的涂料,其中,所述聚天门冬氨酸酯树脂、N-羧甲基N-甲基吡咯以及石墨烯粉体的质量之比为45-55:2-4:0.2-1。The coating according to claim 1, wherein the mass ratio of the polyaspartic acid ester resin, N-carboxymethyl N-methylpyrrole and graphene powder is 45-55: 2-4: 0.2 -1.
  3. 如权利要求1所述的涂料,其中,所述第一组分还包括:防锈颜料、着色颜料、分子筛活化粉、有机消化粉、流变助剂和其它助剂。The coating of claim 1 wherein said first component further comprises: a rust preventive pigment, a coloring pigment, a molecular sieve activated powder, an organic digestive powder, a rheological additive, and other auxiliaries.
  4. 如权利要求3所述的涂料,其中,所述防锈颜料、着色颜料、分子筛活化粉、有机消化粉、流变助剂和其它助剂的质量之比为10-20:3-15:2-5:0-15:0.2-0.6:0.4-0.8。The paint according to claim 3, wherein the ratio of the mass of the rust preventive pigment, the coloring pigment, the molecular sieve activated powder, the organic digestive powder, the rheological assistant and the other auxiliary agent is 10-20:3-15:2 -5:0-15: 0.2-0.6: 0.4-0.8.
  5. 如权利要求4所述的涂料,其中,所述聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯、石墨烯粉体、防锈颜料、着色颜料、分子筛活化粉、流变助剂和其它助剂的质量百分比为:聚天门冬氨酸酯树脂45-55%;N-羧甲基-N-甲基吡咯2-4%;石墨烯粉体0.2-1%;防锈颜料10-20%;着色颜料3-15%;分子筛活化粉2-5%;有机消化粉0-15%;流变助剂0.2-0.6%;其它助剂0.4-0.8%。The coating according to claim 4, wherein the polyaspartate resin, N-carboxymethyl-N-methylpyrrole, graphene powder, rust preventive pigment, coloring pigment, molecular sieve activated powder, stream The mass percentage of the variable auxiliary agent and other auxiliary agents are: 45-55% of polyaspartic acid ester resin; 2-4% of N-carboxymethyl-N-methylpyrrole; 0.2-1% of graphene powder; Rust pigment 10-20%; coloring pigment 3-15%; molecular sieve activated powder 2-5%; organic digestive powder 0-15%; rheological additive 0.2-0.6%; other additives 0.4-0.8%.
  6. 一种石墨烯重防腐环保硬质修补涂料的制备方法,包括:A preparation method of graphene heavy anti-corrosion environmental protection hard repair coating, comprising:
    将包含聚天门冬氨酸酯树脂、N-羧甲基N-甲基吡咯以及石墨烯粉体的原料混合搅拌处理,制得第一组分;The raw material comprising polyaspartic acid ester resin, N-carboxymethyl N-methylpyrrole and graphene powder is mixed and stirred to obtain a first component;
    将作为第二组分的HDI三聚体固化剂加入到所述第一组分中,搅拌均匀,即得。An HDI trimer curing agent as a second component is added to the first component, and the mixture is uniformly stirred.
  7. 如权利要求6所述的制备方法,其中,所述第一组分和第二组分的 质量之比为3-4:1。The production method according to claim 6, wherein the first component and the second component The mass ratio is 3-4:1.
  8. 如权利要求6所述的制备方法,其中,所述的将包含聚天门冬氨酸酯树脂、N-羧甲基N-甲基吡咯以及石墨烯粉体的原料混合搅拌处理,制得第一组分包括:The production method according to claim 6, wherein the raw material containing the polyaspartic acid ester resin, the N-carboxymethyl N-methylpyrrole, and the graphene powder is mixed and stirred to obtain the first Components include:
    将石墨烯粉体加入到表面活性剂的乙醇溶液中,对其进行搅拌及超声处理,抽滤、干燥后,制得活化后的石墨烯粉体;The graphene powder is added to the ethanol solution of the surfactant, stirred and sonicated, filtered and dried to obtain the activated graphene powder;
    将所述活化后的石墨烯粉体与聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯和其它助剂搅拌均匀,制得石墨烯液体原料混合物初料;The activated graphene powder is uniformly stirred with polyaspartic acid ester resin, N-carboxymethyl-N-methylpyrrole and other auxiliary agents to prepare a preliminary material of the graphene liquid raw material mixture;
    将着色颜料、防锈颜料、分子筛活化粉、有机消化粉和流变助剂加入所述石墨烯液体原料混合物初料中,边加边搅拌,使其混合均匀,制得第一组分。The coloring pigment, the rust preventive pigment, the molecular sieve activated powder, the organic digestive powder and the rheological assistant are added to the preliminary material of the graphene liquid raw material mixture, stirred and uniformly mixed to obtain a first component.
  9. 如权利要求8所述的制备方法,其中,所述聚天门冬氨酸酯树脂、N-羧甲基-N-甲基吡咯、石墨烯粉体、防锈颜料、着色颜料、分子筛活化粉、有机消化粉、流变助剂和其它助剂的质量百分比为:聚天门冬氨酸酯树脂45-55%;N-羧甲基-N-甲基吡咯2-4%;石墨烯粉体0.2-1%;防锈颜料10-20%;着色颜料3-15%;分子筛活化粉2-5%;有机消化粉0-15%;流变助剂0.2-0.6%;其它助剂0.4-0.8%。The production method according to claim 8, wherein the polyaspartate resin, N-carboxymethyl-N-methylpyrrole, graphene powder, rust preventive pigment, coloring pigment, molecular sieve activated powder, The mass percentage of organic digestive powder, rheological assistant and other auxiliaries is: 45-55% of polyaspartate resin; 2-4% of N-carboxymethyl-N-methylpyrrole; graphene powder 0.2 -1%; anti-rust pigment 10-20%; coloring pigment 3-15%; molecular sieve activated powder 2-5%; organic digestive powder 0-15%; rheological additive 0.2-0.6%; other additives 0.4-0.8 %.
  10. 如权利要求8所述的制备方法,其中,所述表面活性剂为烷基苯磺酸钠、聚丙烯酸钠、海藻酸钠和硬脂酸钠中的一种或几种。 The production method according to claim 8, wherein the surfactant is one or more selected from the group consisting of sodium alkylbenzenesulfonate, sodium polyacrylate, sodium alginate, and sodium stearate.
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CN110885658A (en) * 2018-09-07 2020-03-17 刘韶锋 Preparation method of two-component polyaspartic acid ester seam beautifying agent
CN109627872A (en) * 2018-11-26 2019-04-16 河北晨阳工贸集团有限公司 A kind of water soluble acrylic acid anticorrosive paint of containing graphene and preparation method thereof
CN111187566A (en) * 2020-02-24 2020-05-22 顺缔高新材料江苏有限公司 Solvent-free self-leveling polyurethane wear-resistant material and preparation method thereof
CN113105818A (en) * 2021-04-13 2021-07-13 江苏天沃重工科技有限公司 Preparation method of corrosion-resistant composite coating for eddy current crushing cavity of sand making machine
CN113717615A (en) * 2021-09-17 2021-11-30 陕西科技大学 Preparation method of wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating
CN113817118A (en) * 2021-09-26 2021-12-21 亚士防水科技(滁州)有限公司 Single-component II type polyurethane waterproof coating and preparation method and application thereof
CN114231100A (en) * 2021-12-23 2022-03-25 陕西煤业化工技术研究院有限责任公司 Skin finish paint for airplane and preparation method and application thereof
CN114231100B (en) * 2021-12-23 2023-08-29 陕西煤业化工技术研究院有限责任公司 Skin finishing paint for airplane and preparation method and application thereof
CN114908581A (en) * 2022-05-07 2022-08-16 常州佳尔科仿真器材有限公司 Coating for PVC sandwich mesh cloth and preparation method thereof
CN115521676A (en) * 2022-05-18 2022-12-27 四川航天职业技术学院(四川航天高级技工学校) Light coating and preparation method and application thereof
CN115521676B (en) * 2022-05-18 2023-09-19 四川航天职业技术学院(四川航天高级技工学校) Light coating and preparation method and application thereof

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