CN110698944A - Graphene oxide modified water-based fireproof coating and preparation method thereof - Google Patents
Graphene oxide modified water-based fireproof coating and preparation method thereof Download PDFInfo
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
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Abstract
The graphene oxide modified water-based fireproof coating provided by the invention comprises the following substances in parts by mass: the graphene oxide modified water-based fireproof coating is different from physical modification, graphene is added into the acrylic emulsion in a chemical connection mode and applied to preparation of the coating, and the dispersibility of the graphene in a water-based fireproof coating system and the compatibility with other base materials can be improved; meanwhile, the graphene with the sheet structure can enhance the strength of a carbon layer of the coating after combustion, and achieves the purposes of flame retardance and smoke suppression.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a graphene oxide modified water-based fireproof coating and a preparation method thereof.
Background
The fireproof coating is brushed on the surface of a flammable material, so that a certain decorative effect can be achieved at ordinary times, once a fire disaster happens, the spreading speed of flame can be slowed down, and the spreading speed of the flame can be slowed down within a certain timePrevent burning, and achieve the purposes of protecting the base material, and enabling people to leave the fire scene for enough time and rescuing tissues. The fire-proof principle of the fire-proof coating can be roughly summarized into the following five points: (1) the fireproof coating has flame retardancy or incombustibility, so that the protected substrate is not directly contacted with air, the ignition of an object is delayed, and the combustion speed is reduced; (2) the fireproof coating has low heat conductivity coefficient besides flame retardancy or incombustibility, and can delay the transmission of flame temperature to a protected substrate; (3) the fire-proof coating is heated to decompose non-combustible inert gas, and dilute combustible gas decomposed by the protected object when heated, so that the protected object is not easy to burn or the burning speed is reduced; (4) the nitrogen-containing fire-proof coating is heated to decompose NO and NH3The groups are combined with organic free radicals, the chain reaction is interrupted, and the temperature is reduced; (5) the expansion type fireproof coating expands and foams by heating to form a carbonaceous foam heat insulation layer to seal a protected object, so that the transfer of heat and a base material is delayed, and the object is prevented from catching fire and burning or the strength is prevented from being reduced due to the rise of temperature.
The existing fireproof coating has poor compatibility with other base materials, and the smoke suppression effect needs to be improved.
Disclosure of Invention
Therefore, it is necessary to provide a graphene oxide modified aqueous fire retardant coating with good compatibility with other base materials and significant smoke suppression effect, aiming at the defects existing in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a graphene oxide modified water-based fireproof coating, which comprises the following steps: the following substances in parts by mass are mixed: 20-40 parts of graphene oxide modified acrylic emulsion, 30-60 parts of intumescent flame retardant, 0.1-10 parts of first neutralizing agent, 2-20 parts of cosolvent, 0.1-10 parts of dispersant, 0.1-10 parts of wetting agent and 10-20 parts of pigment and filler, and mixing and stirring to obtain the graphene oxide modified water-based fireproof coating; the graphene modified acrylic emulsion is prepared by the following method:
under the condition of ice-water bath and at the temperature not exceeding 20 ℃, stirring concentrated sulfuric acid, graphite, solid sodium nitrate and potassium permanganate for reaction, heating to 35 ℃, keeping the stirring state, and adding a proper amount of deionized water and hydrogen peroxide to reduce the residual oxidant, wherein the obtained solvent is yellow and bright;
filtering the solvent while the solvent is hot, washing the solvent with HCl solution and deionized water until no sulfate radical is detected in the filtrate, and drying the filtrate to obtain graphene oxide;
stirring 10-50 parts of methyl methacrylate, 10-40 parts of butyl acrylate, 5-10 parts of methacrylic acid, 5-10 parts of graphene oxide, 80-100 parts of a water loss agent and 20-40 parts of an esterification reaction catalyst according to the following mass ratio for reaction so as to enable an acrylic monomer to be chemically grafted on the surface of the graphene oxide to form graphene oxide-graft-acrylic acid, which is marked as G-AA, and dispersing the G-AA in water for later use;
stirring and mixing 550 parts of methyl methacrylate, 450 parts of butyl acrylate, 10-30 parts of methacrylic acid, G-AA aqueous solution, 75-90 parts of anionic emulsifier, 1-5 parts of nonionic emulsifier and 250 parts of water, wherein the mass ratio of the components is 500-550 parts, the mass ratio of the components is 400-450 parts, and the components are 200-250 parts;
uniformly mixing 10-20 parts of anionic emulsifier, 1-5 parts of reactive emulsifier, 0.1-5 parts of PH regulator and 450 parts of water according to the following mass ratio to obtain initial materials;
heating the initial material to 75-85 ℃, adding a first initiator solution, reacting for 5-10min, adding 5-25% of the monomer emulsion, and stirring to react, wherein the first initiator solution comprises 0.5-3 parts of an initiator and 10-30 parts of water;
after the exothermic reaction is stable, simultaneously dripping the residual monomer emulsion and the second initiator solution, keeping the reaction temperature at 75-85 ℃, and finishing dripping within 1.5-2.5h, wherein the second initiator solution comprises 1-5 parts of initiator and 100-150 parts of water;
and (3) preserving heat for 1-1.5h, cooling to 0-70 ℃, slowly adding 0.1-2 parts of oxidant, reacting for 15-30min, cooling to 30-50 ℃, adding a defoaming agent and a second neutralizing agent, and adjusting the pH value to 7-8 to obtain the graphene modified acrylic emulsion.
In some preferred embodiments, the intumescent flame retardant system comprises A, B and C, A is one of ammonium polyphosphate, melamine phosphate and magnesium ammonium phosphate or a mixture thereof, B is one of pentaerythritol and dipentaerythritol or a mixture thereof, and C is one of melamine, urea and polyamide or a mixture thereof.
In some preferred embodiments, the first neutralizing agent is dimethylethanolamine and the plasticizer is chlorinated paraffin.
In some preferred embodiments, the co-solvent is propylene glycol.
In some preferred embodiments, the dispersant is one of a sodium polycarboxylate, a polyacrylate, or a mixture thereof.
In some preferred embodiments, the wetting agent is a sulfonic anionic surfactant.
In some preferred embodiments, the water loss agent is 4-dimethylaminopyridine, and the esterification catalyst is one of dicyclohexylcarbodiimide and diisopropylcarbodiimide.
In some preferred embodiments, the anionic emulsifier is alkyl sulfate, the nonionic emulsifier is fatty alcohol-polyoxyethylene ether, and the reactive emulsifier is sodium vinyl sulfonate.
In some preferred embodiments, the PH regulator is sodium bicarbonate, the initiator is one or a mixture of ammonium persulfate and potassium persulfate, the oxidant is tert-butyl hydroperoxide, the defoamer is a metal soap defoamer, and the second neutralizer is ammonia.
In some preferred embodiments, the pigment and filler is one of titanium dioxide, aluminum hydroxide, magnesium hydroxide, cenospheres, vermiculite or a mixture thereof.
In addition, the invention also provides the graphene oxide modified water-based fireproof coating prepared by the preparation method.
The invention adopts the technical scheme that the method has the advantages that:
the graphene oxide modified water-based fireproof coating provided by the invention comprises the following substances in parts by mass: the graphene oxide modified water-based fireproof coating is different from physical modification, and can improve the dispersibility of graphene in a water-based fireproof coating system and the compatibility with other base materials by adding the graphene into the acrylic emulsion in a chemical connection mode and applying the graphene to the preparation of the coating.
In addition, the graphene oxide modified water-based fireproof coating provided by the invention has a unique two-dimensional lamellar structure, so that when the coating expands under heating, polymer molecular chain orientation is induced and a 'skeleton' substance is generated, a carbonaceous layer is obviously enhanced, and a flame retardant effect is exerted; meanwhile, the graphene oxide has gas barrier property, and can effectively enhance the escape path of solid particles generated in the coating combustion process and enable the solid particles to be deposited, so that the smoke suppression effect is remarkable.
The graphene oxide modified water-based fireproof coating provided by the invention has the advantages of easily available raw materials, simple process, low cost, environmental friendliness, convenience in construction, easiness in operation and high added value of products.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a graphene oxide modified water-based fireproof coating, which comprises the following steps: the following substances in parts by mass are mixed: 20-40 parts of graphene oxide modified acrylic emulsion, 30-60 parts of intumescent flame retardant, 0.1-10 parts of first neutralizer, 2-20 parts of cosolvent, 0.1-10 parts of dispersant, 0.1-10 parts of wetting agent and 10-20 parts of pigment and filler, and mixing and stirring to obtain the graphene oxide modified water-based fireproof coating.
Wherein: the graphene oxide modified acrylic emulsion is prepared by the following method:
step S110: under the condition of ice-water bath and at the temperature not exceeding 20 ℃, stirring concentrated sulfuric acid, graphite, solid sodium nitrate and potassium permanganate for reaction, heating to 35 ℃, keeping the stirring state, and adding a proper amount of deionized water and hydrogen peroxide to reduce the residual oxidant, wherein the obtained solvent is yellow and bright;
step S120: filtering the solvent while the solvent is hot, washing the solvent with HCl solution and deionized water until no sulfate radical is detected in the filtrate, and drying the filtrate to obtain graphene oxide;
step S130: stirring 10-50 parts of methyl methacrylate, 10-40 parts of butyl acrylate, 5-10 parts of methacrylic acid, 5-10 parts of graphene oxide, 80-100 parts of a water loss agent and 20-40 parts of an esterification reaction catalyst according to the following mass ratio for reaction so as to enable an acrylic monomer to be chemically grafted on the surface of the graphene oxide to oxidize graphene-grade-acrylic acid (G-AA), and dispersing the G-AA in water for later use;
step S140: stirring and mixing 550 parts of methyl methacrylate, 450 parts of butyl acrylate, 10-30 parts of methacrylic acid, G-AA aqueous solution, 75-90 parts of anionic emulsifier, 1-5 parts of nonionic emulsifier and 250 parts of water, wherein the mass ratio of the components is 500-550 parts, the mass ratio of the components is 400-450 parts, and the components are 200-250 parts;
step S150: uniformly mixing 10-20 parts of anionic emulsifier, 1-5 parts of reactive emulsifier, 0.1-5 parts of PH regulator and 450 parts of water according to the following mass ratio to obtain initial materials;
step S160: heating the initial material to 75-85 ℃, adding a first initiator solution, reacting for 5-10min, adding 5-25% of the monomer emulsion, and stirring to react, wherein the first initiator solution comprises 0.5-3 parts of an initiator and 10-30 parts of water;
step S170: after the exothermic reaction is stable, simultaneously dripping the residual monomer emulsion and the second initiator solution, keeping the reaction temperature at 75-85 ℃, and finishing dripping within 1.5-2.5h, wherein the second initiator solution comprises 1-5 parts of initiator and 100-150 parts of water;
step S180: and (3) preserving heat for 1-1.5h, cooling to 0-70 ℃, slowly adding 0.1-2 parts of oxidant, reacting for 15-30min, cooling to 30-50 ℃, adding a defoaming agent and a second neutralizing agent, and adjusting the pH value to 7-8 to obtain the graphene modified acrylic emulsion.
According to the graphene oxide modified water-based fireproof coating provided by the invention, graphene is added into an acrylic emulsion in a chemical connection mode and applied to the preparation of the coating, so that the dispersibility of the graphene in a water-based fireproof coating system and the compatibility with other base materials can be improved.
In addition, the graphene oxide modified water-based fireproof coating provided by the invention has a unique two-dimensional lamellar structure, so that when the coating expands under heating, polymer molecular chain orientation is induced and a 'skeleton' substance is generated, a carbonaceous layer is obviously enhanced, and a flame retardant effect is exerted; meanwhile, the graphene oxide has gas barrier property, and can effectively enhance the escape path of solid particles generated in the coating combustion process and enable the solid particles to be deposited, so that the smoke suppression effect is remarkable.
The present invention is described in further detail below with reference to examples:
example 1
A: preparation of graphene modified acrylic emulsion
(1) Under the condition of ice water bath, adding a proper amount of concentrated sulfuric acid into a reaction kettle, sequentially adding 2g.L-1 of graphite and 1g.L-1 of sodium nitrate solid while stirring, then respectively adding 6g.L-1 of potassium permanganate, stirring and reacting for a period of time under the condition that the temperature is not more than 20 ℃, heating to about 35 ℃, continuously stirring for 30min, slowly adding a proper amount of deionized water, stirring for 20min, adding a small amount of hydrogen peroxide to reduce residual oxidant, and obtaining a yellow bright solvent.
(2) And filtering the solvent while the solvent is hot, washing the solvent by using a 5% HCl solution and deionized water successively until no sulfate radical is detected in the filtrate, fully drying the filter cake in a vacuum drying oven at the temperature of 60 ℃ to obtain graphene oxide, and storing the graphene oxide for later use.
(3) Sequentially adding 10 parts of methyl methacrylate, 10 parts of butyl acrylate, 5 parts of methacrylic acid, 5 parts of GO, 80 parts of a water loss agent and 20 parts of an esterification reaction catalyst into a reaction kettle, stirring and reacting at 30 ℃ for 24 hours, chemically grafting an acrylic monomer on the surface of graphene oxide (graphene oxide-graft-acrylic acid, G-AA), and dispersing the G-AA in water for later use.
(4) According to 500 parts of methyl methacrylate, 400 parts of butyl acrylate, 10 parts of methacrylic acid, G-AA aqueous solution, 75 parts of alkyl sulfate, 1 part of fatty alcohol-polyoxyethylene ether and 200 parts of water, stirring at high speed to mix into monomer emulsion.
(5) The initial material is prepared by evenly mixing 10 parts of alkyl sulfate, 1 part of sodium vinyl sulfonate, 0.1 part of sodium bicarbonate and 350 parts of water.
(6) Heating the initial material to 75 ℃, adding a first initiator solution, reacting for 5min, adding 5% of the monomer emulsion, and stirring to react, wherein the first initiator solution comprises 0.5 part of potassium persulfate and 10 parts of water;
(7) after the exothermic reaction is stable, simultaneously dropwise adding the residual monomer emulsion and the second initiator solution, keeping the reaction temperature at 75 ℃, and finishing dropwise adding within 1.5h, wherein the second initiator solution comprises 1 part of potassium persulfate and 100 parts of water;
(8) and (3) keeping the temperature for 1h, cooling to 0 ℃, slowly adding 0.1 part of tert-butyl hydroperoxide, reacting for 15min, cooling to 30 ℃, adding a metal soap defoaming agent and ammonia water to adjust the pH to 7, and thus obtaining the graphene oxide modified acrylic emulsion.
B: preparation of graphene oxide modified water-based fireproof coating
The following substances in parts by mass are mixed: 20 parts of graphene modified acrylic emulsion, 30 parts of intumescent flame retardant, 0.1 part of dimethylethanolamine, 1 part of chlorinated paraffin, 10 parts of propylene glycol, 0.1 part of sodium polycarboxylate, 0.1 part of wetting agent and 20 parts of pigment and filler are mixed and stirred to obtain the graphene oxide modified water-based fireproof coating, wherein the intumescent flame retardant system comprises A, B and C, A is ammonium polyphosphate, B is pentaerythritol, C is melamine, and the pigment and filler is titanium dioxide.
Example 2
A: preparation of graphene modified acrylic emulsion
(1) Under the condition of ice water bath, adding a proper amount of concentrated sulfuric acid into a reaction kettle, sequentially adding 6g.L-1 of graphite and 3g.L-1 of sodium nitrate solid while stirring, then respectively adding 6g.L-1 of potassium permanganate, stirring and reacting for a period of time under the condition that the temperature is not more than 20 ℃, heating to about 35 ℃, continuously stirring for 30min, slowly adding a proper amount of deionized water, stirring for 20min, adding a small amount of hydrogen peroxide to reduce residual oxidant, and obtaining a yellow bright solvent.
(2) And filtering the solvent while the solvent is hot, washing the solvent by using a 5% HCl solution and deionized water successively until no sulfate radical is detected in the filtrate, fully drying the filter cake in a vacuum drying oven at the temperature of 60 ℃ to obtain graphene oxide, and storing the graphene oxide for later use.
(3) Adding 50 parts of methyl methacrylate, 40 parts of butyl acrylate, 10 parts of methacrylic acid, 10 parts of GO, 100 parts of a water loss agent and 40 parts of an esterification reaction catalyst into a reaction kettle in sequence, stirring and reacting for 24 hours at 30 ℃, chemically grafting an acrylic monomer on the surface of graphene oxide (GO-graft-AA, G-AA), and dispersing the G-AA in water for later use.
(4) According to 550 parts of methyl methacrylate, 450 parts of butyl acrylate, 30 parts of methacrylic acid, a G-AA aqueous solution, 75 parts of alkyl sulfate, 1 part of fatty alcohol-polyoxyethylene ether and 250 parts of water, stirring at a high speed to mix into a monomer emulsion.
(5) 20 parts of alkyl sulfate, 5 parts of sodium vinyl sulfonate, 5 parts of sodium bicarbonate and 450 parts of water are uniformly mixed to form an initial material.
(6) Heating the initial material to 75 ℃, adding a first initiator solution, reacting for 5min, adding 5% of the monomer emulsion, and stirring to react, wherein the first initiator solution comprises 3 parts of ammonium persulfate and 30 parts of water;
(7) after the exothermic reaction is stable, simultaneously dropwise adding the residual monomer emulsion and the second initiator solution, keeping the reaction temperature at 75 ℃, and finishing dropwise adding within 1.5h, wherein the second initiator solution comprises 5 parts of ammonium persulfate and 150 parts of water;
(8) and (3) keeping the temperature for 1.5h, cooling to 70 ℃, slowly adding 0.1 part of tert-butyl hydroperoxide, reacting for 15min, cooling to 30 ℃, adding a metal soap defoaming agent and ammonia water to adjust the pH to 8, and thus obtaining the graphene oxide modified acrylic emulsion.
B: preparation of graphene oxide modified water-based fireproof coating
The following substances in parts by mass are mixed: 40 parts of graphene modified acrylic emulsion, 60 parts of intumescent flame retardant, 10 parts of dimethylethanolamine, 10 parts of chlorinated paraffin, 20 parts of propylene glycol, 10 parts of sodium polycarboxylate, 10 parts of 0.1 part of wetting agent and 20 parts of pigment and filler are mixed and stirred to obtain the graphene oxide modified water-based fireproof coating, wherein the intumescent flame retardant system comprises A and B, the A is diethyl aluminum hypophosphite, and the B is tetraphenyl (bisphenol-A) diphosphate.
Example 3
A: preparation of graphene modified acrylic emulsion
(1) Under the condition of ice water bath, adding a proper amount of concentrated sulfuric acid into a reaction kettle, sequentially adding 4g.L < -1 > of graphite and 2g.L < -1 > of sodium nitrate solid while stirring, then respectively adding 6g.L < -1 > of potassium permanganate, stirring and reacting for a period of time under the condition that the temperature is not more than 20 ℃, heating to about 35 ℃, continuously stirring for 30min, slowly adding a proper amount of deionized water, stirring for 20min, adding a small amount of hydrogen peroxide to reduce residual oxidant, and obtaining a yellow bright solvent.
(2) And filtering the solvent while the solvent is hot, washing the solvent by using a 5% HCl solution and deionized water successively until no sulfate radical is detected in the filtrate, and fully drying a filter cake in a vacuum drying oven at the temperature of 60 ℃ to obtain the graphene oxide for storage and later use.
(3) Adding 30 parts of methyl methacrylate, 20 parts of butyl acrylate, 6 parts of methacrylic acid, 7 parts of GO, 90 parts of a water loss agent and 30 parts of an esterification reaction catalyst into a reaction kettle in sequence, stirring and reacting for 24 hours at 30 ℃, chemically grafting an acrylic monomer on the surface of graphene oxide (graphene oxide-graft-acrylic acid, G-AA), and dispersing the G-AA in water for later use.
(4) According to 520 parts of methyl methacrylate, 420 parts of butyl acrylate, 20 parts of methacrylic acid, G-AA aqueous solution, 85 parts of alkyl sulfate, 3 parts of fatty alcohol-polyoxyethylene ether and 220 parts of water, stirring at high speed to mix into monomer emulsion.
(5) The raw materials are evenly mixed according to 15 parts of alkyl sulfate, 3 parts of sodium vinyl sulfonate, 3 parts of sodium bicarbonate and 400 parts of water to form an initial material.
(6) Heating the initial material to 80 ℃, adding a first initiator solution, reacting for 5min, adding 5% of the monomer emulsion, and stirring for reaction, wherein the first initiator solution comprises 2 parts of ammonium persulfate and 20 parts of water;
(7) after the exothermic reaction is stable, simultaneously dropwise adding the rest monomer emulsion and the second initiator solution, keeping the reaction temperature at 80 ℃, and finishing dropwise adding within 2h, wherein the second initiator solution comprises 3 parts of ammonium persulfate and 120 parts of water;
(8) and (3) keeping the temperature for 1.2h, cooling to 30 ℃, slowly adding 1 part of tert-butyl hydroperoxide, reacting for 20min, cooling to 30 ℃, adding a metal soap defoaming agent and ammonia water to adjust the pH to 8, and thus obtaining the graphene oxide modified acrylic emulsion.
B: preparation of graphene oxide modified water-based fireproof coating
The following substances in parts by mass are mixed: 30 parts of graphene modified acrylic emulsion, 40 parts of intumescent flame retardant, 8 parts of dimethylethanolamine, 6 parts of chlorinated paraffin, 10 parts of propylene glycol, 5 parts of sodium polycarboxylate, 5 parts of wetting agent and 10 parts of pigment and filler are mixed and stirred to obtain the graphene oxide modified water-based fireproof coating, wherein the intumescent flame retardant system comprises A, B and C, A is ammonium polyphosphate, B is dipentaerythritol, C is melamine, and the pigment and filler is aluminum hydroxide.
Of course, the graphene oxide modified aqueous fireproof coating of the present invention may have various changes and modifications, and is not limited to the specific structure of the above embodiment. In conclusion, the scope of the present invention should include those changes or substitutions and modifications which are obvious to those of ordinary skill in the art.
Claims (11)
1. The preparation method of the graphene oxide modified water-based fireproof coating is characterized by comprising the following steps: the following substances in parts by mass are mixed: mixing and stirring 20-40 parts of graphene oxide modified acrylic emulsion, 30-60 parts of intumescent flame retardant, 0.1-10 parts of first neutralizing agent, 2-20 parts of cosolvent, 0.1-10 parts of dispersing agent, 0.1-10 parts of wetting agent and 10-20 parts of pigment and filler to obtain graphene oxide modified water-based fireproof coating; the graphene oxide modified acrylic emulsion is prepared by the following method:
under the condition of ice-water bath and at the temperature not exceeding 20 ℃, stirring concentrated sulfuric acid, graphite, solid sodium nitrate and potassium permanganate for reaction, heating to 35 ℃, keeping the stirring state, and adding a proper amount of deionized water and hydrogen peroxide to reduce the residual oxidant, wherein the obtained solvent is yellow and bright;
filtering the solvent while the solvent is hot, washing the solvent with HCl solution and deionized water until no sulfate radical is detected in the filtrate, and drying the filtrate to obtain graphene oxide;
stirring 10-50 parts of methyl methacrylate, 10-40 parts of butyl acrylate, 5-10 parts of methacrylic acid, 5-10 parts of graphene oxide, 80-100 parts of a water loss agent and 20-40 parts of an esterification reaction catalyst according to the following mass ratio for reaction so as to enable an acrylic monomer to be chemically grafted on the surface of the graphene oxide to form graphene oxide-graft-acrylic acid, which is marked as G-AA, and dispersing the G-AA in water to form an aqueous solution;
stirring and mixing 550 parts of methyl methacrylate, 450 parts of butyl acrylate, 10-30 parts of methacrylic acid, a graphene oxide-g-acrylic acid aqueous solution, 75-90 parts of an anionic emulsifier, 1-5 parts of a nonionic emulsifier and 250 parts of water in the following mass ratio to form a monomer emulsion;
uniformly mixing 10-20 parts of anionic emulsifier, 1-5 parts of reactive emulsifier, 0.1-5 parts of PH regulator and 450 parts of water according to the following mass ratio to obtain initial materials;
heating the initial material to 75-85 ℃, adding a first initiator solution, reacting for 5-10min, adding 5-25% of the monomer emulsion, and stirring to react, wherein the first initiator solution comprises 0.5-3 parts of an initiator and 10-30 parts of water;
after the exothermic reaction is stable, simultaneously dripping the residual monomer emulsion and the second initiator solution, keeping the reaction temperature at 75-85 ℃, and finishing dripping within 1.5-2.5h, wherein the second initiator solution comprises 1-5 parts of initiator and 100-150 parts of water;
and (3) preserving heat for 1-1.5h, cooling to 0-70 ℃, slowly adding 0.1-2 parts of oxidant, reacting for 15-30min, cooling to 30-50 ℃, adding a defoaming agent and a second neutralizing agent, and adjusting the pH value to 7-8 to obtain the graphene oxide modified acrylic emulsion.
2. The method for preparing the graphene oxide modified water-based fireproof coating of claim 1, wherein the intumescent flame retardant system comprises A, B and C, A is one of ammonium polyphosphate, melamine phosphate and magnesium ammonium phosphate or a mixture thereof, B is one of pentaerythritol and dipentaerythritol or a mixture thereof, and C is one of melamine, urea and polyamide or a mixture thereof.
3. The method of claim 1, wherein the first neutralizing agent is dimethylethanolamine and the plasticizer is chlorinated paraffin.
4. The method for preparing the graphene oxide modified water-based fireproof coating of claim 1, wherein the cosolvent is propylene glycol.
5. The method for preparing the graphene oxide modified aqueous fireproof coating according to claim 1, wherein the dispersant is one of a sodium polycarboxylate, a polyacrylate or a mixture thereof.
6. The method for preparing the graphene oxide modified aqueous fireproof coating according to claim 1, wherein the wetting agent is a sulfonic acid-based anionic surfactant.
7. The method for preparing the graphene oxide modified waterborne fire retardant coating as claimed in claim 1, wherein the water loss agent is 4-dimethylaminopyridine, and the esterification catalyst is one of dicyclohexylcarbodiimide and diisopropylcarbodiimide.
8. The method for preparing the graphene oxide modified aqueous fireproof coating of claim 1, wherein the anionic emulsifier is alkyl sulfate, the nonionic emulsifier is fatty alcohol-polyoxyethylene ether, and the reactive emulsifier is sodium vinyl sulfonate.
9. The method for preparing the graphene oxide modified water-based fireproof coating of claim 1, wherein the pH regulator is sodium bicarbonate, the initiator is one or a mixture of ammonium persulfate and potassium persulfate, the oxidant is tert-butyl hydroperoxide, the defoaming agent is a metal soap defoaming agent, and the second neutralizing agent is ammonia water.
10. The method for preparing the graphene oxide modified water-based fireproof coating of claim 1, wherein the pigment and filler is one or a mixture of titanium dioxide, aluminum hydroxide, magnesium hydroxide, cenospheres and vermiculite.
11. The graphene oxide modified water-based fireproof coating is characterized by being prepared by the preparation method of any one of claims 1 to 10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3875547A1 (en) * | 2020-03-05 | 2021-09-08 | Intumescent Systems Ltd | Fire protection and retardant coatings |
| GB2592637A (en) * | 2020-03-05 | 2021-09-08 | Intumescent Systems Ltd | Fire protection and retardant coatings |
| EP3875546A1 (en) * | 2020-03-05 | 2021-09-08 | Intumescent Systems Ltd | Fire protection and retardant coatings |
| GB2592636A (en) * | 2020-03-05 | 2021-09-08 | Intumescent Systems Ltd | Fire protection and retardant coatings |
| GB2592636B (en) * | 2020-03-05 | 2022-03-09 | Intumescent Systems Ltd | Fire protection and retardant coatings |
| IE20200281A1 (en) * | 2020-03-05 | 2022-08-17 | Intumescent Systems Ltd | Fire Protection And Retardant Coatings |
| IE20200284A1 (en) * | 2020-03-05 | 2022-08-17 | Intumescent Systems Ltd | Fire Protection And Retardant Coating |
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| CN113913073A (en) * | 2021-11-05 | 2022-01-11 | 浙江双金粉末涂料有限公司 | Weather-resistant waterproof flame-retardant integrated coating and preparation method thereof |
| CN113913073B (en) * | 2021-11-05 | 2022-07-05 | 浙江双金粉末涂料有限公司 | Weather-resistant waterproof flame-retardant integrated coating and preparation method thereof |
| CN116218301A (en) * | 2022-12-22 | 2023-06-06 | 德清扬泰建筑材料有限公司 | High-toughness thermal expansion microsphere composite graphene fireproof water-based paint |
| CN116478584A (en) * | 2023-04-10 | 2023-07-25 | 广州全系新材料股份有限公司 | Metal roof waterproof coating and preparation method thereof |
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