CN111471365A - Graphene-based water-based intumescent fire retardant coating and preparation method thereof - Google Patents
Graphene-based water-based intumescent fire retardant 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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
Abstract
The invention provides a graphene-based water-based intumescent fire retardant coating and a preparation method thereof, wherein the graphene-based water-based intumescent fire retardant coating comprises a graphene-based acrylic emulsion, and the preparation method of the graphene-based acrylic emulsion comprises the following steps: grafting alcoholic hydroxyl on the surface of graphene to obtain alcohol hydroxylated graphene; grafting an initiator ACVA on alcohol hydroxylated graphene to prepare a graphene-based initiator; initiating the polymerization of an acrylic monomer by using a graphene-based initiator to prepare a graphene-based acrylic emulsion; most of graphene-based initiators inherit the inherent structure and performance of original graphene and have excellent water-soluble characteristics, so that the graphene-based initiators are completely suitable for initiating acrylic monomers, the graphene has many excellent characteristics, and the two-dimensional lamellar structure of the graphene can form a compact isolation layer in a fireproof coating to play a role in flame retardance; meanwhile, the graphene and the matrix are compounded in a crosslinking mode to form a protective layer, so that the overflow of solid particles formed in the combustion process is effectively inhibited, and the smoke inhibiting effect is obvious.
Description
Technical Field
The invention relates to the technical field of water-based fireproof coatings, in particular to a graphene-based water-based intumescent fireproof coating and a preparation method thereof.
Background
The fire-retardant coating is also called as flame-retardant coating, and the intumescent fire-retardant coating has two special properties: one is that the coating itself is non-flammable or flame retardant, i.e. able to prevent ignition by a flame; and secondly, the coating can be foamed and expanded in the combustion process, and the heat is delayed to be diffused to the protected base material, so that the time is saved for fire fighting. Intumescent fire-retardant coatings have been used more commonly in the construction of steel and wood structures.
Most of the existing water-based intumescent fire-retardant coating technologies are prepared by taking acrylic emulsion or vinyl acetate emulsion as a base material and adding intumescent flame-retardant filler, and the problems of poor strength of a carbonaceous layer, short fire-proof time and to-be-improved smoke suppression effect of the fire-retardant coating after combustion generally exist in the technology.
Based on this, there is a need for improvement of existing water-based intumescent fire-retardant coatings.
Disclosure of Invention
In view of the above, the invention provides the graphene-based water-based intumescent fire retardant coating with long fire-retardant time and good smoke suppression effect.
The technical scheme of the invention is realized as follows: the invention provides a graphene-based water-based intumescent fire retardant coating, which comprises the following components in percentage by weight: the preparation method of the graphene-based acrylic emulsion comprises the following steps:
s1, grafting alcoholic hydroxyl on the surface of graphene to obtain alcohol hydroxylated graphene;
s2, grafting an initiator ACVA on the alcohol hydroxylated graphene to prepare a graphene-based initiator;
and S3, initiating the polymerization of the acrylic monomer by using the graphene-based initiator to obtain the graphene-based acrylic emulsion.
On the basis of the above technical solution, preferably, the preparation of the graphene-based initiator in S2 specifically includes:
s21, dissolving EDC in a DMF solvent to obtain a mixed solvent for later use;
s22, dispersing an initiator ACVA in an alcohol-hydroxylated graphene solution, adding DMAP, mixing, dropwise adding a mixed solvent in a nitrogen atmosphere to react, and washing and drying reactants to obtain the graphene-based initiator.
On the basis of the above technical solution, preferably, the preparation of the alcohol-hydroxylated graphene in S1 includes: and adding the solution containing the aromatic amine with hydroxyl and sodium nitrite into the dispersion liquid of o-dichlorobenzene containing graphene, and reacting to obtain the alcohol hydroxylated graphene.
On the basis of the above technical solution, preferably, the preparation method of graphene comprises:
s11, mixing potassium and graphite, putting the mixture into a container, vacuumizing, heating to 140-160 ℃, reacting for 22-26 h, and cooling to room temperature;
s12, adding pyridine into the container, standing, adding ethanol, performing ultrasonic treatment, performing suction filtration to obtain a product, washing the product, dissolving the product in DMF, stirring, and performing suction filtration to obtain the graphene.
On the basis of the above technical scheme, preferably, the preparation method of the graphene-based acrylic emulsion in S3 comprises:
s31, stirring and mixing the acrylic monomer, the water loss agent, the emulsifier and water to obtain monomer emulsion;
s32, uniformly mixing the emulsifier, the pH regulator and water to prepare an initial material;
s33, placing the initial material in a reaction kettle, heating to 70-80 ℃, adding a graphene-based initiator, carrying out an emulsification reaction, adding an oxidant, continuing to react, cooling, adding a defoaming agent, and adjusting the pH to 7-8 to obtain the graphene-based acrylic emulsion.
Preferably, the acrylic acid monomer comprises one or more of methyl methacrylate, butyl acrylate, methacrylic acid and acrylonitrile, the water loss agent is 4-dimethylaminopyridine, the emulsifier comprises at least one of an anionic emulsifier, a reactive emulsifier and a nonionic emulsifier, the anionic emulsifier is an alkyl sulfate, the nonionic emulsifier is fatty alcohol-polyoxyethylene ether, the reactive emulsifier is sodium vinylsulfonate, the oxidant is tert-butyl hydroperoxide, the pH regulator is sodium bicarbonate, and the defoaming agent is a metal soap defoaming agent.
On the basis of the above technical solution, preferably, the fireproof coating further includes: intumescent flame retardant, flame retardant filler, neutralizer, plasticizer, cosolvent, dispersant and stabilizer.
Further preferably, the flame-retardant filler comprises one or more of aluminum hydroxide, magnesium hydroxide and talcum powder, the neutralizing agent is dimethylethanolamine, and the dispersing agent comprises a sodium polycarboxylate salt and/or a polyacrylate.
Further preferably, the mass ratio of the graphene-based acrylic emulsion to the intumescent flame retardant to the flame retardant filler to the neutralizer to the plasticizer to the cosolvent to the dispersant to the stabilizer is 20-30: 30-50: 5-10: 0.1-10: 1-10: 2-20: 0.1-10.
The invention also provides a preparation method of the graphene-based water-based intumescent fire retardant coating, which comprises the following steps:
a1, adding the graphene-based acrylic emulsion into a mixer, adding a neutralizer, stirring, adding a plasticizer, continuously stirring, adding a cosolvent, a dispersant and a stabilizer, and uniformly stirring;
a2, adding the intumescent flame retardant and the flame retardant filler, and uniformly stirring to obtain the graphene-based water-based intumescent fire retardant coating.
Compared with the prior art, the graphene-based water-based intumescent fire retardant coating has the following beneficial effects:
(1) according to the graphene-based water-based intumescent fire retardant coating, a water-soluble initiator ACVA is chemically grafted to the surface of alcohol-hydroxylated graphene, and then the graphene-based acrylic emulsion is prepared by in-situ initiated monomer free radical polymerization, due to the controllable characteristic of the adopted grafting reaction, most of the graphene-based initiator inherits the inherent structure and performance of the original graphene and has excellent water-soluble characteristic, so that the graphene-based water-based intumescent fire retardant coating is completely suitable for initiating an acrylic monomer and a two-dimensional lamellar structure of the graphene, a compact isolation layer can be formed in the fire retardant coating, and the fire retardant effect is achieved; meanwhile, the graphene can be crosslinked and compounded with the matrix to form a protective layer, so that the overflow of solid particles formed in the combustion process is effectively inhibited, and the smoke inhibiting effect is obvious. The graphene is added into a flame-retardant system, so that the orientation of polymer molecular chains and the generation of a 'skeleton' substance are induced when the coating expands under heating, a carbonaceous layer is obviously enhanced, and the flame-retardant effect is exerted;
(2) the graphene-based water-based intumescent fire retardant coating disclosed by the invention is prepared by a solvent liquid phase stripping method to obtain graphene, and the graphene prepared by the method is low in layer number and small in structural damage to the graphene.
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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The invention provides a graphene-based water-based intumescent fire retardant coating, which comprises the following components in percentage by weight: the preparation method of the graphene-based acrylic emulsion comprises the following steps:
s1, grafting alcoholic hydroxyl on the surface of graphene to obtain alcohol hydroxylated graphene;
s2, grafting an initiator ACVA on the alcohol hydroxylated graphene to prepare a graphene-based initiator;
and S3, initiating the polymerization of the acrylic monomer by using the graphene-based initiator to obtain the graphene-based acrylic emulsion.
In particular toThe preparation method of the alcohol hydroxylated graphene comprises the following steps: mixing 5 mg/ml-15 mg/ml of the hydroxyl-containing aromatic amine-1Adding the sodium nitrite solution into an o-dichlorobenzene dispersion liquid containing graphene, heating to 70 ℃, and reacting for 4 hours to obtain the alcohol hydroxylated graphene.
The preparation method of the graphene-based initiator specifically comprises the following steps:
s21, dissolving EDC (water-soluble carbodiimide) in a DMF solvent to obtain a mixed solvent for later use;
s22, dispersing an initiator ACVA (4,4' -azobis (4-cyanopentanoic acid)) in 10mg/ml of alcohol hydroxylated graphene solution, adding DMAP (4-dimethylaminopyridine), mixing, dropwise adding a mixed solvent in a nitrogen atmosphere and an ice water bath, reacting for 48 hours at 30 ℃, washing a reactant with DCM (dichloromethane) after the reaction, and drying in vacuum to obtain the graphene-based initiator. Wherein the molar ratio of ACVA, EDC and DMAP is 1:2.5: 0.35.
The preparation method of the graphene-based acrylic emulsion comprises the following steps:
s31, stirring and mixing the acrylic monomer, the water loss agent, the emulsifier and water to obtain monomer emulsion;
s32, uniformly mixing the emulsifier, the pH regulator and water to prepare an initial material;
and S33, placing the initial material into a reaction kettle, heating to 70 ℃, adding a graphene-based initiator, carrying out an emulsification reaction for 1h, then adding an oxidant, continuing to react for 15min, cooling to 30 ℃, adding a defoaming agent, adding ammonia water, and adjusting the pH value to 7.5 to obtain the graphene-based acrylic emulsion.
The acrylic monomer consists of 400 parts by weight of methyl methacrylate, 500 parts by weight of butyl acrylate and 50 parts by weight of methacrylic acid;
the water loss agent is 80 parts by weight of 4-dimethylamino pyridine;
the emulsifier is composed of 75 parts by weight of anionic emulsifier and 1 part by weight of nonionic emulsifier, wherein the anionic emulsifier adopts alkyl sulfate, and the nonionic emulsifier adopts fatty alcohol-polyoxyethylene ether;
the oxidant is 0.1 part by weight of tert-butyl hydroperoxide;
the pH regulator is 0.1 part by weight of sodium bicarbonate;
the defoaming agent is 0.5 part by weight of metal soap defoaming agent.
Example 2
The invention provides a graphene-based water-based intumescent fire retardant coating, which comprises the following components in percentage by weight: the preparation method of the graphene-based acrylic emulsion comprises the following steps:
s1, grafting alcoholic hydroxyl on the surface of graphene to obtain alcohol hydroxylated graphene;
s2, grafting an initiator ACVA on the alcohol hydroxylated graphene to prepare a graphene-based initiator;
and S3, initiating the polymerization of the acrylic monomer by using the graphene-based initiator to obtain the graphene-based acrylic emulsion.
Specifically, the preparation method of the alcohol-hydroxylated graphene comprises the following steps:
s11, mixing potassium and graphite, placing the mixture into a container, placing the container into an oil bath at 110 ℃, vacuumizing for 30min, heating to 150 ℃, reacting for 24h, and cooling to room temperature, wherein the mass ratio of potassium to graphite is 2: 1;
s12, placing the container in an ice-water bath, then dropwise adding pyridine, then standing the container at room temperature for 24h, after standing, adding ethanol with the same volume as that of the pyridine, performing ultrasonic treatment for 1h, performing suction filtration, respectively performing acid washing, water washing and DMF washing on the obtained product to remove impurities in the product, dispersing the washed product in DMF, stirring for 20min at 4500r/min, standing for 12h, taking supernatant, re-dispersing the lower-layer precipitate in DMF, performing ultrasonic treatment for 1h, then stirring again, and performing suction filtration to obtain graphene;
s13, mixing 5 mg/ml-15mg of the hydroxyl-containing aromatic amine.ml-1Adding the sodium nitrite solution into an o-dichlorobenzene dispersion containing the graphene prepared in S12, heating to 70 ℃, and reacting for 4 hours to obtain the alcohol hydroxylated graphene.
The preparation method of the graphene-based initiator specifically comprises the following steps:
s21, dissolving EDC (water-soluble carbodiimide) in a DMF solvent to obtain a mixed solvent for later use;
s22, dispersing an initiator ACVA (4,4' -azobis (4-cyanopentanoic acid)) in 10mg/ml of alcohol hydroxylated graphene solution, adding DMAP (4-dimethylaminopyridine), mixing, dropwise adding a mixed solvent in a nitrogen atmosphere and an ice water bath, reacting for 48 hours at 30 ℃, washing a reactant with DCM (dichloromethane) after the reaction, and drying in vacuum to obtain the graphene-based initiator. Wherein the molar ratio of ACVA, EDC and DMAP is 1:2.5: 0.35.
The preparation method of the graphene-based acrylic emulsion comprises the following steps:
s31, stirring and mixing the acrylic monomer, the water loss agent, the emulsifier and water to obtain monomer emulsion;
s32, uniformly mixing the emulsifier, the pH regulator and water to prepare an initial material;
and S33, placing the initial material into a reaction kettle, heating to 70 ℃, adding a graphene-based initiator, carrying out an emulsification reaction for 1h, then adding an oxidant, continuing to react for 15min, cooling to 30 ℃, adding a defoaming agent, adding ammonia water, and adjusting the pH value to 7.5 to obtain the graphene-based acrylic emulsion.
The acrylic monomer consists of 400 parts by weight of methyl methacrylate, 500 parts by weight of butyl acrylate and 50 parts by weight of methacrylic acid;
the water loss agent is 80 parts by weight of 4-dimethylamino pyridine;
the emulsifier is composed of 75 parts by weight of anionic emulsifier and 1 part by weight of nonionic emulsifier, wherein the anionic emulsifier adopts alkyl sulfate, and the nonionic emulsifier adopts fatty alcohol-polyoxyethylene ether;
the oxidant is 0.1 part by weight of tert-butyl hydroperoxide;
the pH regulator is 0.1 part by weight of sodium bicarbonate;
the defoaming agent is 0.5 part by weight of metal soap defoaming agent.
Example 3
The invention provides a graphene-based water-based intumescent fire retardant coating, which comprises the following components in percentage by weight: the preparation method of the graphene-based acrylic emulsion comprises the following steps:
s1, grafting alcoholic hydroxyl on the surface of graphene to obtain alcohol hydroxylated graphene;
s2, grafting an initiator ACVA on the alcohol hydroxylated graphene to prepare a graphene-based initiator;
and S3, initiating the polymerization of the acrylic monomer by using the graphene-based initiator to obtain the graphene-based acrylic emulsion.
Specifically, the preparation method of the alcohol-hydroxylated graphene comprises the following steps:
s11, mixing potassium and graphite, placing the mixture into a container, placing the container into an oil bath at 110 ℃, vacuumizing for 30min, heating to 150 ℃, reacting for 24h, and cooling to room temperature, wherein the mass ratio of potassium to graphite is 2: 1;
s12, placing the container in an ice-water bath, then dropwise adding pyridine, then standing the container at room temperature for 24h, after standing, adding ethanol with the same volume as that of the pyridine, performing ultrasonic treatment for 1h, performing suction filtration, respectively performing acid washing, water washing and DMF washing on the obtained product to remove impurities in the product, dispersing the washed product in DMF, stirring for 20min at 4500r/min, standing for 12h, taking supernatant, re-dispersing the lower-layer precipitate in DMF, performing ultrasonic treatment for 1h, then stirring again, and performing suction filtration to obtain graphene;
s13, mixing 5 mg/ml-15 mg/ml of the hydroxyl-containing aromatic amine-1Adding the sodium nitrite solution into an o-dichlorobenzene dispersion containing the graphene prepared in S12, heating to 70 ℃, and reacting for 4 hours to obtain the alcohol hydroxylated graphene.
The preparation method of the graphene-based initiator specifically comprises the following steps:
s21, dissolving EDC (water-soluble carbodiimide) in a DMF solvent to obtain a mixed solvent for later use;
s22, dispersing an initiator ACVA (4,4' -azobis (4-cyanopentanoic acid)) in 10mg/ml of alcohol hydroxylated graphene solution, adding DMAP (4-dimethylaminopyridine), mixing, dropwise adding a mixed solvent in a nitrogen atmosphere and an ice water bath, reacting for 48 hours at 30 ℃, washing a reactant with DCM (dichloromethane) after the reaction, and drying in vacuum to obtain the graphene-based initiator. Wherein the molar ratio of ACVA, EDC and DMAP is 1:2.5: 0.35.
The preparation method of the graphene-based acrylic emulsion comprises the following steps:
s31, mixing 400 parts by weight of methyl methacrylate, 500 parts by weight of butyl acrylate and 50 parts by weight of methacrylic acid to form an acrylic monomer, 80 parts by weight of a water loss agent, 75 parts by weight of an anionic emulsifier, 1 part by weight of a nonionic emulsifier and 200 parts by weight of water to form a monomer emulsion;
s32, stirring and mixing 10 parts by weight of anionic emulsifier, 1 part by weight of reactive emulsifier, 0.1 part by weight of pH regulator and 350 parts by weight of water to obtain an initial material;
s33, uniformly mixing 3 parts by weight of graphene-based initiator and 10 parts by weight of water to obtain a first initiator solution, and uniformly mixing 10 parts by weight of graphene-based initiator and 50 parts by weight of water to obtain a second initiator solution;
s34, placing the initial material in a reaction kettle, heating to 70 ℃, adding a first initiator solution, adding a monomer emulsion with the mass dispersion of 5% after 5min, stirring and emulsifying, then simultaneously dropwise adding the rest monomer emulsion and a second initiator solution, keeping the reaction temperature at 80 ℃, keeping the temperature for 1h, cooling to 60 ℃, adding an oxidant of 0.1, continuing to react for 15min, cooling to 30 ℃, adding a defoaming agent, and adjusting the pH to 7.5 with ammonia water to obtain the graphene-based acrylic emulsion.
The water loss agent is 4-dimethylamino pyridine;
the anionic emulsifier adopts alkyl sulfate, the nonionic emulsifier adopts fatty alcohol-polyoxyethylene ether, and the reactive emulsifier adopts sodium vinylsulfonate;
the oxidant is tert-butyl hydroperoxide;
the pH regulator is sodium bicarbonate;
the defoaming agent is a metal soap defoaming agent.
Example 4
The invention provides a graphene-based water-based intumescent fire retardant coating, which comprises the following components in percentage by weight: 20 parts by weight of graphene-based acrylic emulsion, 30 parts by weight of intumescent flame retardant, 5 parts by weight of flame retardant filler, 0.1 part by weight of neutralizing agent, 1 part by weight of plasticizer, 2 parts by weight of cosolvent, 0.1 part by weight of dispersant and 0.1 part by weight of stabilizer; the intumescent flame retardant comprises ammonium polyphosphate, dipentaerythritol and melamine, the flame-retardant filler comprises one or more of aluminum hydroxide, magnesium hydroxide and talcum powder, the neutralizer is dimethylethanolamine, the plasticizer is chlorinated paraffin, the dispersant comprises sodium polycarboxylate and/or polyacrylate, the cosolvent is propylene glycol, and the stabilizer is a calcium soap stabilizer;
the preparation method of the graphene-based acrylic emulsion comprises the following steps:
s1, grafting alcoholic hydroxyl on the surface of graphene to obtain alcohol hydroxylated graphene;
s2, grafting an initiator ACVA on the alcohol hydroxylated graphene to prepare a graphene-based initiator;
and S3, initiating the polymerization of the acrylic monomer by using the graphene-based initiator to obtain the graphene-based acrylic emulsion.
Specifically, the preparation method of the alcohol-hydroxylated graphene comprises the following steps:
s11, mixing potassium and graphite, placing the mixture into a container, placing the container into an oil bath at 110 ℃, vacuumizing for 30min, heating to 150 ℃, reacting for 24h, and cooling to room temperature, wherein the mass ratio of potassium to graphite is 2: 1;
s12, placing the container in an ice-water bath, then dropwise adding pyridine, then standing the container at room temperature for 24h, after standing, adding ethanol with the same volume as that of the pyridine, performing ultrasonic treatment for 1h, performing suction filtration, respectively performing acid washing, water washing and DMF washing on the obtained product to remove impurities in the product, dispersing the washed product in DMF, stirring for 20min at 4500r/min, standing for 12h, taking supernatant, re-dispersing the lower-layer precipitate in DMF, performing ultrasonic treatment for 1h, then stirring again, and performing suction filtration to obtain graphene;
s13, mixing 5 mg/ml-15 mg/ml of the hydroxyl-containing aromatic amine-1Adding the sodium nitrite solution into an o-dichlorobenzene dispersion containing the graphene prepared in S12, heating to 70 ℃, and reacting for 4 hours to obtain the alcohol hydroxylated graphene.
The preparation method of the graphene-based initiator specifically comprises the following steps:
s21, dissolving EDC (water-soluble carbodiimide) in a DMF solvent to obtain a mixed solvent for later use;
s22, dispersing an initiator ACVA (4,4' -azobis (4-cyanopentanoic acid)) in 10mg/ml of alcohol hydroxylated graphene solution, adding DMAP (4-dimethylaminopyridine), mixing, dropwise adding a mixed solvent in a nitrogen atmosphere and an ice water bath, reacting for 48 hours at 30 ℃, washing a reactant with DCM (dichloromethane) after the reaction, and drying in vacuum to obtain the graphene-based initiator. Wherein the molar ratio of ACVA, EDC and DMAP is 1:2.5: 0.35.
The preparation method of the graphene-based acrylic emulsion comprises the following steps:
s31, stirring and mixing the acrylic monomer, the water loss agent, the emulsifier and water to obtain monomer emulsion;
s32, uniformly mixing the emulsifier, the pH regulator and water to prepare an initial material;
and S33, placing the initial material into a reaction kettle, heating to 70 ℃, adding a graphene-based initiator, carrying out an emulsification reaction for 1h, then adding an oxidant, continuing to react for 15min, cooling to 30 ℃, adding a defoaming agent, adding ammonia water, and adjusting the pH value to 7.5 to obtain the graphene-based acrylic emulsion.
The acrylic monomer consists of 400 parts by weight of methyl methacrylate, 500 parts by weight of butyl acrylate and 50 parts by weight of methacrylic acid;
the water loss agent is 80 parts by weight of 4-dimethylamino pyridine;
the emulsifier is composed of 75 parts by weight of anionic emulsifier and 1 part by weight of nonionic emulsifier, wherein the anionic emulsifier adopts alkyl sulfate, and the nonionic emulsifier adopts fatty alcohol-polyoxyethylene ether;
the oxidant is 0.1 part by weight of tert-butyl hydroperoxide;
the pH regulator is 0.1 part by weight of sodium bicarbonate;
the defoaming agent is 0.5 part by weight of metal soap defoaming agent.
The preparation method of the fireproof coating comprises the following steps:
a1, adding the graphene-based acrylic emulsion into a mixer, adding a neutralizer, stirring for 5min, adding a plasticizer, continuously stirring for 5min, adding a cosolvent, a dispersant and a stabilizer, and uniformly stirring;
a2, adding the intumescent flame retardant and the flame retardant filler, and uniformly stirring to obtain the graphene-based water-based intumescent fire retardant coating.
Experiments show that the expansion multiple of the fireproof coating prepared in the embodiment 4 is 48 times, the carbon layer has certain strength, the fire-resistant time can reach 3.6 hours, the smoke and fire prevention and combustion toxicity of the material meet EN 45545-2H L3 level, and the product quality is stable after laboratory pilot experiments and workshop production verification for many times.
Example 5
The invention provides a graphene-based water-based intumescent fire retardant coating, which comprises the following components in percentage by weight: 30 parts by weight of graphene-based acrylic emulsion, 50 parts by weight of intumescent flame retardant, 10 parts by weight of flame retardant filler, 10 parts by weight of neutralizer, 10 parts by weight of plasticizer, 20 parts by weight of cosolvent, 10 parts by weight of dispersant and 10 parts by weight of stabilizer; the intumescent flame retardant comprises ammonium polyphosphate, dipentaerythritol and melamine, the flame-retardant filler comprises one or more of aluminum hydroxide, magnesium hydroxide and talcum powder, the neutralizer is dimethylethanolamine, the plasticizer is chlorinated paraffin, the dispersant comprises sodium polycarboxylate and/or polyacrylate, the cosolvent is propylene glycol, the stabilizer is calcium soap stabilizer, in the implementation, the flame-retardant filler is talcum powder, and the dispersant is polyacrylate;
the preparation method of the graphene-based acrylic emulsion comprises the following steps:
s1, grafting alcoholic hydroxyl on the surface of graphene to obtain alcohol hydroxylated graphene;
s2, grafting an initiator ACVA on the alcohol hydroxylated graphene to prepare a graphene-based initiator;
and S3, initiating the polymerization of the acrylic monomer by using the graphene-based initiator to obtain the graphene-based acrylic emulsion.
Specifically, the preparation method of the alcohol-hydroxylated graphene comprises the following steps:
s11, mixing potassium and graphite, placing the mixture into a container, placing the container into an oil bath at 110 ℃, vacuumizing for 30min, heating to 150 ℃, reacting for 24h, and cooling to room temperature, wherein the mass ratio of potassium to graphite is 2: 1;
s12, placing the container in an ice-water bath, then dropwise adding pyridine, then standing the container at room temperature for 24h, after standing, adding ethanol with the same volume as that of the pyridine, performing ultrasonic treatment for 1h, performing suction filtration, respectively performing acid washing, water washing and DMF washing on the obtained product to remove impurities in the product, dispersing the washed product in DMF, stirring for 20min at 4500r/min, standing for 12h, taking supernatant, re-dispersing the lower-layer precipitate in DMF, performing ultrasonic treatment for 1h, then stirring again, and performing suction filtration to obtain graphene;
s13, mixing 5 mg/ml-15 mg/ml of the hydroxyl-containing aromatic amine-1Adding the sodium nitrite solution into an o-dichlorobenzene dispersion containing the graphene prepared in S12, heating to 70 ℃, and reacting for 4 hours to obtain the alcohol hydroxylated graphene.
The preparation method of the graphene-based initiator specifically comprises the following steps:
s21, dissolving EDC (water-soluble carbodiimide) in a DMF solvent to obtain a mixed solvent for later use;
s22, dispersing an initiator ACVA (4,4' -azobis (4-cyanopentanoic acid)) in 10mg/ml of alcohol hydroxylated graphene solution, adding DMAP (4-dimethylaminopyridine), mixing, dropwise adding a mixed solvent in a nitrogen atmosphere and an ice water bath, reacting for 48 hours at 30 ℃, washing a reactant with DCM (dichloromethane) after the reaction, and drying in vacuum to obtain the graphene-based initiator. Wherein the molar ratio of ACVA, EDC and DMAP is 1:2.5: 0.35.
The preparation method of the graphene-based acrylic emulsion comprises the following steps:
s31, stirring and mixing 500 parts by weight of methyl methacrylate, 600 parts by weight of butyl acrylate and 80 parts by weight of methacrylic acid to form an acrylic monomer, 100 parts by weight of a water loss agent, 90 parts by weight of an anionic emulsifier, 5 parts by weight of a nonionic emulsifier and 250 parts by weight of water to form a monomer emulsion;
s32, stirring and mixing 20 parts by weight of anionic emulsifier, 5 parts by weight of reactive emulsifier, 5 parts by weight of pH regulator and 450 parts by weight of water to obtain an initial material;
s33, uniformly mixing 6 parts by weight of graphene-based initiator and 30 parts by weight of water to obtain a first initiator solution, and uniformly mixing 20 parts by weight of graphene-based initiator and 100 parts by weight of water to obtain a second initiator solution;
s34, placing the initial material in a reaction kettle, heating to 80 ℃, adding a first initiator solution, adding a monomer emulsion with the mass dispersion of 25% after 10min, stirring and emulsifying, then simultaneously dropwise adding the rest monomer emulsion and a second initiator solution, keeping the reaction temperature at 80 ℃, keeping the temperature for 1.5h, cooling to 60 ℃, adding an oxidant of 2, continuing to react for 30min, cooling to 40 ℃, adding a defoaming agent, and adjusting the pH to 7.5 with ammonia water to obtain the graphene-based acrylic emulsion.
The water loss agent is 4-dimethylamino pyridine;
the anionic emulsifier adopts alkyl sulfate, the nonionic emulsifier adopts fatty alcohol-polyoxyethylene ether, and the reactive emulsifier adopts sodium vinylsulfonate;
the oxidant is tert-butyl hydroperoxide;
the pH regulator is sodium bicarbonate;
the defoaming agent is a metal soap defoaming agent.
The preparation method of the fireproof coating comprises the following steps:
a1, adding the graphene-based acrylic emulsion into a mixer, adding a neutralizer, stirring for 5min, adding a plasticizer, continuously stirring for 5min, adding a cosolvent, a dispersant and a stabilizer, and uniformly stirring;
a2, adding the intumescent flame retardant and the flame retardant filler, and uniformly stirring to obtain the graphene-based water-based intumescent fire retardant coating.
Experiments show that the expansion multiple of the fireproof coating prepared in the embodiment 5 is 50 times, the carbon layer has certain strength, the fire-resistant time can reach 4 hours, the smoke and fire prevention and combustion toxicity of the material meet EN 45545-2H L3 level, and the product quality is stable after laboratory experiments and workshop production verification for many times.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A graphene-based water-based intumescent fire retardant coating is characterized in that: the fireproof coating comprises: the preparation method of the graphene-based acrylic emulsion comprises the following steps:
s1, grafting alcoholic hydroxyl on the surface of graphene to obtain alcohol hydroxylated graphene;
s2, grafting an initiator ACVA on the alcohol hydroxylated graphene to prepare a graphene-based initiator;
and S3, initiating the polymerization of the acrylic monomer by using the graphene-based initiator to obtain the graphene-based acrylic emulsion.
2. The graphene-based aqueous intumescent fire retardant coating of claim 1, wherein: the preparation of the graphene-based initiator in S2 specifically includes:
s21, dissolving EDC in a DMF solvent to obtain a mixed solvent for later use;
s22, dispersing an initiator ACVA in an alcohol-hydroxylated graphene solution, adding DMAP, mixing, dropwise adding a mixed solvent in a nitrogen atmosphere to react, and washing and drying reactants to obtain the graphene-based initiator.
3. The graphene-based aqueous intumescent fire retardant coating of claim 1, wherein: the preparation of the alcohol hydroxylated graphene in S1 includes: and adding aromatic amine containing hydroxyl and sodium nitrite into the o-dichlorobenzene dispersion liquid containing graphene, and reacting to obtain the alcohol hydroxylated graphene.
4. The graphene-based aqueous intumescent fire retardant coating of claim 1, wherein: the preparation method of the graphene comprises the following steps:
s11, mixing potassium and graphite, putting the mixture into a container, vacuumizing, heating to 140-160 ℃, reacting for 22-26 h, and cooling to room temperature;
s12, adding pyridine into the container, standing, adding ethanol, performing ultrasonic treatment, performing suction filtration to obtain a product, washing the product, dissolving the product in DMF, stirring, and performing suction filtration to obtain the graphene.
5. The graphene-based aqueous intumescent fire retardant coating of claim 1, wherein: the preparation method of the graphene-based acrylic emulsion in S3 comprises the following steps:
s31, stirring and mixing the acrylic monomer, the water loss agent, the emulsifier and water to obtain monomer emulsion;
s32, uniformly mixing the emulsifier, the pH regulator and water to prepare an initial material;
s33, placing the initial material in a reaction kettle, heating to 70-80 ℃, adding a graphene-based initiator, carrying out an emulsification reaction, adding an oxidant, continuing to react, cooling, adding a defoaming agent, and adjusting the pH to 7-8 to obtain the graphene-based acrylic emulsion.
6. The graphene-based aqueous intumescent fire retardant coating of claim 5, wherein: the acrylic acid monomer comprises one or more of methyl methacrylate, butyl acrylate, methacrylic acid and acrylonitrile, the water loss agent is 4-dimethylaminopyridine, the emulsifier comprises at least one of an anionic emulsifier, a reactive emulsifier and a nonionic emulsifier, the anionic emulsifier is alkyl sulfate, the nonionic emulsifier is fatty alcohol-polyoxyethylene ether, the reactive emulsifier is sodium vinylsulfonate, the oxidant is tert-butyl hydroperoxide, the pH regulator is sodium bicarbonate, and the defoaming agent is a metal soap defoaming agent.
7. The graphene-based aqueous intumescent fire retardant coating of claim 1, wherein: the fire retardant coating further comprises: intumescent flame retardant, flame retardant filler, neutralizer, plasticizer, cosolvent, dispersant and stabilizer.
8. The graphene-based aqueous intumescent fire retardant coating of claim 7, wherein: the flame-retardant filler comprises one or more of aluminum hydroxide, magnesium hydroxide and talcum powder, the neutralizing agent is dimethylethanolamine, and the dispersing agent comprises sodium polycarboxylate and/or polyacrylate.
9. The graphene-based aqueous intumescent fire retardant coating of claim 7, wherein: the mass ratio of the graphene-based acrylic emulsion to the intumescent flame retardant to the flame retardant filler to the neutralizer to the plasticizer to the cosolvent to the dispersant to the stabilizer is 20-30: 30-50: 5-10: 0.1-10: 1-10: 2-20: 0.1-10.
10. The preparation method of the graphene-based water-based intumescent fire retardant coating as claimed in any one of claims 7 to 9, characterized in that: the method comprises the following steps:
a1, adding the graphene-based acrylic emulsion into a mixer, adding a neutralizer, stirring, adding a plasticizer, continuously stirring, adding a cosolvent, a dispersant and a stabilizer, and uniformly stirring;
a2, adding the intumescent flame retardant and the flame retardant filler, and uniformly stirring to obtain the graphene-based water-based intumescent fire retardant coating.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838183A (en) * | 2016-04-01 | 2016-08-10 | 常州华科聚合物股份有限公司 | Aqueous anticorrosive modified graphene coating material, and preparation method and application thereof |
| CN107805442A (en) * | 2017-11-14 | 2018-03-16 | 青岛爱尔家佳新材料股份有限公司 | Graphene modified water-soluble anticorrosive paint and preparation method thereof |
| CN110698944A (en) * | 2019-11-06 | 2020-01-17 | 青岛爱尔家佳新材料股份有限公司 | Graphene oxide modified water-based fireproof coating and preparation method thereof |
-
2020
- 2020-06-04 CN CN202010499470.2A patent/CN111471365A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838183A (en) * | 2016-04-01 | 2016-08-10 | 常州华科聚合物股份有限公司 | Aqueous anticorrosive modified graphene coating material, and preparation method and application thereof |
| CN107805442A (en) * | 2017-11-14 | 2018-03-16 | 青岛爱尔家佳新材料股份有限公司 | Graphene modified water-soluble anticorrosive paint and preparation method thereof |
| CN110698944A (en) * | 2019-11-06 | 2020-01-17 | 青岛爱尔家佳新材料股份有限公司 | Graphene oxide modified water-based fireproof coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李银峰等: "《碳纳米材料制备及其应用研究》", 31 March 2019, 中国原子能出版社 * |
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