CN108676427B - Water-based microencapsulated ultra-thin steel structure fireproof coating and preparation method thereof - Google Patents

Water-based microencapsulated ultra-thin steel structure fireproof coating and preparation method thereof Download PDF

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CN108676427B
CN108676427B CN201810387232.5A CN201810387232A CN108676427B CN 108676427 B CN108676427 B CN 108676427B CN 201810387232 A CN201810387232 A CN 201810387232A CN 108676427 B CN108676427 B CN 108676427B
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water
melamine
formaldehyde
aluminum hypophosphite
shell
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CN108676427A (en
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刘治田
胡清华
刘诗
柯贤忠
张旗
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Wuhan Institute of Technology
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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
    • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Abstract

The invention discloses a water-based microencapsulated ultra-thin steel structure fireproof coating, which is prepared by taking aluminum hypophosphite microcapsules, ammonium polyphosphate microcapsules, pentaerythritol, melamine, hydroxyethyl cellulose, a defoaming agent, a dispersing agent, water-based styrene-acrylic core-shell emulsion and water as raw materials. According to the invention, the problem that aluminum hypophosphite is easy to decompose and easily causes paint cracking is solved by using the aluminum hypophosphite microcapsule coated with the modified urea melamine formaldehyde resin, the thermal stability of the aluminum hypophosphite is improved, the water absorption of the aluminum hypophosphite is reduced, the high-efficiency synergistic flame-retardant effect of the aluminum hypophosphite microcapsule and the ammonium polyphosphate microcapsule is utilized, the fireproof flame-retardant property of the fireproof paint is greatly improved, the smoke emission of the fireproof paint is greatly reduced, and the problems that the ammonium polyphosphate is easy to hydrolyze, migrate and separate out in a humid environment and the like are solved; the obtained fireproof coating has high-efficiency flame retardance and smoke suppression, excellent film forming property, water resistance and weather resistance, environment friendliness, simple preparation and suitability for popularization and application.

Description

Water-based microencapsulated ultra-thin steel structure fireproof coating and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based microencapsulated ultra-thin steel structure fireproof coating and a preparation method thereof.
Background
The ultrathin steel structure fireproof paint is widely applied to steel structure fireproof protection due to the thin thickness of the coating, convenient construction and good decoration. However, the expansion fireproof system in the ultrathin fireproof coating is very large in proportion, and particularly, acid sources such as ammonium polyphosphate and ammonium polyphosphate are good in water solubility, easy to migrate when meeting water and poor in compatibility, so that the coating is poor in adhesive force and durability; meanwhile, when the ultrathin steel structure fireproof coating expands and foams under heating, the smoke quantity is large, the life health and safety of people are harmed, and the environment is seriously polluted.
Patent CN201410341750.5 provides an aqueous ultrathin intumescent fire-retardant coating for steel structure, which has poor durability and large smoke generation. The aluminum hypophosphite is a novel, excellent-performance, environment-friendly, halogen-free and non-toxic efficient flame retardant, has high phosphorus content (41.89%), can be efficiently cooperated with ammonium polyphosphate to retard flame, promote char formation and greatly reduce smoke generated by the coating in expansion foaming. However, aluminum hypophosphite has poor compatibility and high water absorption, and is easy to crack when being added into the coating, and can be slowly decomposed into corrosive and spontaneous combustible phosphine gas when being exposed to air, and even can form an explosive mixture under extreme conditions. Therefore, when the aluminum hypophosphite is applied, the surface of the aluminum hypophosphite needs to be coated and modified, for example, in patent CN201510410213.6, a preparation method of microencapsulated aluminum hypophosphite is provided, in which aluminum hypophosphite is used as a capsule core, and melamine/formaldehyde resin, melamine/formaldehyde/polyetheramine copolymer or melamine/formaldehyde/KH 550 copolymer is used as a capsule wall material, and the prepared aluminum hypophosphite microcapsule has the advantages that the capsule wall material is difficult to coat a core material, the microencapsulation yield is low, the cost is high, and the microcapsule is not suitable for industrial production.
Disclosure of Invention
The invention mainly aims to provide a water-based microencapsulated ultra-thin steel structure fireproof coating and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a water-based microencapsulated ultra-thin steel structure fireproof coating comprises the following components in percentage by mass: 2-10% of aluminum hypophosphite microcapsule, 30-36% of ammonium polyphosphate microcapsule, 10-20% of pentaerythritol, 10-15% of melamine, 20-30% of water-based styrene-acrylic core-shell emulsion, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octyl alcohol and the balance of water.
In the scheme, the aluminum hypophosphite microcapsule is a composite material of modified urea melamine formaldehyde resin coated aluminum hypophosphite, and is prepared by taking the aluminum hypophosphite, urea, melamine, formaldehyde, resorcinol, ammonium chloride and an emulsifier as main raw materials, firstly carrying out prepolymerization reaction on urea, melamine and a formaldehyde solution to obtain a urea melamine formaldehyde prepolymer, then adding an even suspension prepared from the aluminum hypophosphite, the emulsifier and an organic solvent (ethanol and the like), then adding the resorcinol and the ammonium chloride, and carrying out in-situ polymerization reaction; wherein the mass ratio of the total mass of the urea, the melamine and the formaldehyde to the aluminum hypophosphite is 1 (1-3); the total mass of the resorcinol and the ammonium chloride is 2-6% of the mass of the aluminum hypophosphite, the mass ratio of the resorcinol to the ammonium chloride is 1:1, and the emulsifier is 1-5% of the mass of the aluminum hypophosphite; the emulsifier is polyethylene glycol octyl phenyl ether.
In the scheme, the molar ratio of the urea to the formaldehyde in the formaldehyde solution is 1 (1-3), and the melamine accounts for 5-10% of the total mass of the urea and the formaldehyde.
In the above scheme, the prepolymerization process comprises: uniformly mixing urea, melamine and formaldehyde solution, adding amine solution to adjust the pH value to 8-9, heating to 75-85 ℃, and reacting for 1-2 h.
In the above scheme, the in-situ polymerization reaction conditions are as follows: the pH value is 3-5, the reaction temperature is 65-75 ℃, and the reaction time is 3-4 h.
In the scheme, the ammonium polyphosphate microcapsule is a composite material of melamine formaldehyde resin coated ammonium polyphosphate, and is prepared by using ammonium polyphosphate, melamine and formaldehyde as main raw materials, firstly carrying out prepolymerization reaction on melamine and formaldehyde solution to obtain a melamine formaldehyde prepolymer, then adding an even suspension formed by ammonium polyphosphate and an organic solvent, and carrying out in-situ polymerization reaction; wherein the mass ratio of the total mass of the melamine and the formaldehyde to the ammonium polyphosphate is 1 (1.5-3).
In the above scheme, the prepolymerization process comprises: evenly mixing melamine and formaldehyde solution, and adding NaHCO3Adjusting the pH value of the solution to 8-9, and then heatingReacting for 0.5-1 h at 70-80 ℃; wherein the molar ratio of the melamine to the formaldehyde in the formaldehyde solution is 1 (1.5-3).
In the above scheme, the in-situ polymerization reaction conditions are as follows: the pH value is 4-6, the reaction temperature is 70-80 ℃, and the reaction time is 2-3 h.
In the scheme, the specific preparation steps of the aluminum hypophosphite microcapsule comprise:
1) preparing a prepolymer: mixing urea, melamine and a formaldehyde solution (wherein the molar ratio of the urea to the formaldehyde in the formaldehyde solution is 1: 1-3, and the melamine is 5-10% of the total mass of the urea and the formaldehyde), then dropwise adding an amine liquid to adjust the pH value to 8-9, heating to 75-85 ℃, and reacting for 1-2 hours to obtain a urea-melamine-formaldehyde prepolymer;
2) preparing a suspension: adding an emulsifier into an organic solvent, fully stirring, adding aluminum hypophosphite, and stirring at the rotating speed of 1000-3000 r/min for 0.5-1 h to obtain an aluminum hypophosphite suspension;
3) shell polymerization: adding the aluminum hypophosphite suspension obtained in the step 2) into the urea melamine formaldehyde prepolymer obtained in the step 1), stirring and mixing, adding resorcinol and ammonium chloride (the total mass of the resorcinol and the ammonium chloride is 2-6% of the mass of the aluminum hypophosphite, and the mass ratio of the resorcinol to the ammonium chloride is 1:1), continuing stirring, adjusting the pH value to 3-5, heating to 65-75 ℃, reacting for 3-4 h, cooling, filtering, washing and drying to obtain the aluminum hypophosphite microcapsule.
In the above scheme, the preparation steps of the ammonium polyphosphate microcapsule comprise:
1) preparing a prepolymer: mixing melamine and formaldehyde solution (the molar ratio of the melamine to the formaldehyde introduced into the formaldehyde solution is 1: 1.5-3), and then dropwise adding NaHCO3Adjusting the pH value of the solution to 8-9, heating to 70-80 ℃, and reacting for 0.5-1 h to obtain a melamine formaldehyde prepolymer;
2) preparing a suspension: weighing ammonium polyphosphate, adding the ammonium polyphosphate into an organic solvent, wherein the mass ratio of the total mass of melamine and formaldehyde to the mass of the ammonium polyphosphate is 1 (1.4-3), and stirring at the rotating speed of 1000-3000 r/min for 0.5-1 h to obtain an ammonium polyphosphate suspension;
3) shell polymerization: adding the ammonium polyphosphate suspension obtained in the step 2) into a melamine formaldehyde prepolymer, fully stirring and mixing, then adjusting the pH to 4-6, heating to 70-80 ℃, reacting for 1.5-2 h, and finally cooling, filtering, washing and drying to obtain the ammonium polyphosphate microcapsule.
In the scheme, the mass concentration of the formaldehyde solution is 37-40%.
In the scheme, the amine liquid is one or more of triethanolamine, triethylamine and diethylamine.
In the above scheme, said NaHCO3The mass concentration of the solution is 10-20%.
In the scheme, the organic solvent can be one or more of ethanol, acetone and isopropanol.
In the scheme, the water-based styrene-acrylic core-shell emulsion is prepared by polymerizing the core-shell emulsion by taking a composite emulsifier, a core monomer mixture and a shell monomer mixture as raw materials, and the preparation method comprises the following steps:
1) preparing a seed emulsion: adding 1/5-3/5 of composite emulsifier aqueous solution and prepared buffer agent aqueous solution, stirring uniformly, heating to 75-85 ℃, dropwise adding all nuclear monomer mixtures into the mixture within 0.5-1 h, continuing stirring and emulsifying for 10-30 min after dropwise adding, continuing introducing nitrogen to discharge air, taking 1/5-3/5 of initiator aqueous solution, slowly dropwise adding within 30-60 min, and preserving heat for 30-60 min when the emulsion is in a blue-light milky color to obtain seed emulsion; wherein the nuclear monomer mixture comprises methyl methacrylate, butyl acrylate and styrene;
2) pre-emulsifying shell monomers: adding all shell monomer mixtures into the rest of the composite emulsifier aqueous solution, fully stirring at room temperature, and pre-emulsifying for 1-1.5 h to obtain milky shell pre-emulsion; wherein, the shell layer monomer mixture comprises methyl methacrylate, acrylic acid, styrene and butyl acrylate;
3) shell polymerization: and (3) dripping the residual initiator aqueous solution and the milky shell pre-emulsion into the seed emulsion within 2-3 h, heating to 80-90 ℃, curing for 1-2 h, cooling to 40-50 ℃, and adjusting the pH value to 7-8 by using triethylamine to obtain the water-based styrene-acrylic core-shell emulsion.
In the scheme, the mass ratio of the core monomer mixture to the shell monomer mixture is 2: 3-3: 2; the nuclear monomer mixture consists of methyl methacrylate, butyl acrylate and styrene, and the mass ratio of the methyl methacrylate to the butyl acrylate to the styrene is 1 (1-2) to 3-10; the shell monomer mixture consists of methyl methacrylate, acrylic acid, styrene and butyl acrylate in a mass ratio of 1 (1-2) to (2-4) to (8-40).
In the scheme, the emulsifier is composed of an anionic emulsifier and a nonionic emulsifier according to a mass ratio of 1: 3-3: 1, the anionic emulsifier is one of sodium dodecyl benzene sulfate or sodium dodecyl sulfate, and the nonionic emulsifier is polyethylene glycol octyl phenyl ether; the dosage of the emulsifier is 3-4% of the total mass of all monomers (the sum of the core monomer mixture and the shell monomer mixture) in the raw materials, and the dosage of water in the emulsifier aqueous solution is 70-90% of the total mass of all monomers in the raw materials.
In the scheme, the buffer is one of sodium bicarbonate, disodium hydrogen phosphate or sodium dihydrogen phosphate; the dosage of the buffering agent is 0.3-0.4% of the total mass of all monomers in the raw materials.
In the scheme, the initiator is one of potassium persulfate or ammonium persulfate; the amount of the initiator is 0.5-0.8% of the total mass of all monomers in the raw materials, and the amount of water in the initiator aqueous solution is 10-30% of the total mass of all monomers in the raw materials.
In the scheme, the dispersant can be wetting dispersant 5040 and the like.
In the scheme, the defoaming agent can be selected from silicone defoaming agent 470 and the like.
In the above scheme, the water is deionized water.
The preparation method of the water-based microencapsulated ultra-thin steel structure fireproof coating comprises the following preparation steps:
1) weighing raw materials, wherein the raw materials comprise the following components in percentage by mass: 2-10% of aluminum hypophosphite microcapsule, 30-36% of ammonium polyphosphate microcapsule, 10-20% of pentaerythritol, 10-15% of melamine, 20-30% of water-based styrene-acrylic core-shell emulsion, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octyl alcohol and the balance of water;
2) mixing aluminum hypophosphite microcapsules, ammonium polyphosphate microcapsules, pentaerythritol, melamine and water, and grinding and uniformly mixing; then adding hydroxyethyl cellulose, a defoaming agent and a dispersing agent, and continuously grinding;
3) and finally, adding the water-based styrene-acrylic core-shell emulsion and n-octanol, grinding and uniformly mixing to obtain the water-based microencapsulated ultra-thin steel structure fireproof coating.
The principle of the invention is as follows: the aluminum hypophosphite is heated to be decomposed to generate aluminum salts such as phosphoric acid, aluminum pyrophosphate, aluminum phosphate, alumina and the like, and water molecules are released; the generated aluminum salts such as aluminum pyrophosphate, aluminum phosphate and aluminum oxide catalyze and promote ammonium polyphosphate to be decomposed into acidic substances such as phosphoric acid and polyphosphoric acid under heating, meanwhile, the aluminum salts such as aluminum pyrophosphate, aluminum phosphate and aluminum oxide catalyze and promote the acidic substances such as phosphoric acid and polyphosphoric acid to react with polyhydroxy pentaerythritol, and the acidic substances are dehydrated into carbon, and a compact aluminum oxide film reinforced carbon layer can be formed; aluminum salts such as aluminum pyrophosphate, aluminum phosphate and aluminum oxide ensure the firmness of the expanded carbon layer, so that the expanded carbon layer is not easily broken by flame. Therefore, the fire resistance and flame retardance of the coating are better, and the smoke generated when the coating is foamed and expanded is reduced, so that the effects of flame retardance and smoke suppression are achieved; in addition, the invention further provides good film-forming property, water resistance, adhesiveness and the like for the coating by optimizing the water-based styrene-acrylic core-shell emulsion, and effectively widens the application field of the obtained coating system.
Compared with the prior art, the invention has the beneficial effects that:
1) the aluminum hypophosphite microcapsule is prepared by coating the modified urea melamine formaldehyde resin on the aluminum hypophosphite, so that the compatibility of the aluminum hypophosphite and other components of the coating is improved, the problem that the aluminum hypophosphite is easy to crack the coating is solved, and the problems that the aluminum hypophosphite is slowly decomposed into corrosive and spontaneous combustible hydrogen phosphide gas and the like when exposed in the air are effectively avoided.
2) By utilizing the efficient synergistic flame-retardant effect among the aluminum hypophosphite microcapsule, the ammonium polyphosphate microcapsule, the pentaerythritol and the melamine, the flame-retardant performance of the obtained coating can be effectively improved, the smoke amount generated during foaming and expansion of the coating is reduced, and the dual effects of flame retardance and smoke suppression are achieved;
3) the invention combines the core-shell structure of the water-based styrene-acrylic core-shell emulsion, the microencapsulation of aluminum hypophosphite, the microencapsulation of ammonium polyphosphate and other improvement means, so that the obtained fireproof coating has excellent water resistance and weather resistance, strong adhesive force, good stability, wide adaptability and durability.
Detailed Description
In order to better understand the present invention, the following embodiments are further illustrated, but the present invention is not limited to the following embodiments.
In the following examples, the dispersant used was wetting dispersant 5040; the defoaming agent is a silicone defoaming agent 470.
In the following examples, the preparation method of the aqueous styrene-acrylic core-shell emulsion comprises the following steps:
4) dissolving 2g of polyethylene glycol octyl phenyl ether and 1g of sodium dodecyl sulfate in 90m of L deionized water to prepare an emulsifier aqueous solution, and dissolving 0.5g of NaHCO in the emulsifier aqueous solution3Dissolving in 30ml deionized water to prepare a buffer solution; dissolving 0.8g of ammonium persulfate in 40ml of deionized water to prepare an initiator solution; uniformly mixing 45g of styrene, 5g of methyl methacrylate and 10g of butyl acrylate to obtain a nuclear monomer mixture; uniformly mixing 5g of styrene, 2g of methyl methacrylate, 35g of butyl acrylate and 4g of acrylic acid to obtain a shell monomer mixture;
5) adding 1/3 emulsifier aqueous solution and all buffer agent aqueous solution into a four-neck flask provided with a stirrer, a condenser pipe, a nitrogen gas introduction device and a constant pressure dropping funnel, heating to 80 ℃, dropwise adding a nuclear monomer mixture, continuously stirring and emulsifying for 20min after completing dropwise adding within 50min, introducing nitrogen gas, exhausting air, taking 1/3 initiator aqueous solution, continuously dropwise adding within 30min, and preserving heat for 30min when the emulsion is in a blue-light milk white color to obtain the seed emulsion.
6) Adding the mixture of the residual emulsifier aqueous solution and the shell monomer into the flask, and stirring (pre-emulsifying) for 1h at 600r/min to obtain milky shell pre-emulsion.
7) And (3) continuously dripping the residual initiator aqueous solution and the milky shell pre-emulsion into the seed emulsion within 2h, heating to 85 ℃, curing for 1h, cooling to 40 ℃, and adjusting the pH value to 7-8 by using triethylamine to obtain the water-based styrene-acrylic core-shell emulsion.
In the following examples, the aluminum hypophosphite microcapsules were prepared by:
1) preparing a prepolymer: adding 5g of urea, 1g of melamine and 13.5g of formaldehyde solution (mass fraction is 37%) into a 250ml three-neck flask, adjusting the pH to 8-9 by using triethanolamine, and then heating to 80 ℃ for reaction for 1h to obtain a urea-melamine-formaldehyde prepolymer;
2) preparing a suspension: adding 100ml of ethanol, adding 0.8g of polyethylene glycol octyl phenyl ether, fully stirring, weighing 20g of aluminum hypophosphite, and stirring at the rotating speed of 3000r/min for 40min to obtain an aluminum hypophosphite suspension;
3) adding the aluminum hypophosphite suspension obtained in the step 2) into the urea melamine formaldehyde prepolymer obtained in the step 1), stirring and mixing, adding 0.5g of resorcinol and 0.5g of ammonium chloride, continuing stirring, adjusting the pH to 4 by using dilute hydrochloric acid, heating to 70 ℃, reacting for 3 hours, cooling, filtering, washing and drying to obtain the aluminum hypophosphite microcapsule.
In the following examples, the preparation method of the ammonium polyphosphate microcapsule is as follows:
1) preparing a prepolymer: 15.75g of melamine and 22.5g of formaldehyde solution (mass fraction: 37%) were added to a 500ml three-neck flask using 10% NaHCO3Adjusting the pH value of the solution to 8-9, then heating to 70 ℃ and reacting at constant temperature for 40min to obtain a melamine formaldehyde prepolymer;
2) preparing a suspension: weighing 35g of ammonium polyphosphate, adding 140ml of ethanol, and stirring at the rotating speed of 2000r/min for 40min to obtain an ammonium polyphosphate suspension;
3) shell polymerization: adding the ammonium polyphosphate suspension obtained in the step 2) into the three-neck flask filled with the melamine formaldehyde prepolymer in the step 1), stirring to fully mix the ammonium polyphosphate suspension and the melamine formaldehyde prepolymer, adjusting the pH value to 5 by using dilute hydrochloric acid, heating to 80 ℃, reacting at a constant temperature for 2 hours, cooling, filtering, washing and drying to obtain the ammonium polyphosphate microcapsule.
Example 1
A water-based microencapsulated ultra-thin steel structure fireproof coating comprises the following components in percentage by mass: 4% of aluminum hypophosphite microcapsule, 35% of ammonium polyphosphate microcapsule, 15% of pentaerythritol, 12% of melamine, 20% of water-based styrene-acrylic core-shell emulsion, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octanol and 12% of water, wherein the preparation method comprises the following steps:
1) weighing the raw materials according to the mass percentage of the components;
2) grinding aluminum hypophosphite microcapsules, ammonium polyphosphate microcapsules, pentaerythritol and melamine into powder, and then adding water, fully grinding and uniformly mixing; then adding hydroxyethyl cellulose, a defoaming agent and a dispersing agent, and continuously and fully grinding;
3) and finally, adding the water-based styrene-acrylic core-shell emulsion and n-octanol, fully grinding and uniformly mixing to obtain the water-based microencapsulated ultra-thin steel structure fireproof coating.
Example 2
A water-based microencapsulated ultra-thin steel structure fireproof coating comprises the following components in percentage by mass: 6% of aluminum hypophosphite microcapsule, 33% of ammonium polyphosphate microcapsule, 15% of pentaerythritol, 12% of melamine, 20% of water-based styrene-acrylic core-shell emulsion, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octanol and 12% of water, and the preparation steps are the same as those in example 1.
Example 3
A water-based microencapsulated ultra-thin steel structure fireproof coating comprises the following components in percentage by mass: 8% of aluminum hypophosphite microcapsule, 31% of ammonium polyphosphate microcapsule, 15% of pentaerythritol, 12% of melamine, 20% of water-based styrene-acrylic core-shell emulsion, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octanol and 12% of water, and the preparation steps are the same as those in example 1.
Comparative example 1
A water-based microencapsulated ultra-thin steel structure fireproof coating comprises the following components in percentage by mass: 6% of aluminum hypophosphite, 33% of ammonium polyphosphate microcapsule, 15% of pentaerythritol, 12% of melamine, 20% of water-based styrene-acrylic core-shell emulsion, 0.5% of hydroxyethyl cellulose, 0.5% of dispersant, 0.5% of defoamer, 0.5% of n-octanol and 12% of water, and the preparation steps are the same as those in example 1.
Comparative example 2
A water-based microencapsulated ultra-thin steel structure fireproof coating comprises the following components in percentage by mass: 6% of aluminum hypophosphite, 33% of ammonium polyphosphate, 15% of pentaerythritol, 12% of melamine, 20% of water-based styrene-acrylic core-shell emulsion, 0.5% of hydroxyethyl cellulose, 0.5% of dispersant, 0.5% of defoamer, 0.5% of n-octanol and 12% of water, and the preparation steps are the same as in example 1.
Comparative example 3
A water-based microencapsulated ultra-thin steel structure fireproof coating comprises the following components in percentage by mass: 6% of aluminum hypophosphite microcapsule, 33% of ammonium polyphosphate microcapsule, 15% of pentaerythritol, 12% of melamine, 20% of water-based styrene-acrylic emulsion, 0.5% of hydroxyethyl cellulose, 0.5% of dispersant, 0.5% of defoamer, 0.5% of n-octanol and 12% of water, and the preparation steps are the same as in example 1.
The performance tests of the aqueous microencapsulated ultra-thin steel structure fire-retardant coating prepared in examples 1-3 and the aqueous ultra-thin steel structure fire-retardant coating obtained in comparative examples 1 and 2 are performed, and the test results are shown in table 1.
Table 1 Performance test results of the aqueous microencapsulated ultra-thin steel structure fire-retardant coating obtained in examples 1-3 and comparative example
Figure BDA0001642554710000071
Figure BDA0001642554710000081
The test structure shows that: the water-based microencapsulated ultra-thin steel structure fireproof coating prepared by the invention has the advantages of small maximum smoke density, long fire-resistant time, excellent water resistance, corrosion resistance, heat-resistant cold cycle property and adhesive force, short drying time, good crack resistance, environmental friendliness and wide application prospect.
The invention can be realized by the upper and lower limit values and interval values of all raw materials, and the invention can be realized by the lower limit values and interval values of the process parameters (such as temperature, time and the like), and the examples are not listed. The above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various modifications and changes without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.

Claims (10)

1. A water-based microencapsulated ultra-thin steel structure fireproof coating is characterized by comprising the following components in percentage by mass: 2-10% of aluminum hypophosphite microcapsule, 30-36% of ammonium polyphosphate microcapsule, 10-20% of pentaerythritol, 10-15% of melamine, 20-30% of water-based styrene-acrylic core-shell emulsion, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octyl alcohol and the balance of water;
the aluminum hypophosphite microcapsule is a composite material of modified urea melamine formaldehyde resin coated with aluminum hypophosphite;
the water-based styrene-acrylic core-shell emulsion is prepared by polymerizing core-shell emulsion by taking a composite emulsifier, a core monomer mixture and a shell layer monomer mixture as raw materials;
the nuclear monomer mixture consists of methyl methacrylate, butyl acrylate and styrene; the shell layer monomer mixture consists of methyl methacrylate, acrylic acid, styrene and butyl acrylate.
2. The water-based microencapsulated ultra-thin steel structure fire retardant coating as claimed in claim 1, wherein the aluminum hypophosphite microcapsule is prepared by using aluminum hypophosphite, urea, melamine, formaldehyde, resorcinol, ammonium chloride and an emulsifier as main raw materials, firstly carrying out prepolymerization reaction on urea, melamine and formaldehyde solution to obtain a urea-melamine-formaldehyde prepolymer, then adding a uniform suspension prepared from aluminum hypophosphite, an emulsifier and an organic solvent, then adding resorcinol and ammonium chloride, and carrying out in-situ polymerization reaction; wherein the mass ratio of the total mass of the urea, the melamine and the formaldehyde to the aluminum hypophosphite is 1 (1-3); the total mass of the resorcinol and the ammonium chloride is 2-6% of the mass of the aluminum hypophosphite, the mass ratio of the resorcinol to the ammonium chloride is 1:1, and the addition amount of the emulsifier is 1-5% of the mass of the aluminum hypophosphite; the emulsifier is polyethylene glycol octyl phenyl ether.
3. The water-based microencapsulated ultra-thin steel structure fireproof coating as claimed in claim 2, wherein the molar ratio of urea to formaldehyde in the formaldehyde solution is 1 (1-3), and the melamine is 5-10% of the total mass of urea and formaldehyde.
4. The aqueous microencapsulated ultra-thin steel structure fire retardant coating as claimed in claim 2, wherein the pre-polymerization reaction process is as follows: uniformly mixing urea, melamine and formaldehyde solution, adding amine solution to adjust the pH value to 8-9, heating to 75-85 ℃, and reacting for 1-2 h; the in-situ polymerization reaction conditions are as follows: the pH value is 3-5, the reaction temperature is 65-75 ℃, and the reaction time is 3-4 h.
5. The water-based microencapsulated ultra-thin steel structure fire retardant coating as claimed in claim 1, wherein the ammonium polyphosphate microcapsule is a composite material of melamine formaldehyde resin coated ammonium polyphosphate, which is prepared by using ammonium polyphosphate, melamine and formaldehyde as main raw materials, firstly carrying out prepolymerization reaction on melamine and formaldehyde solution to obtain a melamine formaldehyde prepolymer, then adding an even suspension formed by ammonium polyphosphate and an organic solvent, and carrying out in-situ polymerization reaction; wherein the mass ratio of the total mass of the melamine and the formaldehyde to the ammonium polyphosphate is 1 (1.4-3).
6. The aqueous microencapsulated ultra-thin steel structure fireproof coating as claimed in claim 5, wherein the pre-polymerization reaction process comprises: uniformly mixing melamine and formaldehyde solution, adjusting the pH value to 8-9, heating to 70-80 ℃, and reacting for 0.5-1 h; wherein the molar ratio of the melamine to the formaldehyde in the formaldehyde solution is 1 (1.5-3); the in-situ polymerization reaction conditions are as follows: the pH value is 4-6, the reaction temperature is 70-80 ℃, and the reaction time is 2-3 h.
7. The water-based microencapsulated ultra-thin steel structure fire retardant coating as claimed in claim 1, wherein the preparation method of the water-based styrene-acrylic core-shell emulsion comprises the following steps:
1) preparing a seed emulsion: adding 1/5-3/5 volume of composite emulsifier aqueous solution and prepared buffer agent aqueous solution, stirring uniformly, heating to 75-85 ℃, dropwise adding all nuclear monomer mixtures into the mixture within 0.5-1 h, continuing stirring and emulsifying for 10-30 min after dropwise adding, continuing introducing nitrogen to discharge air, taking 1/5-3/5 volume of initiator aqueous solution, slowly dropwise adding within 30-60 min, and preserving heat for 30-60 min when the emulsion is in a blue-light milky color to obtain seed emulsion;
2) pre-emulsifying shell monomers: adding all shell monomer mixtures into the rest of the composite emulsifier aqueous solution, fully stirring at room temperature, and pre-emulsifying for 1-1.5 h to obtain milky shell pre-emulsion;
3) shell polymerization: and (3) dripping the residual initiator aqueous solution and the milky shell pre-emulsion into the seed emulsion within 2-3 h, heating to 80-90 ℃, curing for 1-2 h, cooling to 40-50 ℃, and adjusting the pH to be 7-8 by using triethylamine to obtain the water-based styrene-acrylic core-shell emulsion.
8. The water-based microencapsulated ultra-thin steel structure fireproof coating as claimed in claim 1, wherein the mass ratio of the core monomer mixture to the shell monomer mixture is 2: 3-3: 2; the nuclear monomer mixture consists of methyl methacrylate, butyl acrylate and styrene, and the mass ratio of the methyl methacrylate to the butyl acrylate to the styrene is 1 (1-2) to 3-10; the shell monomer mixture consists of methyl methacrylate, acrylic acid, styrene and butyl acrylate in a mass ratio of 1 (1-2) to (2-4) to (8-40).
9. The water-based microencapsulated ultra-thin steel structure fireproof coating of claim 7, wherein for the water-based styrene-acrylic core-shell emulsion, the emulsifier comprises an anionic emulsifier and a nonionic emulsifier in a mass ratio of 1: 3-3: 1, the anionic emulsifier is one of sodium dodecyl benzene sulfate or sodium dodecyl sulfate, and the nonionic emulsifier is polyethylene glycol octyl phenyl ether; the dosage of the emulsifier is 3-4% of the total mass of all monomers in the raw materials, and the dosage of water in the emulsifier aqueous solution is 70-90% of the total mass of all monomers in the raw materials.
10. The preparation method of the water-based microencapsulated ultra-thin steel structure fireproof coating of any one of claims 1 to 9, characterized by comprising the following preparation steps:
1) weighing raw materials, wherein the raw materials comprise the following components in percentage by mass: 2-10% of aluminum hypophosphite microcapsule, 30-36% of ammonium polyphosphate microcapsule, 10-20% of pentaerythritol, 10-15% of melamine, 20-30% of water-based styrene-acrylic core-shell emulsion, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octyl alcohol and the balance of water;
2) mixing aluminum hypophosphite microcapsules, ammonium polyphosphate microcapsules, pentaerythritol, melamine and water, and grinding and uniformly mixing; then adding hydroxyethyl cellulose, a defoaming agent and a dispersing agent, and continuously grinding;
3) and finally, adding the water-based styrene-acrylic core-shell emulsion and n-octanol, grinding and uniformly mixing to obtain the water-based microencapsulated ultra-thin steel structure fireproof coating.
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