CN109401406B - Intumescent smoke-suppressing fire retardant for water-based paint and preparation method thereof - Google Patents

Intumescent smoke-suppressing fire retardant for water-based paint and preparation method thereof Download PDF

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CN109401406B
CN109401406B CN201811273558.1A CN201811273558A CN109401406B CN 109401406 B CN109401406 B CN 109401406B CN 201811273558 A CN201811273558 A CN 201811273558A CN 109401406 B CN109401406 B CN 109401406B
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water
smoke
intumescent
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retardant
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CN109401406A (en
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李竑靓
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Zhongchuang (Chongqing) fireproof material Co.,Ltd.
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Zhongchuang Chongqing Fireproof Material Co ltd
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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
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates
    • 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
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Fireproofing Substances (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to an intumescent smoke-suppressing fire retardant for water-based paint and a preparation method thereof, wherein the smoke-suppressing fire retardant comprises the following components in parts by weight: 20-24 parts of boric acid, 36-38 parts of ammonium polyphosphate, 20-24 parts of guanylurea phosphate, 36-40 parts of pentaerythritol, 30-34 parts of melamine, 1.0-1.4 parts of sulfonated carbon, 3.6-4.0 parts of zinc borate and 2.0-2.4 parts of ammonium octamolybdate. The water-based fire-retardant coating prepared by the intumescent smoke-suppressing fire retardant is used for coating the surface of a wood material, can greatly retard the combustion of the wood material in the heating process and suppress the fire spread; the water-based fireproof flame-retardant coating for the wood material prepared by the intumescent smoke-suppressing flame retardant has good smoke suppression performance, can delay the time of smoke generation, reduce the release amount of smoke and the generation of toxic gas, and provides more safe time and space for escape and rescue of people under the fire condition.

Description

Intumescent smoke-suppressing fire retardant for water-based paint and preparation method thereof
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to an intumescent smoke-suppressing flame retardant for water-based paint, and a preparation method of the intumescent smoke-suppressing flame retardant for water-based paint.
Background
The wood material has the advantages of environmental protection, no toxicity, strong processability and reproducibility, and is widely applied to the fields of furniture, buildings, interior decoration and the like. However, the untreated wood material is not fire-resistant, flammable and has ignition propagation property, so that the fire hazard of a use place can be increased, and serious potential safety hazard exists. In order to effectively reduce the occurrence of fire, a series of laws and regulations and safety standards are established by the nation, and the material products used in buildings, indoor places or public places are required to reach the corresponding flame retardant level, so that the wood materials used are required to have better fireproof and flame retardant properties. The surface of the wood material is covered with the flame-retardant coating, so that the combustibility of the wood material is inhibited, the fire resistance limit of the wood material is improved, the occurrence of fire is reduced or avoided, and the wood material is a more effective flame-retardant treatment technology. The flame-retardant coating is coated on the surface of a base body of inflammable materials such as solid wood, fiber boards, shaving boards and the like to form a fireproof flame-retardant protective coating film, which can isolate flame, delay the ignition time of a base material, delay the propagation speed of the flame on the surface of the material and prevent or delay the spread of fire, and has the characteristics of simple operation, strong adaptability and very wide application space.
The flame retardant coating can be divided into water-based coating and solvent-based coating according to different dispersion media, wherein the solvent of the solvent-based coating volatilizes during construction, so that the environment is easily polluted and the human body is easily damaged; the water-based paint taking water as a dispersion medium has the characteristics of green, health, environmental protection and the like, and becomes the trend and direction of the development of the paint industry. Flame-retardant coatings are further classified into intumescent flame-retardant coatings and non-intumescent flame-retardant coatings according to the combustion characteristics. After the intumescent flame-retardant coating is formed into a film, the film is not different from a common paint film at normal temperature, but the coating is vigorously foamed and carbonized under flame or high temperature to form a flame-retardant foam carbonized layer which is dozens to hundreds of times thicker than the original coating, the heat conductivity coefficient is low, the heat transfer is prevented, and oxygen is effectively isolated; meanwhile, the decomposition reaction releases incombustible gases (water vapor, ammonia gas, carbon dioxide and the like) to dilute the combustible gases, so that the heat conduction and the flame spread are slowed down or stopped. The original coating of the intumescent flame-retardant coating is thin (generally not more than 1mm), meets the decoration requirement, is relatively low in cost, has good fireproof and heat-insulating effects, and is gradually developed in recent years.
The intumescent flame-retardant coating system generally comprises an acid source, a carbon source, a gas source and coating resin, and can be rapidly foamed to react to form a carbon protective layer and release non-combustible gas to play a role in fire prevention and flame retardation. However, in the expansion process of the flame-retardant coating, along with the release of a large amount of non-combustible gas, the coating layer is also heated to release a large amount of smoke and toxic gas, including smoke particles, CO and the like, which seriously affect the health and life safety of the disaster-stricken people and the disaster relief people and hinder the evacuation and rescue actions of the people. Therefore, how to reduce the smoke generation amount of the intumescent flame retardant coating and improve the smoke suppression performance on the basis of effective fire prevention and flame retardation is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide an intumescent smoke-suppressing fire retardant for water-based paint, which has good fireproof fire-retardant property and smoke-suppressing property.
The second purpose of the invention is to provide a preparation method of the intumescent smoke-suppressing fire retardant for the water-based paint.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an intumescent smoke-suppressing fire retardant for water-based paint comprises the following components in parts by weight: 20-24 parts of boric acid, 36-38 parts of ammonium polyphosphate, 20-24 parts of guanylurea phosphate, 36-40 parts of pentaerythritol, 30-34 parts of melamine, 1.0-1.4 parts of sulfonated carbon, 3.6-4.0 parts of zinc borate and 2.0-2.4 parts of ammonium octamolybdate.
The polymerization degree of the ammonium polyphosphate is not less than 1000.
The carbon sulfide is prepared by the following method: mixing the activated carbon and fuming sulfuric acid according to the mass ratio of 1:3.5-4.0, sulfonating for 1.5-2.5h at the temperature of 75-85 ℃, cooling, washing to be neutral, and drying to obtain the catalyst.
The particle size of the used active carbon is 10-15 μm.
The zinc borate is powder, and the average particle size is 2-3 mu m; the ammonium octamolybdate is powder with the average particle size of 2-3 mu m.
The flame retardant is used for water-based paint taking melamine modified urea resin emulsion as a base material.
In the water-based paint, the dosage of the flame retardant satisfies the following conditions: the mass ratio of solids contained in the melamine modified urea resin emulsion to the polyphosphoric acid amine is 100 (36-38).
Further, the intumescent water-based fireproof flame-retardant coating for the wood material, which adopts the intumescent smoke-suppressing flame retardant, comprises water and the following components in parts by weight: 200 parts of melamine modified urea-formaldehyde resin emulsion, 120 parts of ethylene-vinyl acetate copolymer emulsion 110-one, 20-24 parts of boric acid, 36-38 parts of ammonium polyphosphate, 20-24 parts of guanyl urea phosphate, 36-40 parts of pentaerythritol, 30-34 parts of melamine, 1.0-1.4 parts of sulfonated carbon, 3.6-4.0 parts of zinc borate, 2.0-2.4 parts of ammonium octamolybdate, 16-20 parts of a coating additive and 0-44 parts of pigment and filler. The solid content of the coating is 48-52%.
The coating auxiliary agent comprises a film-forming auxiliary agent, a dispersing agent, a defoaming agent, a wetting agent, a thickening agent and a flatting agent, wherein the mass ratio of the film-forming auxiliary agent to the dispersing agent to the defoaming agent to the flatting agent is 10 (1.0-1.5) to (1.0-2.0) to (1.0-1.5) to (2.0-3.0): (1.0-2.0).
The pigment and filler is titanium dioxide or zinc oxide powder or a mixture of other pigments and fillers. Useful pigments include, but are not limited to, carbon black, iron oxide-based inorganic pigments, phthalocyanine blue, ultramarine, phthalocyanine green, toluidine violet, and the like; useful fillers include, but are not limited to, calcium carbonate, barium sulfate, mica powder, kaolin, talc, diatomaceous earth, silica, and the like. In the pigment filler formed by mixing the pigment and the filler, the mass percentage of the filler is not more than 30 percent.
The preparation method of the intumescent smoke-suppressing fire retardant for the water-based paint comprises the following steps:
1) adding boric acid and pentaerythritol in a formula amount into a proper amount of water, uniformly dispersing, then adding guanylurea phosphate, ammonium polyphosphate and melamine in a formula amount, and stirring to uniformly disperse the guanylurea phosphate, the ammonium polyphosphate and the melamine to obtain an intumescent flame retardant premix;
placing the sulfonated carbon, zinc borate, ammonium octamolybdate and a proper amount of water in a planetary ball mill according to the formula ratio, and ball-milling at the rotating speed of 60-100r/min for 30-50min to uniformly disperse the sulfonated carbon, the zinc borate, the ammonium octamolybdate and the proper amount of water to obtain the synergistic smoke suppression premix;
2) mixing the intumescent flame retardant premix obtained in the step 1) with the synergistic smoke suppression premix to obtain the water dispersant of the intumescent smoke suppression flame retardant for the water-based paint.
In the step 1), the solid content of the premix is not lower than 55%. Preferably, the solid content of the premix is 55-60%.
On the basis of a basic expansion flame-retardant system consisting of ammonium polyphosphate, pentaerythritol and melamine, the intumescent smoke-suppressing flame retardant for the water-based paint disclosed by the invention has the advantages that boric acid and guanyl urea phosphate are adopted to replace part of ammonium polyphosphate to be used as a dehydration catalyst for preventing excessive ammonium polyphosphate from excessively and quickly curing melamine modified urea-formaldehyde resin, so that on one hand, the excessive solidification of the melamine modified urea-formaldehyde resin by the ammonium polyphosphate is relieved, and the paint can be stably stored and transported and forms a coating film with a smooth and flat surface after being coated; on the other hand, the guanyl urea phosphate can effectively capture harmful substances such as free formaldehyde and the like in the resin, and the environment-friendly property of the coating product is improved; a small amount of boric acid can gradually float on the surface of the coating film in the curing process of the coating film, and a compact barrier layer is quickly formed on the surface in the foaming expansion process of the coating film which is heated and decomposed into carbon, so that heat transfer and gas exchange are prevented, and the flame retardant and smoke suppression synergistic with other components is realized. Boric acid, ammonium polyphosphate, guanylurea phosphate, pentaerythritol and melamine form a phosphorus-nitrogen-boron ternary expansion type flame retardant system, the boric acid, the ammonium polyphosphate and the guanylurea phosphate are composite dehydration catalysts, the pentaerythritol is a char forming agent, the melamine is a main foaming agent, the melamine modified urea-formaldehyde resin is an auxiliary foaming agent, a coating film is heated and decomposed into carbon, the carbon is foamed and expanded, the foaming is good, the formed carbon layer is high and continuous in height, hard in surface and compact in interior, can be firmly fixed on a base material, and has good heat blocking and combustion-supporting gas isolating effects.
The intumescent smoke-suppressing fire retardant for the water-based paint is prepared by compounding sulfonated carbon, zinc borate and ammonium octamolybdate on the basis of the phosphorus-nitrogen-boron ternary intumescent fire retardant system to form a synergistic smoke-suppressing agent. Wherein, the sulfonated carbon has sulfonic acid groups and has good adsorptivity and catalytic activity; the catalytic activity of the sulfonated carbon can promote the low-temperature carbonization of the material, and the material can inhibit the high-temperature degradation and incomplete combustion of the material after being carbonized and cured in advance, thereby effectively reducing the heat release of the material and leading high-temperature degradation substances such as smoke, CO and CO2The release of smoke is reduced, the release of smoke is inhibited, and the generation of toxic gas is reduced. Due to the catalytic carbonization of the sulfonated carbon, an expanded carbon layer formed by the coating film which is decomposed and foamed by heating is harder, has a more compact structure and better isolation effect; the carbon layer contains a very small amount of S, most of the catalytic activity factors remain in the carbon layer, and only a very small amount of SO is used along with combustion2The form is dissipated into the air, and the human body and the environment are not affected. The zinc borate and the boric acid are cooperated, so that the zinc borate and the boric acid are easy to float on the surface of a coating in the coating curing process, a glass state inorganic layer is formed by heating and attached to the surface, the carbon production is promoted, a hard isolation layer is formed, the contact with air is isolated, and the smoke and the smoldering are effectively inhibited. Ammonium octamolybdate also has good flame-retardant and smoke-inhibiting effects, and has a synergistic effect with zinc borate and sulfonated carbon, and through metal bonding and reduction coupling, a parent body which is likely to form an aromatic smoke point is firmly bonded in a metal-aromatic system compound, so that the formation of carbon containing metal, oxygen-containing heterocyclic ring, S-containing heterocyclic ring and a plurality of carbohydrate structures is promoted, aromatic benzene cyclic compounds cannot be formed through cyclization, smoke release is reduced, and a good smoke-inhibiting effect is achieved.
The intumescent smoke-suppressing fire retardant for the water-based paint is suitable for intumescent water-based fire prevention for wood materialsThe fire-retardant coating is based on a melamine modified urea-formaldehyde resin-based coating, and adopts a smoke suppression system consisting of sulfonated carbon, zinc borate and ammonium octamolybdate and an intumescent flame retardant system compounded by boric acid, ammonium polyphosphate, guanyl urea phosphate, pentaerythritol and melamine to realize synergistic flame retardance. The detection shows that the water-based fireproof flame-retardant coating prepared by the intumescent smoke-suppressing flame retardant disclosed by the invention is coated on the surface of a wood material, the limiting oxygen index of the coating reaches more than 43%, and the coating belongs to a flame-retardant grade, so that the intumescent smoke-suppressing flame retardant disclosed by the invention can well play the effects of heat insulation and oxygen isolation of an intumescent flame-retardant system, and has good fireproof flame-retardant performance. In a heat measurement experiment, the wood material coated with the water-based fireproof flame-retardant coating prepared by the intumescent smoke-suppressing flame retardant has the ignition time of more than 650s, which is far more than that of a sample without the flame-retardant smoke-suppressing agent coating and a sample without the coating, and the maximum heat release efficiency is not more than 93kW/m2The intumescent smoke-suppressing fire retardant can greatly retard the combustion of the base material in the heating process, reduce the rate of material pyrolysis and volatile substance generation, suppress the spread of fire, effectively reduce the danger of the fire and provide longer safety time for the escape and rescue of personnel under the fire condition. The maximum smoke release rate of the wood material coated by the water-based fire-retardant coating prepared by the intumescent smoke-suppressing fire retardant is not more than 0.0023m2(s) total smoke release no more than 0.21m2While CO, CO2The release amount is greatly reduced, which shows that the intumescent smoke-suppressing fire retardant has good smoke suppression property, can delay the smoke generation time when a fire disaster occurs, reduce the release amount of smoke and the generation of toxic gas, and reduce the harm of the smoke to human bodies.
The preparation method of the intumescent smoke-suppressing fire retardant for the water-based paint reasonably arranges the feeding sequence and technical parameters of each raw material component, and has simple process and convenient operation; the coating has the advantages of no flocculation, precipitation and layering phenomena when used for coating finished products, stable property, long-time storage and transportation resistance, and suitability for popularization and use.
Detailed Description
The present invention will be further described with reference to the following embodiments.
In the specific embodiment, the melamine modified urea-formaldehyde resin emulsion is prepared by mixing melamine modified urea-formaldehyde resin rubber powder and water, and the solid content is 50%; during synthesis, the melamine modified urea resin has the F/(U + M) molar ratio of 1.15:1 and the mass ratio of M/MUF of 10%. The solid content of the ethylene-vinyl acetate copolymer emulsion (EVA emulsion) is 45%, and the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 75%. The ammonium polyphosphate is II type ammonium polyphosphate with polymerization degree of more than 1000, and the average polymerization degree is 1200. The water used was deionized water.
In the used coating auxiliary agent, the film-forming auxiliary agent is a mixture of dipropylene glycol methyl ether and N-methyl pyrrolidone in a mass ratio of 1.5: 1. The dispersant is an aqueous dispersant Disper-715(Tego Digao), a commercial product. The defoaming agent is a BYK-019 defoaming agent (BYK chemical) which is a commercial product. The wetting agent was Wet245 wetting agent (Tego Digao), a commercially available product. The thickening agent is hydroxyethyl cellulose, and the viscosity specification (2 percent, 25 ℃ aqueous solution) is 50000mpa & s. The leveling agent is a water-based leveling agent Glidl450(Tego Digao) which is a commercial product. The zinc borate is commercial 3.5 water zinc borate (formula amount is calculated according to zinc borate) powder, and the granularity is 2-3 mu m. The ammonium octamolybdate is powder with the granularity of 2-3 mu m.
In a specific embodiment, the fuming sulfuric acid used for preparing the carbon sulfide is 40% fuming sulfuric acid (containing 40% of sulfur trioxide by mass fraction); the activated carbon is commercial activated carbon powder with the granularity of 10-15 μm.
In a specific embodiment, the planetary ball mill used has a grinding ball diameter of 5 mm.
In a specific embodiment, in order to enable the solid content of the finally obtained water-based fireproof flame-retardant coating to meet the requirement, in the preparation method, the solid content of each premix obtained in the step 1) is controlled to be not less than 55%.
Example 1
The intumescent smoke suppression flame retardant for the water-based paint comprises water and the following components in parts by weight: 24 parts of boric acid, 36 parts of ammonium polyphosphate, 20 parts of guanylurea phosphate, 36 parts of pentaerythritol, 30 parts of melamine, 1.4 parts of sulfonated carbon, 3.6 parts of zinc borate and 2.4 parts of ammonium octamolybdate.
The intumescent water-based fireproof flame retardant coating for the wood material prepared by the intumescent smoke-suppressing flame retardant also comprises water and the following components in parts by weight: 200 parts of melamine modified urea-formaldehyde resin emulsion, 110 parts of ethylene-vinyl acetate copolymer emulsion, 18 parts of coating additive and 36 parts of pigment filler titanium dioxide; the solids content of the coating was 50%.
The coating auxiliary agent consists of a film-forming auxiliary agent, a dispersing agent, a defoaming agent, a wetting agent, a thickening agent and a flatting agent, wherein the mass ratio of the film-forming auxiliary agent to the dispersing agent to the defoaming agent to the thickening agent to the flatting agent to the thickening agent to the flatting agent is 10:1.3:1.2:1.5:2.5: 1.5.
The sulfonated carbon is prepared by the following method: mixing the activated carbon and fuming sulfuric acid according to the mass ratio of 1:3.8, sulfonating for 1.5h at the temperature of 80 ℃, cooling to room temperature, washing with deionized water to be neutral, and drying to obtain the catalyst.
The preparation method of the intumescent water-based fireproof flame-retardant coating for the wood material comprises the following steps:
1) mixing the melamine modified urea-formaldehyde resin emulsion and the ethylene-vinyl acetate copolymer emulsion according to the formula ratio, and stirring to uniformly disperse the mixture to obtain a film-forming base material;
adding boric acid and pentaerythritol in a formula amount into a proper amount of water, uniformly dispersing, then adding guanylurea phosphate, ammonium polyphosphate and melamine in a formula amount, and stirring to uniformly disperse the guanylurea phosphate, the ammonium polyphosphate and the melamine to obtain an intumescent flame retardant premix;
placing the sulfonated carbon, zinc borate, ammonium octamolybdate and a proper amount of water in a planetary ball mill according to the formula ratio, and ball-milling at the rotating speed of 60r/min for 40min to uniformly disperse the sulfonated carbon, the zinc borate, the ammonium octamolybdate and the proper amount of water to obtain the synergistic smoke suppression premix;
adding the film coating auxiliary agent with the formula amount into a proper amount of water, and stirring to uniformly disperse the film coating auxiliary agent to obtain an auxiliary agent premix;
placing the pigment and filler and a proper amount of water in a formula ratio into a planetary ball mill, and carrying out ball milling at a rotating speed of 100r/min for 30min to uniformly disperse the pigment and filler to obtain pigment and filler premix;
2) mixing the expanded flame-retardant premix obtained in the step 1) with the synergistic smoke-suppressing premix, and carrying out ball milling at a rotating speed of 60r/min for 40min to uniformly disperse the mixture to obtain the smoke-suppressing flame-retardant premix (namely the water dispersant of the expanded smoke-suppressing flame retardant for the water-based paint);
3) placing the pigment-filler premix obtained in the step 1) and an auxiliary agent premix into a planetary ball mill, carrying out ball milling for 30min at a rotating speed of 100r/min to uniformly disperse the pigment-filler premix and the auxiliary agent premix, adding the smoke-suppressing and flame-retardant premix obtained in the step 2), carrying out ball milling for 30min continuously, adding a film-forming base material, adjusting the solid content to 50%, and carrying out ball milling for 50min continuously until the dispersion is uniform, thereby obtaining the intumescent waterborne fireproof flame-retardant coating for the wood material.
Example 2
The intumescent smoke suppression flame retardant for the water-based paint comprises water and the following components in parts by weight: 22 parts of boric acid, 38 parts of ammonium polyphosphate, 22 parts of guanylurea phosphate, 38 parts of pentaerythritol, 32 parts of melamine, 1.3 parts of sulfonated carbon, 4.0 parts of zinc borate and 2.0 parts of ammonium octamolybdate.
The intumescent water-based fireproof flame retardant coating for the wood material prepared by the intumescent smoke-suppressing flame retardant also comprises water and the following components in parts by weight: 200 parts of melamine modified urea-formaldehyde resin emulsion, 115 parts of ethylene-vinyl acetate copolymer emulsion, 16 parts of coating additive and 34 parts of pigment filler titanium dioxide; the solids content of the coating was 51%.
The coating auxiliary agent consists of a film-forming auxiliary agent, a dispersing agent, a defoaming agent, a wetting agent, a thickening agent and a flatting agent, wherein the mass ratio of the film-forming auxiliary agent to the dispersing agent to the defoaming agent to the thickening agent to the flatting agent to the thickening agent to the flatting agent is 10:1.0:1.0: 2.0: 1.0.
The sulfonated carbon is prepared by the following method: mixing the activated carbon and fuming sulfuric acid according to the mass ratio of 1:3.5, sulfonating for 2.5 hours at 85 ℃, cooling to room temperature, washing with deionized water to be neutral, and drying to obtain the catalyst.
The preparation method of the intumescent water-based fireproof flame-retardant coating for the wood material comprises the following steps:
1) mixing the melamine modified urea-formaldehyde resin emulsion and the ethylene-vinyl acetate copolymer emulsion according to the formula ratio, and stirring to uniformly disperse the mixture to obtain a film-forming base material;
adding boric acid and pentaerythritol in a formula amount into a proper amount of water, uniformly dispersing, then adding guanylurea phosphate, ammonium polyphosphate and melamine in a formula amount, and stirring to uniformly disperse the guanylurea phosphate, the ammonium polyphosphate and the melamine to obtain an intumescent flame retardant premix;
placing the sulfonated carbon, zinc borate, ammonium octamolybdate and a proper amount of water in a planetary ball mill according to the formula ratio, and ball-milling at the rotating speed of 100r/min for 40min to uniformly disperse the sulfonated carbon, the zinc borate, the ammonium octamolybdate and the proper amount of water to obtain the synergistic smoke suppression premix;
adding the film coating auxiliary agent with the formula amount into a proper amount of water, and stirring to uniformly disperse the film coating auxiliary agent to obtain an auxiliary agent premix;
placing the pigment and filler and a proper amount of water in a formula ratio into a planetary ball mill, and carrying out ball milling at a rotating speed of 60r/min for 30min to uniformly disperse the pigment and filler to obtain pigment and filler premix;
2) mixing the expanded flame-retardant premix obtained in the step 1) with the synergistic smoke-suppressing premix, and carrying out ball milling at a rotating speed of 60r/min for 40min to uniformly disperse the mixture to obtain the smoke-suppressing flame-retardant premix (namely the water dispersant of the expanded smoke-suppressing flame retardant for the water-based paint);
3) placing the pigment-filler premix obtained in the step 1) and an auxiliary premix into a planetary ball mill, carrying out ball milling for 30min at a rotating speed of 100r/min to uniformly disperse the pigment-filler premix and the auxiliary premix, adding the smoke-suppressing flame-retardant premix, carrying out ball milling for 30min continuously, adding the film-forming base material, adjusting the solid content to 51%, and carrying out ball milling for 50min continuously until the dispersion is uniform, thus obtaining the intumescent waterborne fireproof flame-retardant coating for the wood material.
Example 3
The intumescent smoke suppression flame retardant for the water-based paint comprises water and the following components in parts by weight: 20 parts of boric acid, 38 parts of ammonium polyphosphate, 24 parts of guanylurea phosphate, 40 parts of pentaerythritol, 30-34 parts of melamine, 1.2 parts of sulfonated carbon, 3.8 parts of zinc borate and 2.2 parts of ammonium octamolybdate.
The intumescent water-based fireproof flame retardant coating for the wood material prepared by the intumescent smoke-suppressing flame retardant also comprises water and the following components in parts by weight: 200 parts of melamine modified urea-formaldehyde resin emulsion, 120 parts of ethylene-vinyl acetate copolymer emulsion, 20 parts of coating additive and 38 parts of pigment filler titanium dioxide; the solids content of the coating was 52%.
The coating auxiliary agent consists of a film-forming auxiliary agent, a dispersing agent, a defoaming agent, a wetting agent, a thickening agent and a flatting agent, wherein the mass ratio of the film-forming auxiliary agent to the dispersing agent to the defoaming agent to the thickening agent to the flatting agent to the thickening agent to the flatting agent is 10:1.5:2.0:1.5:3.0: 2.0.
The sulfonated carbon is prepared by the following method: mixing the activated carbon and fuming sulfuric acid according to the mass ratio of 1:4.0, sulfonating for 2.0 hours at the temperature of 75 ℃, cooling to room temperature, washing with deionized water to be neutral, and drying to obtain the catalyst.
The preparation method of the intumescent water-based fireproof flame-retardant coating for the wood material comprises the following steps:
1) mixing the melamine modified urea-formaldehyde resin emulsion and the ethylene-vinyl acetate copolymer emulsion according to the formula ratio, and stirring to uniformly disperse the mixture to obtain a film-forming base material;
adding boric acid and pentaerythritol in a formula amount into a proper amount of water, uniformly dispersing, then adding guanylurea phosphate, ammonium polyphosphate and melamine in a formula amount, and stirring to uniformly disperse the guanylurea phosphate, the ammonium polyphosphate and the melamine to obtain an intumescent flame retardant premix;
placing the sulfonated carbon, zinc borate, ammonium octamolybdate and a proper amount of water in a planetary ball mill according to the formula ratio, and ball-milling at the rotating speed of 100r/min for 40min to uniformly disperse the sulfonated carbon, the zinc borate, the ammonium octamolybdate and the proper amount of water to obtain the synergistic smoke suppression premix;
adding the film coating auxiliary agent with the formula amount into a proper amount of water, and stirring to uniformly disperse the film coating auxiliary agent to obtain an auxiliary agent premix;
placing the pigment and filler and a proper amount of water in a formula ratio into a planetary ball mill, and carrying out ball milling at a rotating speed of 60r/min for 30min to uniformly disperse the pigment and filler to obtain pigment and filler premix;
2) mixing the expanded flame-retardant premix obtained in the step 1) with the synergistic smoke-suppressing premix, and carrying out ball milling at a rotating speed of 60r/min for 40min to uniformly disperse the mixture to obtain the smoke-suppressing flame-retardant premix (namely the water dispersant of the expanded smoke-suppressing flame retardant for the water-based paint);
3) placing the pigment-filler premix obtained in the step 1) and an auxiliary premix into a planetary ball mill, carrying out ball milling for 30min at a rotating speed of 100r/min to uniformly disperse the pigment-filler premix and the auxiliary premix, adding the smoke-suppressing flame-retardant premix, carrying out ball milling for 30min continuously, adding the film-forming base material, adjusting the solid content to 52%, and carrying out ball milling for 50min continuously until the dispersion is uniform, thus obtaining the intumescent waterborne fireproof flame-retardant coating for the wood material.
Experimental example 1
In this experimental example, the basic performance of the intumescent water-based fire-retardant coating for wood materials obtained in examples 1-3 was tested according to GB/T12441-.
Table 1 results of basic property test of intumescent aqueous fire-retardant coating for wooden material obtained in examples 1-3
Figure BDA0001846517600000081
As can be seen from Table 1, the performance indexes of the intumescent water-based fire-retardant coatings for wood materials obtained in examples 1-3 are all within the range of national standard requirements. Experimental results show that the intumescent water-based fire-retardant coating for the wood material, which adopts the intumescent smoke-suppressing fire retardant, meets the fire-retardant qualification test of products, and belongs to water-based fire-retardant coating with excellent performance.
Experimental example 2
The experimental example detects the use performance of the intumescent water-based fire-retardant coating for the wood material obtained in the examples 1 to 3. The experimental contents are as follows:
in experimental groups 1 to 3, the wood material obtained in the examples 1 to 3 was coated on the surface of a poplar plywood (sample) with the thickness of 100mm × 100mm × 5mm with an intumescent water-based fire-retardant coating, and the sample was polished in advance to ensure that the surface was smooth and flat and the side surface was edge-sealed; the wet coating weight was 500g/m2. The test piece was dried to a constant weight (change in mass within 24 hours of not more than 0.5%) under natural conditions at room temperature after application of the paint, and the dry film thickness was about 0.2mm, and then subjected to inspection.
Control 1 was an uncoated poplar plywood (test specimen) without any coating.
The water-based paint used in the control group 2 consists of water and the following components in parts by weight: 200 parts of melamine modified urea-formaldehyde resin emulsion, 110 parts of ethylene-vinyl acetate copolymer emulsion, 60 parts of polyphosphoric acid amine, 20 parts of guanyl urea phosphate, 36 parts of pentaerythritol, 18 parts of coating additive and 36 parts of pigment filler titanium dioxide; the solids content of the coating was 50%. The rest is the same as experimental group 1.
Each set of assays was repeated 3 times and the average was taken. The results are shown in Table 2.
TABLE 2 test results of usability of the intumescent aqueous fire-retardant coating for wooden materials obtained in examples 1 to 3
Figure BDA0001846517600000091
As can be seen from table 1, compared with the control group, the limit oxygen index of the experimental group sample coated with the intumescent aqueous fire-retardant coating for the wood material obtained in examples 1 to 3 reaches more than 43%, which belongs to the flame-retardant grade, and thus, the aqueous fire-retardant coating prepared by using the intumescent smoke-suppressing fire retardant of the invention can well exert the effects of heat insulation and oxygen isolation of an intumescent fire-retardant system, and has good fire-retardant performance. In the heat measurement experiment, the ignition time of the test sample of the experimental group coated with the intumescent water-based fireproof flame-retardant coating for the wood material obtained in the examples 1-3 reaches more than 650s, far exceeds 138s of a control group 1 (adopting the test sample without the flame-retardant smoke-inhibitor coating) and 23s of a control group 2 (adopting the test sample without the flame-retardant smoke-inhibitor coating), and the maximum heat release efficiency is not more than 93kW/m2The water-based fire-retardant coating prepared by the intumescent smoke-suppressing fire retardant is far lower than a control group, so that the combustion of a wood material can be greatly delayed in the heating process, the material pyrolysis and volatile substance generation rates are reduced, the fire spread is suppressed, the fire hazard is effectively reduced, and longer safety time is provided for escape and rescue of personnel under the fire condition. The maximum smoke release rate of the experimental groups 1-3 was not more than 0.0023m compared to the control group2(s) is about 10% of that of control group 1, and the total smoke release amount is not more than 0.21m2About 15% of control 1; CO and CO simultaneously2The release amount is greatly reduced, which shows that the water-based fire-proof flame-retardant coating adopting the intumescent smoke-suppressing flame retardant has good smoke suppression performance and can delay the generation of smoke when a fire disaster happensTime, reduce the release amount of smoke and the generation of toxic gas, and reduce the harm of the smoke to human bodies.

Claims (7)

1. An intumescent smoke-suppressing fire retardant for water-based paint is characterized in that: the paint consists of water and the following components in parts by weight: 20-24 parts of boric acid, 36-38 parts of ammonium polyphosphate, 20-24 parts of guanylurea phosphate, 36-40 parts of pentaerythritol, 30-34 parts of melamine, 1.0-1.4 parts of sulfonated carbon, 3.6-4.0 parts of zinc borate and 2.0-2.4 parts of ammonium octamolybdate;
the intumescent smoke-suppressing fire retardant for the water-based paint is prepared by the following steps:
1) adding boric acid and pentaerythritol in a formula amount into a proper amount of water, uniformly dispersing, then adding guanylurea phosphate, ammonium polyphosphate and melamine in a formula amount, and stirring to uniformly disperse the guanylurea phosphate, the ammonium polyphosphate and the melamine to obtain an intumescent flame retardant premix;
placing the sulfonated carbon, zinc borate, ammonium octamolybdate and a proper amount of water in a planetary ball mill according to the formula ratio, and ball-milling at the rotating speed of 60-100r/min for 30-50min to uniformly disperse the sulfonated carbon, the zinc borate, the ammonium octamolybdate and the proper amount of water to obtain the synergistic smoke suppression premix;
2) mixing the intumescent flame retardant premix obtained in the step 1) with the synergistic smoke suppression premix to obtain the intumescent smoke suppression flame retardant for the water-based paint.
2. An intumescent smoke-suppressing flame retardant for water-borne coatings according to claim 1, characterized in that: the polymerization degree of the ammonium polyphosphate is not less than 1000.
3. An intumescent smoke-suppressing flame retardant for water-borne coatings according to claim 1, characterized in that: the particle size of the used active carbon is 10-15 μm.
4. An intumescent smoke-suppressing flame retardant for water-borne coatings according to claim 1, characterized in that: the zinc borate is powder, and the average particle size is 2-3 mu m; the ammonium octamolybdate is powder with the average particle size of 2-3 mu m.
5. An intumescent smoke-suppressing flame retardant for water-borne coatings according to claim 1, characterized in that: the flame retardant is used for water-based paint taking melamine modified urea resin emulsion as a base material.
6. An intumescent smoke-suppressing flame retardant for water-borne coatings according to claim 5, characterized in that: in the water-based paint, the dosage of the flame retardant satisfies the following conditions: the mass ratio of solids contained in the melamine modified urea resin emulsion to ammonium polyphosphate is 100 (36-38).
7. A process for the preparation of an intumescent smoke suppressant for water borne coatings according to any of claims 1 to 6, characterized in that: the method comprises the following steps:
1) adding boric acid and pentaerythritol in a formula amount into a proper amount of water, uniformly dispersing, then adding guanylurea phosphate, ammonium polyphosphate and melamine in a formula amount, and stirring to uniformly disperse the guanylurea phosphate, the ammonium polyphosphate and the melamine to obtain an intumescent flame retardant premix;
placing the sulfonated carbon, zinc borate, ammonium octamolybdate and a proper amount of water in a planetary ball mill according to the formula ratio, and ball-milling at the rotating speed of 60-100r/min for 30-50min to uniformly disperse the sulfonated carbon, the zinc borate, the ammonium octamolybdate and the proper amount of water to obtain the synergistic smoke suppression premix;
2) mixing the intumescent flame retardant premix obtained in the step 1) with the synergistic smoke suppression premix to obtain the intumescent smoke suppression flame retardant for the water-based paint.
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