CN113817093A - Polyacrylate composite emulsion, fireproof coating, preparation method and application thereof - Google Patents

Polyacrylate composite emulsion, fireproof coating, preparation method and application thereof Download PDF

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CN113817093A
CN113817093A CN202111143423.5A CN202111143423A CN113817093A CN 113817093 A CN113817093 A CN 113817093A CN 202111143423 A CN202111143423 A CN 202111143423A CN 113817093 A CN113817093 A CN 113817093A
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composite emulsion
polyacrylate composite
emulsion
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nanoparticles
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CN113817093B (en
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张旗
杨俊锋
舒永俊
涂伟强
周良志
张恒
刘治田
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Wuhan Institute of Technology
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    • 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
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    • 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
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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    • 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
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    • 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
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Abstract

The invention discloses a polyacrylate composite emulsion, a fireproof coating, and a preparation method and application thereof, and belongs to the technical field of coatings. A preparation method of polyacrylate composite emulsion comprises the following steps: mixing inorganic nanoparticles with an oxidant for reaction to obtain oxidized inorganic nanoparticles; mixing the inorganic nano particle with a modified solvent to obtain an inorganic nano particle dispersion liquid; continuously adding a modifier, carrying out ultrasonic dispersion on the modified nanoparticles by using water, and then adding an oil phase for ultrasonic dispersion to prepare a Pickering emulsion; and (3) dropwise adding an initiator into the Pickering emulsion at 75-85 ℃ for reaction, and then adjusting the pH to 7-8 to obtain the polyacrylate composite emulsion. The invention also comprises the polyacrylate composite emulsion prepared by the method. The invention also provides the application of the polyacrylate composite emulsion in the preparation of the fireproof coating. The polyacrylate composite emulsion improves the fire resistance of the fire-retardant coating and is not easy to migrate.

Description

Polyacrylate composite emulsion, fireproof coating, preparation method and application thereof
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a polyacrylate composite emulsion, a fireproof coating, and preparation methods and applications thereof.
Background
The emulsifier is a surfactant with hydrophilic and lipophilic groups, and can remarkably reduce the surface tension of a system when in action, so that one of immiscible oil or water can be dispersed in the other liquid to form a stable emulsion. The water-based intumescent fire-retardant coating is increasingly selected due to the huge environmental protection value, and the film is widely researched for years as one of the most critical components. In the production process of traditional film forming materials, such as styrene-acrylic emulsion, silicone-acrylic emulsion and the like, pre-emulsification of monomers by using an emulsifier is one of necessary steps, and common emulsifiers are alkyl sulfate, polyoxyethylene ether, lecithin and the like.
In patent CN 104530890B, sodium-based montmorillonite is dispersed in deionized water by surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), and polyethylene glycol octyl phenyl ether (Triton X-100) and Sodium Dodecyl Sulfate (SDS) are used as composite emulsifiers to prepare montmorillonite modified acrylic emulsion, and through tests, the emulsion has better film-forming property and fireproof performance. However, the above-mentioned additive emulsifier may volatilize with water and migrate to the surface of the coating after a long time use, resulting in a decrease in the water resistance and fire resistance of the fire retardant coating. Patent CN 111995919A adopts reactive anionic emulsifier SR-10 to emulsify core layer monomer, reactive nonionic emulsifier ER-10 and PAM100 to emulsify and stabilize shell layer monomer to prepare acrylic polymer emulsion, and uses it in fire-proof coating, its advantage is that emulsifier polymerizes with it in polymerization process, which solves the problem of easy migration, and at the same time, it also does not contain Alkylphenol Ethoxylates (AEPO), which avoids a series of ecological environment problems in production, use and degradation process, but its high price limits its wide use.
Pickering emulsions, a class of emulsions in which the traditional emulsifier was replaced by solid nanoparticles of colloidal size, were found and studied since the last century by Ramsden and Pickering et al, such as Silica (SiO)2) Titanium dioxide (TiO)2) The nano particles are used for preparing Pickering emulsion and are widely applied to the fields of drug sustained release, cosmetics, food and the like. Regarding the action mechanism, it is generally considered that the solid nanoparticles are adsorbed on the oil-water interface, a single layer or several layers of solid films are formed between the liquid drops, and the liquid drops are prevented from approaching or merging with each other in a physical barrier mode; some nano particles can form a three-dimensional network structure in a water phase, so that the liquid drops are limited to be close to each other to a certain extent, and the effect of stabilizing the emulsion is achieved. The stability of the Pickering emulsion is influenced by various factors, such as the hydrophile-lyophobicity, the concentration, the granularity, the oil-water volume ratio, the pH value of a continuous phase and the like of the nano particles, to a certain extent. The Pickering emulsion requires that the solid nanoparticles can be wetted by oil and water at the same time and stably adsorbed on an oil-water interface, so that the Pickering emulsion has high requirements on the surface properties of the solid particles. How to doIt is a great problem in the prior art to obtain polyacrylate composite emulsion which is not easy to migrate in the coating and can improve the fire resistance of the coating.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a polyacrylate composite emulsion, a fireproof coating, and a preparation method and application thereof, and solves the technical problem of how to obtain the polyacrylate composite emulsion which is difficult to migrate in the coating and can improve the fire resistance of the coating in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention provides a preparation method of polyacrylate composite emulsion, which comprises the following steps:
s1, mixing and reacting the inorganic nanoparticles with an oxidant to obtain oxidized inorganic nanoparticles;
s2, mixing the oxidized inorganic nanoparticles with a modified solvent and performing ultrasonic dispersion to obtain an inorganic nanoparticle dispersion liquid;
s3, adding a modifier into the inorganic nanoparticle dispersion liquid for oil bath modification, adding the modified nanoparticles into an oil phase after water ultrasonic dispersion, and fully stirring and ultrasonically emulsifying to obtain a Pickering emulsion with stable nanoparticles;
s4, dropwise adding an initiator into the Pickering emulsion at 65-85 ℃ in an inert atmosphere for reaction, and then adding triethylamine to adjust the pH value of the emulsion to 7-8 to obtain the polyacrylate composite emulsion.
Further, in step S4, the initiator is added dropwise to carry out the reaction for 2-3 h.
Further, in step S1, the oxidizing agent is hydrogen peroxide.
Further, in step S1, the temperature of the oxidation reaction is 50 to 60 ℃, and the time of the oxidation reaction is 5 to 6 hours.
Further, in step S3, the modifier is one or more of γ -aminopropyltriethoxysilane (KH-550), γ -methacryloxypropyltrimethoxysilane (KH-570), Hexamethyldisilazane (HMDS), Vinyltriethoxysilane (VTES), and Vinyltrimethoxysilane (VTMS).
Further, in step S2, the ultrasound time is 30-40 minutes.
Further, in step S1, the inorganic nanoparticles are one or more of silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide, zinc oxide, nickel oxide, bismuth oxide, and halloysite nanotubes.
In addition, the invention also provides the polyacrylate composite emulsion prepared by the preparation method of the polyacrylate composite emulsion.
Furthermore, the invention also provides an application of the polyacrylate composite emulsion in preparation of a fireproof coating.
The invention also provides a fireproof coating, which comprises the following components in percentage by mass: 2 to 4 percent of titanium dioxide, 8 to 12 percent of melamine, 10 to 15 percent of pentaerythritol, 20 to 25 percent of ammonium polyphosphate, 18 to 23 percent of polyacrylate composite emulsion of claim 7, 0.3 to 0.8 percent of hydroxyethyl cellulose, 0.3 to 0.7 percent of dispersant and 0.3 to 0.7 percent of defoaming agent; 0.3 to 0.8 percent of n-octanol and the balance of water.
In addition, the invention also provides a preparation method of the fireproof coating, which comprises the following steps: according to the proportion of the components, titanium dioxide, hydroxyethyl cellulose and melamine are ground and mixed, then pentaerythritol and ammonium polyphosphate are added to continue grinding and mixing, then water, a dispersing agent and a defoaming agent are added to continue grinding and mixing, and then a film forming material and n-octanol are added to continue grinding and mixing to obtain the fireproof coating.
Compared with the prior art, the invention has the beneficial effects that: the inorganic nano particles are oxidized on the surface under the action of an oxidant to generate hydroxylation so as to improve the hydrophilicity of the inorganic nano particles, then the inorganic nano particles are mixed with water to form inorganic nano particle dispersion liquid, a modifier is further added into the inorganic nano particle dispersion liquid for modification, the modified nano particles are ultrasonically dispersed by water and then added with oil phase for ultrasonic dispersion to prepare Pickering emulsion, the Pickering emulsion is simultaneously wetted by oil and water and stably adsorbed on an oil-water interface, the inorganic nano particle flame retardant effect is achieved, then the Pickering emulsion is used as a template to prepare polyacrylate composite emulsion, an initiator is continuously dripped into the Pickering emulsion at 75-85 ℃ under inert atmosphere for reaction, and then triethylamine is added to adjust the pH value of the emulsion to 7-8 so as to prepare the polyacrylate composite emulsion which is used as a film forming matter and has both inorganic nano materials and organic emulsions, so that the polyacrylate composite emulsion has both functions, the polyacrylate composite emulsion is used for preparing the fireproof coating, the prepared fireproof coating has good compatibility of all components and uniform dispersion in water, the effects of improving the density and the thermal stability of the expanded carbon layer can be achieved in the combustion process, the fireproof performance of the fireproof coating is improved, the nano material is not easy to migrate in the coating, and the weather resistance of the coating is improved.
Drawings
FIG. 1 is an SEM image of a fireproof coating prepared in example 5 of the invention.
FIG. 2 is an SEM image of a fireproof coating prepared in example 6 of the invention.
Detailed Description
The specific embodiment provides a preparation method of polyacrylate composite emulsion, which comprises the following steps:
s1, mixing inorganic nanoparticles with 30% hydrogen peroxide as an oxidant according to a material ratio of 1 g: 20-25mL of the mixture is stirred and reacted for 5-6h at 50-60 ℃ to obtain oxidized inorganic nanoparticles, the inorganic nanoparticles are centrifuged after the reaction is finished, the oxidized inorganic nanoparticles are washed by deionized water and dried in a baking oven at 50-60 ℃ for 12-15h in vacuum; further, the inorganic nano-particles are one or more of silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide, zinc oxide, nickel oxide, bismuth oxide and halloysite nanotubes; the inorganic nano particles have better fireproof performance;
s2, mixing the oxidized inorganic nanoparticles with a modified solvent, and performing ultrasonic dispersion for 30-40 minutes to obtain an inorganic nanoparticle dispersion liquid; the modified solvent is formed by mixing absolute ethyl alcohol and deionized water according to the volume ratio of 30-50: 1; the mass ratio of the modified solvent to the inorganic nanoparticles is 1 g: 20-25 mL;
s3, adding a modifier into the inorganic nanoparticle dispersion liquid, carrying out oil bath reaction for 5-8h at the temperature of 100-150 ℃, dropwise adding dilute hydrochloric acid or dilute sodium hydroxide aqueous solution to maintain the pH of the water bath reaction to be 4-5, centrifugally washing and drying the modified particle dispersion liquid after the reaction is finished to obtain modified nanoparticles, then adding water into the modified nanoparticles, carrying out ultrasonic dispersion for 30-40min to obtain a modified nanoparticle dispersion liquid, adding an oil phase, carrying out magnetic stirring for 30-40min, and then carrying out ultrasonic emulsification for 30-40min to obtain Pickering emulsion; the oil phase is a mixture of methyl methacrylate and n-butyl acrylate, and the mass ratio of Methyl Methacrylate (MMA) to n-Butyl Acrylate (BA) is 1 (0.5-1.2); the modifier is one or more of gamma-aminopropyl triethoxysilane (KH-550), gamma-methacryloxypropyl trimethoxysilane (KH-570), Hexamethyldisilazane (HMDS), Vinyl Triethoxysilane (VTES) and Vinyl Trimethoxysilane (VTMS); the adding mass of the modifier is 2-8% of the mass of the inorganic nano particles;
s4, introducing nitrogen to exhaust air in the device before the reaction starts, ensuring that the whole reaction is completed in a nitrogen atmosphere, dropwise adding an initiator potassium persulfate aqueous solution into the Pickering emulsion at 65-85 ℃ in an inert atmosphere to react for 2-3h, and then adding triethylamine to adjust the pH value of the emulsion to 7-8 to obtain the polyacrylate composite emulsion; the addition amount of the initiator is 2-8% of the mass of the Pickering emulsion.
The specific embodiment also comprises the polyacrylate composite emulsion prepared by the preparation method of the polyacrylate composite emulsion.
Furthermore, the specific embodiment also comprises an application of the polyacrylate composite emulsion in preparing a fireproof coating.
The specific embodiment further provides a fire retardant coating, which comprises the following components in percentage by mass: 2-4% of titanium dioxide, 8-12% of melamine, 10-15% of pentaerythritol, 20-25% of ammonium polyphosphate, 18-23% of polyacrylate composite emulsion, 0.3-0.8% of hydroxyethyl cellulose, and 5040% of dispersing agent: 0.3-0.7%, defoaming agent 470: 0.3 to 0.7 percent; 0.3 to 0.8 percent of n-octanol and the balance of water.
In addition, the specific embodiment also provides a preparation method of the fireproof coating, which comprises the following steps: according to the proportion of the components, titanium dioxide, hydroxyethyl cellulose and melamine are ground and mixed for 10-15min, then pentaerythritol and ammonium polyphosphate are added and continuously ground and mixed for 10-15min, then water, a dispersing agent and a defoaming agent are added and continuously ground and mixed for 10-15min, and then a film forming material and n-octanol are added and continuously ground and mixed for 10-15min to obtain the fireproof coating.
The principle of the invention is as follows:
pickering emulsion is an emulsion stabilized by solid particles of colloidal size. The invention selects a part of nano particles with flame retardant property to prepare Pickering emulsion stabilized by solid nano particles, and then prepares polyacrylate emulsion with excellent flame retardant property to be used as film forming material of water-based expansion type fireproof coating. The Pickering emulsion requires that the solid nanoparticles can be wetted by oil and water at the same time and stably adsorbed on an oil-water interface, so that the Pickering emulsion has high requirements on the surface properties of the solid particles. The invention adopts a method of grafting a silane coupling agent containing hydrophobic groups on the surface of nanoparticles by using hydroxyl groups to perform hydrophobic modification on the nanoparticles, so as to prepare the stable pickering emulsion of the nanoparticles.
Many inorganic nanoparticles have good flame retardant properties in previous researches and are widely used in fire-retardant coatings as inorganic fillers, however, the blending addition mode causes the compatibility of the inorganic fillers and film-forming emulsion to be poor. In addition, the surface effect of the nanoparticles leads to a large specific surface area and an excessively high surface energy, so that agglomeration is inevitable, and the inorganic filler is difficult to uniformly disperse in the fireproof coating, thereby reducing the properties of the coating, such as fire resistance and water resistance. The invention adopts Pickering emulsion with stable nano particles to replace the traditional emulsifier, and simultaneously takes the Pickering emulsion as a template to prepare the composite polyacrylate emulsion as a film forming material of the fireproof coating, and the film forming material has both inorganic filler and organic emulsion, so the invention has the whole functions of the inorganic filler and the organic emulsion.
Specifically, due to the existence of chemical bonds and acting forces such as hydrogen bonds, van der waals forces, electrostatic repulsion and the like, before the fireproof coating burns, the nano particles wrap the polymer in an emulsifier-like manner to form emulsion particles, and the emulsion particles are relatively stably dispersed in water to form emulsion. After the fireproof coating is burnt, on one hand, most of nano particles have higher hardness and melting point, so that the expanded carbon layer can be obviously reinforced, and the thermal stability is improved; on the other hand, along with the decomposition and mutual reaction of the intumescent flame retardant system, under the action of high temperature, some inorganic nano particles can catalyze the interaction of the intumescent flame retardant system to generate crosslinking or dehydration to form ester, so that the char forming capability and efficiency of the fireproof coating are improved, and some inorganic nano particles can even generate more compact and stable compounds (such as titanium pyrophosphate, zirconium phosphate and the like), and the compounds migrate outwards due to the difference of Gibbs free energy and cover the surface of the intumescent carbon layer to realize condensed phase flame retardance together with the intumescent carbon layer. In addition, it has been found that a few nanoparticles such as ceria also have the effects of trapping and quenching radicals, preventing the progress of combustion reaction, and retarding gas-phase flame. In addition, the organic-inorganic composite emulsion used as a film forming material can greatly improve the compatibility of other organic and inorganic components in the fireproof coating, and the components are more uniformly dispersed in a medium, so that the overall weather resistance of the fireproof coating is improved.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a polyacrylate composite emulsion, which is prepared by the following steps:
s1, mixing 10g of inorganic nanoparticles with 200mL of 30% oxydol oxidant at 60 ℃, stirring for oxidation reaction for 6h to obtain oxidized inorganic nanoparticles, centrifuging after the reaction is finished, washing the oxidized inorganic nanoparticles with deionized water, and drying in a 60 ℃ oven in vacuum for 12 h; the inorganic nanoparticles in this example are ceria;
s2, mixing the oxidized inorganic nanoparticles with 250mL of a modified solvent, and performing ultrasonic dispersion for 30 minutes to obtain an inorganic nanoparticle dispersion liquid; the modified solvent is formed by mixing absolute ethyl alcohol and deionized water according to the volume ratio of 30: 1;
s3, transferring the inorganic nanoparticle dispersion liquid into a four-neck flask, connecting a stirring paddle in the middle, using a constant-pressure dropping funnel on one side, dropping a modifier within 3h, connecting a condensation pipe on the other side, plugging one port with a plug, and placing the four-neck flask into a 120 ℃ oil bath to react for 6 h; dropwise adding 1mol/L dilute hydrochloric acid or dilute sodium hydroxide aqueous solution in the reaction process to maintain the pH of the inorganic nanoparticle dispersion liquid to be 4, centrifuging the modified particle dispersion liquid in a high-speed centrifuge at the rotating speed of 1500rpm for 10min after the reaction is finished, discarding supernatant, washing the sediment at the bottom of the centrifuge tube with deionized water, centrifuging for multiple times, and then carrying out vacuum drying at 50 ℃ for 24h to obtain modified nanoparticles, then putting 2g of the modified nanoparticles into a beaker, adding 80mL of deionized water for ultrasonic dispersion for 35min, adding 30g of oil-phase methyl methacrylate and 36g of n-butyl acrylate, magnetically stirring for 30min, and then carrying out ultrasonic emulsification for 30min to obtain Pickering emulsion; the modifier is obtained by uniformly stirring 0.5g of vinyl trimethoxy silane (VTMS) and 20mL of modified solvent;
s4, transferring the prepared Pickering emulsion into a four-mouth flask, introducing nitrogen to exhaust air in a device before the reaction starts, ensuring that the whole reaction is finished under the nitrogen atmosphere, connecting a stirring paddle in the middle of the flask, connecting a condensing tube at one side of the flask, immersing the flask into an oil bath pot of a constant-temperature heating magnetic stirrer, heating to 80 ℃, starting stirring, adjusting the rotation speed to 500rpm, slowly dripping an initiator aqueous solution into the flask through a constant-pressure dropping funnel within 1h, then reacting for 2h, removing the oil bath pot, naturally cooling to 40 ℃, adjusting the pH of the emulsion to 7 by triethylamine, pouring out the emulsion, and sieving by a 200-mesh sieve to obtain the polyacrylate composite emulsion; a20 mL aqueous solution of the initiator potassium persulfate was prepared from 3g of potassium persulfate in deionized water.
Example 2
The embodiment provides a polyacrylate composite emulsion, which is prepared by the following steps:
s1, mixing 10g of inorganic nanoparticles with 250mL of 30% oxydol oxidant at 50 ℃, stirring for carrying out oxidation reaction for 5h to obtain oxidized inorganic nanoparticles, centrifuging after the reaction is finished, washing the oxidized inorganic nanoparticles with deionized water, and carrying out vacuum drying for 15h in a 50 ℃ oven; the inorganic nanoparticles in this example are zirconium dioxide;
s2, mixing the oxidized inorganic nanoparticles with 200mL of modified solvent, and performing ultrasonic dispersion for 40 minutes to obtain inorganic nanoparticle dispersion liquid; the modified solvent is formed by mixing absolute ethyl alcohol and deionized water according to the volume ratio of 40: 1;
s3, transferring the inorganic nanoparticle dispersion liquid into a four-neck flask, connecting a stirring paddle in the middle, using a constant-pressure dropping funnel on one side, dropping a modifier within 3h, connecting a condensation pipe on the other side, plugging one port with a plug, and placing the four-neck flask into a 110 ℃ oil bath to react for 5 h; dropwise adding 1mol/L dilute hydrochloric acid or dilute sodium hydroxide aqueous solution in the reaction process to maintain the pH of the inorganic nanoparticle dispersion liquid to be 5, centrifuging the modified particle dispersion liquid in a high-speed centrifuge at the rotating speed of 1500rpm for 10min after the reaction is finished, discarding supernatant, washing the sediment at the bottom of the centrifuge tube with deionized water, centrifuging for multiple times, and then drying in vacuum at 50 ℃ for 24h to obtain modified nanoparticles, then adding 50mL of deionized water into 1.5g of the modified nanoparticles for ultrasonic dispersion for 40min, adding 24g of oil-phase methyl methacrylate and 23g of n-butyl acrylate, magnetically stirring for 30min, and then performing ultrasonic emulsification for 30min to obtain Pickering emulsion; the modifier is obtained by uniformly stirring 0.5g of gamma-aminopropyltriethoxysilane (KH-550) and 20mL of modified solvent;
s4, transferring the prepared Pickering emulsion into a four-mouth flask, introducing nitrogen to exhaust air in a device before the reaction starts, ensuring that the whole reaction is finished under the nitrogen atmosphere, connecting a stirring paddle in the middle of the flask, connecting a condensing tube at one side of the flask, immersing the flask into an oil bath pot of a constant-temperature heating magnetic stirrer, heating to 85 ℃, starting stirring, adjusting the rotation speed to 500rpm, slowly dripping an initiator aqueous solution into the flask through a constant-pressure dropping funnel within 1h, then reacting for 2h, removing the oil bath pot, naturally cooling to 50 ℃, adjusting the pH of the emulsion to 8 by triethylamine, pouring out the emulsion, and sieving by a 200-mesh sieve to obtain the polyacrylate composite emulsion; a20 mL aqueous solution of the initiator potassium persulfate was prepared from 3g of potassium persulfate in deionized water.
Example 3
The embodiment provides a polyacrylate composite emulsion, which is prepared by the following steps:
s1, mixing 10g of inorganic nanoparticles with 230mL of 30% oxydol oxidant at 55 ℃, stirring for carrying out oxidation reaction for 5.5h to obtain oxidized inorganic nanoparticles, centrifuging after the reaction is finished, washing the oxidized inorganic nanoparticles with deionized water, and carrying out vacuum drying in an oven at 60 ℃ for 12 h; the inorganic nanoparticles of this example are zinc oxide;
s2, mixing the oxidized inorganic nanoparticles with 220mL of modified solvent, and performing ultrasonic dispersion for 35 minutes to obtain inorganic nanoparticle dispersion liquid; the modified solvent is formed by mixing absolute ethyl alcohol and deionized water according to the volume ratio of 45: 1;
s3, transferring the inorganic nanoparticle dispersion liquid into a four-neck flask, connecting a stirring paddle in the middle, using a constant-pressure dropping funnel on one side, dropping a modifier within 3h, connecting a condensation pipe on the other side, plugging one port with a plug, and placing the four-neck flask into a 150 ℃ oil bath to react for 5.5 h; dropwise adding 1mol/L dilute hydrochloric acid or dilute sodium hydroxide aqueous solution in the reaction process to maintain the pH of the inorganic nanoparticle dispersion liquid to be 4, centrifuging the modified particle dispersion liquid in a high-speed centrifuge at the rotating speed of 1500rpm for 10min after the reaction is finished, removing supernatant, washing precipitates at the bottom of the centrifuge tube with deionized water, centrifuging for multiple times, and then carrying out vacuum drying at 50 ℃ for 24h to obtain modified nanoparticles, then adding 50mL of deionized water into 2g of the modified nanoparticles for ultrasonic dispersion for 30min, adding 30g of oil-phase methyl methacrylate and 20g of n-butyl acrylate, magnetically stirring for 35min, and then carrying out ultrasonic emulsification for 35min to obtain Pickering emulsion; the modifier is obtained by uniformly stirring 0.5g of vinyl trimethoxy silane (VTMS) and 20mL of modified solvent;
s4, transferring the prepared Pickering emulsion into a four-mouth flask, introducing nitrogen to exhaust air in a device before the reaction starts, ensuring that the whole reaction is finished under the nitrogen atmosphere, connecting a stirring paddle in the middle of the flask, connecting a condensing tube at one side of the flask, immersing the flask into an oil bath pot of a constant-temperature heating magnetic stirrer, heating to 75 ℃, starting stirring, adjusting the rotation speed to 500rpm, slowly dripping an initiator aqueous solution into the flask through a constant-pressure dropping funnel within 1h, then reacting for 2.5h, removing the oil bath pot, naturally cooling to 40 ℃, adjusting the pH of the emulsion to 8 by triethylamine, pouring out the emulsion, and sieving by a 200-mesh sieve to obtain the polyacrylate composite emulsion; a20 mL aqueous solution of the initiator potassium persulfate was prepared from 3g of potassium persulfate in deionized water.
Example 4
The embodiment provides a polyacrylate composite emulsion, which is prepared by the following steps:
s1, mixing 10g of inorganic nanoparticles with 220mL of 30% oxydol oxidant at 50 ℃, stirring for carrying out oxidation reaction for 5h to obtain oxidized inorganic nanoparticles, centrifuging after the reaction is finished, washing the oxidized inorganic nanoparticles with deionized water, and carrying out vacuum drying in an oven at 60 ℃ for 12 h; the inorganic nanoparticles of this example are nickel oxide;
s2, mixing the oxidized inorganic nanoparticles with 220mL of modified solvent, and performing ultrasonic dispersion for 30 minutes to obtain inorganic nanoparticle dispersion liquid; the modified solvent is formed by mixing absolute ethyl alcohol and deionized water according to the volume ratio of 50: 1;
s3, transferring the inorganic nanoparticle dispersion liquid into a four-neck flask, introducing nitrogen to exhaust air in a device before the reaction starts, ensuring that the whole reaction is completed in the nitrogen atmosphere, connecting a stirring paddle in the middle, using a constant-pressure dropping funnel at one side, dropping a modifier within 3h, connecting a condenser pipe at the other side, plugging one port with a plug, and placing the four-neck flask into a 100 ℃ oil bath pot for reaction for 6 h; dropwise adding 1mol/L dilute hydrochloric acid or dilute sodium hydroxide aqueous solution in the reaction process to maintain the pH of the inorganic nanoparticle dispersion liquid to be 5, centrifuging the modified particle dispersion liquid in a high-speed centrifuge at the rotating speed of 1500rpm for 10min after the reaction is finished, discarding supernatant, washing the sediment at the bottom of the centrifuge tube with deionized water, centrifuging for multiple times, drying in vacuum at 50 ℃ for 24h to obtain modified nanoparticles, adding 60mL of deionized water into 1.8g of the modified nanoparticles, ultrasonically dispersing for 30min, adding 30g of oil-phase methyl methacrylate and 32g of n-butyl acrylate, magnetically stirring for 35min, and ultrasonically emulsifying for 30min to obtain Pickering emulsion; the modifier is obtained by uniformly stirring 0.5g of Vinyl Triethoxysilane (VTES) and 20mL of modified solvent;
s4, transferring the prepared Pickering emulsion into a four-mouth flask, introducing nitrogen to exhaust air in a device before the reaction starts, ensuring that the whole reaction is finished under the nitrogen atmosphere, connecting a stirring paddle in the middle of the flask, connecting a condensing tube at one side of the flask, immersing the flask into an oil bath pot of a constant-temperature heating magnetic stirrer, heating to 65 ℃, starting stirring, adjusting the rotation speed to 500rpm, slowly dripping an initiator aqueous solution into the flask through a constant-pressure dropping funnel within 1h, then reacting for 2.5h, removing the oil bath pot, naturally cooling to 40 ℃, adjusting the pH of the emulsion to 7 by triethylamine, pouring out the emulsion, and sieving by a 200-mesh sieve to obtain the polyacrylate composite emulsion; a20 mL aqueous solution of the initiator potassium persulfate was prepared from 3g of potassium persulfate in deionized water.
Example 5
The embodiment provides a fireproof coating, which comprises, by mass, 2% of titanium dioxide, 9% of melamine, 11% of pentaerythritol, 25% of ammonium polyphosphate, 20% of a film forming material, 0.3% of hydroxyethyl cellulose, and a dispersing agent 5040: 0.3%, defoamer 470: 0.4 percent; n-octanol 0.3%, deionized water 31.7%. Wherein the film-forming material was the polyacrylate composite emulsion (P (BA-MMA) -m-CeO) prepared in example 12)。
The fireproof coating of the embodiment is prepared by the following steps:
adding weighed titanium dioxide, hydroxyethyl cellulose and melamine into a mortar, grinding for 15min until no obvious agglomeration exists and no gravel feeling exists, adding pentaerythritol and ammonium polyphosphate, continuing uniformly grinding for 15min, adding deionized water, a dispersing agent 5040 and a defoaming agent 470, fully stirring and grinding for 10min, finally adding a film forming material and n-octanol, and continuing stirring and grinding for 10min to obtain the required water-based intumescent fire-retardant coating.
Example 6
The embodiment provides a fireproof coating, which comprises the following components in percentage by mass: 2% of titanium dioxide, 8% of melamine, 10% of pentaerythritol, 25% of ammonium polyphosphate, 18% of film forming material, 0.3% of hydroxyethyl cellulose, and 5040% of dispersing agent: 0.3%, defoamer 470: 0.4 percent; n-octanol 0.3%, deionized water 35.7%. Wherein the film-forming material was the polyacrylate composite emulsion (P (BA-MMA) -m-ZrO) prepared in example 22)。
The fireproof coating in the embodiment is prepared by the following steps: adding weighed titanium dioxide, hydroxyethyl cellulose and melamine into a mortar, grinding for 15min until no obvious agglomeration exists and no gravel feeling exists, adding pentaerythritol and ammonium polyphosphate, continuing uniformly grinding for 15min, adding deionized water, a dispersing agent 5040 and a defoaming agent 470, fully stirring and grinding for 10min, finally adding a film forming material and n-octanol, and continuing stirring and grinding for 10min to obtain the required water-based intumescent fire-retardant coating.
Example 7
The embodiment provides a fireproof coating, which comprises the following components in percentage by mass: 4% of titanium dioxide, 8% of melamine, 15% of pentaerythritol, 22% of ammonium polyphosphate, 23% of the polyacrylate composite emulsion prepared in example 2, 0.8% of hydroxyethyl cellulose, and 5040% of a dispersant: 0.3-0.7%, defoaming agent 470: 0.5 percent; n-octanol is 0.3%, and the rest is water.
The fireproof coating in the embodiment is prepared by the following steps: according to the ratio of the components, titanium dioxide, hydroxyethyl cellulose and melamine are ground and mixed for 10min, then pentaerythritol and ammonium polyphosphate are added and continuously ground and mixed for 10min, then water, a dispersing agent 5040 and a defoaming agent 470 are added and continuously ground and mixed for 15min, and then a film forming material and n-octanol are added and continuously ground and mixed for 15min to obtain the fireproof coating.
Example 8
The embodiment provides a fireproof coating, which comprises the following components in percentage by mass: 2% of titanium dioxide, 9% of melamine, 11% of pentaerythritol, 21% of ammonium polyphosphate, 21% of the polyacrylate composite emulsion prepared in example 2, 0.4% of hydroxyethyl cellulose, and 5040% of a dispersant: 0.6%, defoamer 470: 0.6 percent; n-octanol (0.7%) and water (rest).
The fireproof coating in the embodiment is prepared by the following steps: according to the ratio of the components, titanium dioxide, hydroxyethyl cellulose and melamine are ground and mixed for 12min, then pentaerythritol and ammonium polyphosphate are added and continuously ground and mixed for 12min, then water, a dispersing agent 5040 and a defoaming agent 470 are added and continuously ground and mixed for 13min, and then a film forming material and n-octanol are added and continuously ground and mixed for 13min to obtain the fireproof coating.
Comparative example 1
In order to further characterize the practical application effect of the nanoparticles in the present invention, the fire retardant coating proposed in comparative example 1 is substantially the same as the preparation process of example 4, except that the acrylic emulsion prepared by using the conventional emulsifier is used as a film-forming material, and no nanoparticles are added to prepare the aqueous intumescent fire retardant coating, and the preparation process is as follows:
preparing a fireproof coating:
the fireproof coating comprises the following components in percentage by mass: titanium dioxide: 2% and melamine: 9%, pentaerythritol: 12%, ammonium polyphosphate: 25%, film-forming material: 21%, hydroxyethyl cellulose: 0.3%, dispersant 5040: 0.3%, defoamer 470: 0.4 percent; n-octanol: 0.3%, deionized water: 29.7 percent.
Secondly, adding the weighed titanium dioxide, hydroxyethyl cellulose and melamine into a mortar, grinding for 15min until no obvious agglomeration exists and no sense of grit, adding pentaerythritol and ammonium polyphosphate, continuing to grind uniformly for 15min, adding deionized water, a dispersing agent 5040 and a defoaming agent 470, fully stirring and grinding for 10min, finally adding a film forming material and n-octanol, continuing to stir and grind for 10min to obtain the required water-based intumescent fire-retardant coating.
Comparative example 2
In order to further characterize the practical application effect of the modified nanoparticles prepared in the present invention, the comparative example is substantially the same as the preparation process in example 1, except that nano ceria nanoparticles without surface modification are used as inorganic filler, and acrylic emulsion prepared by conventional emulsifier is used as film forming material to prepare the aqueous intumescent fire retardant coating, and the preparation process is as follows:
preparing a fireproof coating:
the fireproof coating comprises the following components in percentage by mass: nano cerium dioxide: 3% and titanium dioxide: 2% and melamine: 9%, pentaerythritol: 12%, ammonium polyphosphate: 25%, film-forming material: 18%, hydroxyethyl cellulose: 0.3%, dispersant 5040: 0.3%, defoamer 470: 0.4 percent; n-octanol: 0.3%, deionized water: 29.7 percent.
Secondly, adding the weighed modified nano cerium dioxide, titanium dioxide, hydroxyethyl cellulose and melamine into a mortar, grinding for 15min until no obvious agglomeration exists, adding pentaerythritol and ammonium polyphosphate after no sense of sand exists, continuing to grind uniformly for 15min, adding deionized water, a dispersing agent 5040 and a defoaming agent, fully stirring and grinding for 10min, finally adding a film forming material and n-octanol, and continuing to stir and grind for 10min to obtain the required water-based intumescent fire-retardant coating.
Comparative example 3
To further characterize the practical effect of the composite emulsion prepared in the present invention, comparative example 3 was substantially the same as the preparation process of example 1, except that modified nano-ceria (m-CeO) prepared in example 1 was used2) The water-based intumescent fire-retardant coating is prepared by taking acrylic emulsion prepared by a conventional emulsifier as an inorganic filler and taking the acrylic emulsion as a film-forming material, and the preparation process comprises the following steps:
1) modified nano cerium dioxide (m-CeO)2) The specific procedure for the preparation of (1) was the same as in example 1.
2) Preparing a fireproof coating:
the fireproof coating comprises the following components in percentage by mass: modified nano cerium dioxide: 3% and titanium dioxide: 2% of melamine: 9%, pentaerythritol: 12%, ammonium polyphosphate: 25%, film-forming material: 18%, hydroxyethyl cellulose: 0.3%, dispersant 5040: 0.3%, defoamer 470: 0.4 percent; n-octanol: 0.3%, deionized water: 29.7 percent.
Secondly, adding the weighed modified nano cerium dioxide, titanium dioxide, hydroxyethyl cellulose and melamine into a mortar, grinding for 15min until no obvious agglomeration exists, adding pentaerythritol and ammonium polyphosphate after no sense of sand exists, continuing to grind uniformly for 15min, adding deionized water, a dispersing agent 5040 and a defoaming agent, fully stirring and grinding for 10min, finally adding a film forming material and n-octanol, and continuing to stir and grind for 10min to obtain the required water-based intumescent fire-retardant coating.
The fireproof coatings prepared in the above examples and comparative examples were subjected to sample preparation, and a simulated large panel combustion test method was used to test the fire resistance of the samples, the sample preparation process was as follows:
firstly, taking a steel plate with the thickness of 150mm multiplied by 100mm multiplied by 3mm, polishing the steel plate by using coarse sand paper under the washing of water flow until the surface has no obvious rust or other impurities, wiping off the water on the surface of the steel plate, naturally drying the steel plate, weighing the steel plate, and storing the steel plate to a shade place.
Secondly, polishing the used steel plate by using fine sand paper until the surface is bright, uniformly coating the water-based intumescent fire retardant coating prepared according to the formula on one surface of the steel plate without surface pollution by using a plastic dropper, marking the other surface, airing at room temperature until the surface is dry and does not flow (one to two days), putting the steel plate into a 60 ℃ oven for drying for 12 hours, taking out, measuring the thickness of the coating, and weighing the mass of the steel plate.
Preparing two samples according to each formula, measuring the thickness of the coatings by using a vernier caliper, ensuring that the thickness difference of the coatings of the two samples is not more than 1mm, weighing the mass of the samples, and ensuring that the mass difference of the steel plates before and after coating is not more than 1 g.
TABLE 1 comparison of coatings prepared in examples 5-8 and comparative examples 1-2 before and after fire performance testing
Figure BDA0003284518760000171
The fire endurance is: the time required for the expanded carbon layer formed after the flame contact coating and the fireproof coating are burnt to be completely broken and the back temperature of the steel plate to be suddenly changed;
the microscopic morphology of the expanded carbon layers of the fireproof coatings prepared in the examples 5 and 6 in the fire resistance test is observed by using a scanning electron microscope, and the result is shown in fig. 1 and 2, and as can be seen by combining fig. 1, fig. 2 and table 1, the polyacrylate composite emulsion prepared by the pickering emulsion polymerization with the stable modified nanoparticles greatly improves the fire resistance and the compatibility among the components of the aqueous expanded fireproof coating, and the expanded carbon layers are compact and firm, have good thermal stability, better isolate air convection and obstruct heat propagation, and thus have more excellent fire resistance.
Compared with the prior art, the invention has the following other beneficial effects:
1) the Pickering emulsion is used for replacing the traditional emulsifier, so that the serious ecological pollution caused by excessive use and degradation of the emulsifier in recent years is greatly reduced, and the production cost is also reduced. Meanwhile, most of the nano particles are insoluble in water, so that heavy metal ion pollution to the water environment is avoided, and the development concept of green, environmental protection and economy is realized.
2) The invention uses Pickering emulsion to replace the traditional emulsifier and uses the Pickering emulsion as the template to prepare the composite polyacrylate emulsion as the film forming material of the fireproof coating, thereby realizing the integration of inorganic filler and organic film forming material emulsion, greatly improving the defect of poor compatibility of organic and inorganic components of the fireproof coating, and being beneficial to the uniform dispersion of the components in water.
3) According to the invention, the Pickering emulsion is prepared by selecting the nano particles with a certain flame retardant effect, and the acrylic acid composite emulsion is prepared by using the nano particles, so that the nano particles play a role in improving the density and the thermal stability of the expanded carbon layer in the combustion process of the fireproof coating.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The preparation method of the polyacrylate composite emulsion is characterized by comprising the following steps:
s1, mixing and reacting the inorganic nanoparticles with an oxidant to obtain oxidized inorganic nanoparticles;
s2, mixing the oxidized inorganic nanoparticles with a modified solvent and performing ultrasonic dispersion to obtain an inorganic nanoparticle dispersion liquid;
s3, adding a modifier into the inorganic nanoparticle dispersion liquid for modification, adding an oil phase into the modified nanoparticles after ultrasonic dispersion by using water, and performing ultrasonic dispersion to obtain a Pickering emulsion;
s4, dropwise adding an initiator into the Pickering emulsion at 75-85 ℃ in an inert atmosphere for reaction, and then adding triethylamine to adjust the pH value of the emulsion to 7-8 to obtain the polyacrylate composite emulsion.
2. The method for preparing a polyacrylate composite emulsion according to claim 1, wherein in step S4, the initiator is added dropwise to react for 2-3 h.
3. The method for preparing the polyacrylate composite emulsion according to claim 1, wherein in step S1, the oxidant is hydrogen peroxide.
4. The method for preparing a polyacrylate composite emulsion according to claim 1, wherein in step S1, the temperature of the oxidation reaction is 50-60 ℃ and the time of the oxidation reaction is 5-6 h.
5. The method for preparing a polyacrylate composite emulsion according to claim 1, wherein in step S2, the time of the ultrasonic treatment is 30 to 40 minutes.
6. The method of claim 1, wherein in step S1, the inorganic nanoparticles are one or more of silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide, zinc oxide, nickel oxide, bismuth oxide, and halloysite nanotubes.
7. A polyacrylate composite emulsion obtained by the method for preparing a polyacrylate composite emulsion according to any one of claims 1 to 6.
8. Use of the polyacrylate composite emulsion according to claim 7 for the preparation of fire-retardant coatings.
9. The fireproof coating is characterized by comprising the following components in percentage by mass: 2 to 4 percent of titanium dioxide, 8 to 12 percent of melamine, 10 to 15 percent of pentaerythritol, 20 to 25 percent of ammonium polyphosphate, 18 to 23 percent of polyacrylate composite emulsion of claim 7, 0.3 to 0.8 percent of hydroxyethyl cellulose, 0.3 to 0.7 percent of dispersant and 0.3 to 0.7 percent of defoaming agent; 0.3 to 0.8 percent of n-octanol and the balance of water.
10. A method for preparing the fire retardant coating of claim 9, comprising the steps of: according to the proportion of the components, titanium dioxide, hydroxyethyl cellulose and melamine are ground and mixed, then pentaerythritol and ammonium polyphosphate are added to continue grinding and mixing, then water, a dispersing agent and a defoaming agent are added to continue grinding and mixing, and then a film forming material and n-octanol are added to continue grinding and mixing to obtain the fireproof coating.
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CN117186755A (en) * 2023-08-18 2023-12-08 青岛格林沃德新材料科技有限公司 Nano modified single-component high-strength elastic protective coating and preparation method and application thereof

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