CN112831224A - Color-adjustable water-based flame-retardant coating with fire circulation early warning function and preparation method and application thereof - Google Patents
Color-adjustable water-based flame-retardant coating with fire circulation early warning function and preparation method and application thereof Download PDFInfo
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- 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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
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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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/26—Cellulose ethers
- C09D101/28—Alkyl ethers
- C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
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- 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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
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Abstract
The invention discloses a color-adjustable water-based flame-retardant coating with a fire circulation early warning functionAnd a preparation method and application thereof. The raw material composition of the water-based flame-retardant coating comprises TiO2MMT, cellulose nanofibers and a thickener; TiO 22The mass ratio of the titanium oxide to the MMT is 1-9: 1, and TiO2And the mass sum of the MMT and the water-based flame-retardant coating accounts for 10-20% of the total mass of the water-based flame-retardant coating. The preparation method comprises the following steps: (1) adding TiO into the mixture2Respectively preparing the aqueous solution and the MMT into aqueous solution, and respectively carrying out ultrasonic treatment to obtain TiO2Solutions and MMT solutions; (2) adding TiO into the mixture2And mixing the solution and the MMT solution, adding cellulose nanofiber and a thickening agent for dissolving, uniformly stirring, and performing ultrasonic dispersion to obtain the water-based flame-retardant coating with the fire circulation early warning function and adjustable color. The water-based flame-retardant coating can be used on the surfaces of inflammable materials such as walls or fabrics, is green and flame-retardant, has adjustable color, and can provide a sensitive fire circulation quick early warning signal after being in point connection with an alarm device.
Description
Technical Field
The invention relates to the technical field of water-based flame-retardant coatings, in particular to a water-based flame-retardant coating with a fire circulation early warning function and adjustable color, and a preparation method and application thereof.
Background
With the continuous development of science and technology, flammable materials such as high polymers and the like are widely applied to daily life from fast-forwarding packaging materials to interior decoration materials, textile materials and building exterior wall heat insulation materials. However, the high molecular material is easy to ignite and spread quickly, which is likely to cause fire accidents, resulting in serious casualties and economic losses. In particular, in recent years, high-rise fires frequently occur, and the high-rise fire extinguishing device has the characteristics of rapid fire spread, difficulty in evacuating people, great difficulty in fighting fire and the like. Therefore, it is urgently needed to develop a fire alarm sensor which can quickly send out an alarm signal after a fire disaster occurs and can realize repeated and cyclic quick early warning, so that the fire disaster is reduced and even avoided, and the fire alarm sensor has great significance.
At present, photosensitive sensors, infrared sensors, gas sensors, smoke sensors and the like are rapidly developed and applied in fire early warning, but have some defects. For example, the smoke alarm sensor has long detection time, is easily influenced by the environment, has a limited application range, and cannot meet the outdoor complex environment or climate conditions. In some fire accidents, it is difficult for such fire sensing to provide efficient and rapid early warning. Recently, a coating prepared from nano materials such as graphene oxide and the like is developed to be used for preparing a novel high-sensitivity resistance sensor, for example, the invention patent with the publication number of CN 109021983A mentions a preparation method of a modified graphene oxide flame-retardant coating and a fire early warning application thereof, L-type ascorbic acid is utilized to promote the graphene oxide to be reduced at a medium and low temperature (100-250 ℃), so that low-temperature rapid alarm is realized, but the sensor cannot realize multi-cycle alarm. In addition, patent with publication number CN 111254737 a reports a multifunctional MXene coating, a preparation method thereof and application thereof in fire detection and early warning, and proposes that a recyclable fire alarm sensor is prepared by introducing a proper amount of high polymer materials based on MXene as a raw material. However, functional coatings based on nanomaterials such as graphene oxide or MXene still have many problems and challenges. Firstly, the nano materials are black, and the color of the coating can not be adjusted, so that the wide potential application of the coating is greatly limited. Secondly, the preparation process of the nano material is complex and time-consuming, and involves organic solvent and strong oxidant, thus polluting the environment and being high in cost, which is not beneficial to the practical use of the coating. In addition, MXene has excellent conductivity, the alarm response can be triggered only by oxidation under flame, and the prepared coating has certain conductivity and cannot meet the actual application requirement of good insulating property.
Conventional coatings are largely classified as paints, water-borne paints, powder coatings, and generally contain film-forming substances (resins, emulsions), pigments, solvents, and adjuvants. However, the existing coating still has the following problems: (1) solvent type coating is usually formed into coating dispersion liquid by organic solvent, which not only pollutes environment, but also has certain harm to human health, such as stimulation to skin, eyes and upper respiratory tract, and cancerogenesis in serious cases; (2) most water-based coatings do not have a flame retardant function and cannot provide a sensitive circulating alarm under the condition of flame attack. Therefore, the development of a water-based flame retardant coating with a fire circulation early warning function and adjustable color is urgently needed to solve the bottleneck problem of the traditional coating.
Disclosure of Invention
Aiming at the defects of fire safety and monitoring of the existing flammable material systems such as fabrics and the like in the field, the invention provides the color-adjustable water-based flame-retardant coating with the fire circulation early warning function, which is prepared from white titanium dioxide (TiO)2) Montmorillonite (MMT) is the main raw material, can be used for fire circulation early warning, can directly coat on flammable materials such as fabrics or wall surfaces, and can obtain quick and sensitive circulation alarm response while realizing green flame retardance. Before the color is not adjusted, the water-based flame-retardant coating is white, so that the corresponding required color can be obtained by adding various pigments, and then flammable materials such as fabrics with various colors and colorful wall surface effects can be obtained by coating, and the water-based flame-retardant coating is attractive and practical.
A color-adjustable water-based flame-retardant coating with a fire circulation early warning function comprises TiO as a raw material2MMT, functional nanofiber film-forming auxiliaries and thickeners;
the TiO is2The mass ratio of the TiO to the MMT is 1-9: 1, and the mass ratio of the TiO to the MMT is2The mass sum of the MMT and the water-based flame-retardant coating accounts for 10-20% of the total mass of the water-based flame-retardant coating;
the functional nanofiber film-forming auxiliary agent is Cellulose Nanofiber (CNF).
According to the invention, the water-soluble coating formed by drying the water-based flame-retardant coating has good insulativity at normal temperature by adjusting the raw materials and the proportion thereof. The functional nano-fiber film-forming additive cellulose nano-fiber added in the coating is biomass-derived environment-friendly cellulose, and the water-based flame-retardant coating body of the inventionHaving its particularity with TiO2Synergistic dispersion and flame-retardant effect between the components. Researches show that the CNF surface contains abundant hydroxyl to be beneficial to TiO2Uniformly dispersed in the coating to form a flexible and hydrophilic film, and easily carbonized at high temperature to form a protective coating which is beneficial to flame retardance. TiO in coatings2Embedded in the MMT lamellar structure, when flame attacks, a compact network can be formed, electron transition occurs to form current, the resistance value of the coating is rapidly reduced on the original basis, and devices such as an alarm lamp and the like are triggered; when the flame is removed, the circuit is immediately disconnected, the alarm signal disappears, and the conversion between the conductor and the insulator can be realized. When the flame attacks again, the circuit is switched on again, and after the flame is removed, the circuit is switched off immediately, so that stable cyclic fire early warning is realized.
When CNF is used as the film-forming auxiliary agent, the mass percentage of the functional nanofiber film-forming auxiliary agent in the water-based flame-retardant coating is preferably 4-15%, and the functional nanofiber film-forming auxiliary agent is added with the TiO in the above-mentioned amount2Can form better synergistic dispersion effect and improve the flame retardant property, and a coating formed by the water-based flame retardant coating has excellent flexibility and is more suitable for soft and flammable materials such as fabrics and the like.
In the aqueous flame retardant coating system of the present invention, the thickener is preferably hydroxymethyl cellulose. The hydroxymethyl cellulose is easy to dissolve in water and is transparent jelly, which is beneficial to increasing the viscosity of the coating and does not influence the color of the coating.
When hydroxymethyl cellulose is used as the thickening agent, the thickening agent accounts for 1-5% of the total mass of the water-based flame-retardant coating. The obtained water-based flame-retardant coating has proper viscosity and can enhance the adhesion of the coating.
The inventor researches and discovers that TiO2And the mass ratio of the MMT influences the initial resistance value and the flame retardant effect of a coating formed by the water-based flame retardant coating. The uniform layered structure of MMT in the coating ensures the stability of the cyclic early warning and also provides flame retardance for the coating, but if the content of MMT is too high, TiO can be affected2The continuity of the network influences the stability and the cyclicity of fire early warning; if TiO2The content is too highThe lamellar structure of MMT is hindered and the flame retardancy of the coating is affected. The TiO is2The mass ratio of MMT to MMT is preferably 2-4: 1.
The raw material composition of the water-based flame-retardant coating can also comprise pigment which is added according to needs so as to enable the water-based flame-retardant coating to obtain corresponding color.
The invention also provides a preparation method of the water-based flame-retardant coating, which comprises the following steps:
(1) adding TiO into the mixture2Respectively preparing the aqueous solution and the MMT into aqueous solution, and respectively carrying out ultrasonic treatment to obtain TiO2Solutions and MMT solutions;
(2) subjecting the TiO to a reaction2And mixing the solution and the MMT solution, adding the functional nanofiber film-forming auxiliary agent and the thickening agent for dissolving, uniformly stirring, and performing ultrasonic dispersion to obtain the water-based flame-retardant coating with the fire circulation early warning function and adjustable color.
Preferably, in the step (1), the TiO is2The concentration of the solution is 350-450 mg/g, and the concentration of the MMT solution is 50-100 mg/g;
the ultrasonic time is 0.5-2 h.
Preferably, in the step (2), the stirring time is 3-12 hours, and the ultrasonic dispersion time is 0.5-1 hour.
Preferably, the preparation method further comprises the following steps:
(3) and (3) adding a pigment into the water-based flame-retardant coating obtained in the step (2), and uniformly stirring to obtain the water-based flame-retardant coating with the corresponding color.
The invention also provides application of the water-based flame-retardant coating in fire circulation early warning, the water-based flame-retardant coating has the characteristics of green flame retardance and adjustable color, after the water-based flame-retardant coating is electrically connected with an alarm device, a sensitive fire circulation quick early warning signal can be provided, and the alarm response time is not more than 3-5 s.
Preferably, the water-based flame-retardant coating is coated on a wall surface or a surface of a flammable material, dried to form a coating, and the coating is electrically connected with an alarm device. Such as fabrics and the like. The drying temperature is preferably 20-100 ℃.
Compared with the prior art, the invention has the main advantages that:
1. the preparation process and the product are environment-friendly, the preparation method is simple, the cost is lower, the reaction is controllable, and stable cyclic alarm can be realized.
2. The prepared composite coating is white, and the color can be adjusted by adding pigments through simple operation, so that multifunctional coatings with different colors can be obtained.
3. The prepared water-soluble composite coating can be uniformly dispersed and can be used on different substrates, and can be brushed on the surfaces of flammable materials such as fabrics and the like or wall surfaces, so that green flame retardance and rapid circulating fire early warning are realized.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a red, yellow and blue modified cotton fabric composite material with cotton fabric as a substrate;
FIG. 2 is a photograph showing the flame retardant properties of pure cotton fabric (a) and the white modified cotton fabric composite (b), the red modified cotton fabric composite (c), the yellow modified cotton fabric composite (d), and the blue modified cotton fabric composite (e) of example 2;
fig. 3 is an experimental photograph showing that a fire alarm occurs rapidly when the blue modified cotton fabric composite material (a) of example 2, the cotton fabric (b) coated with the commercial water-based paint, and the pure cotton fabric (c) of the comparative example are attacked by flames, and an alarm signal disappears rapidly when the flames are removed, wherein the duration of each flame attack is 30s, and the duration of each flame removal is 60 s.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
As shown in FIG. 1, 72g of TiO was taken2And 72g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose to dissolve, stirring for 12 hours, uniformly mixing, and performing ultrasonic dispersion for 0.5-1 hour, wherein part of water is volatilized to obtain a white water-based flame-retardant coating with the mass fraction of 240 mg/g; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in a 50 ℃ drying oven, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Example 2
As shown in FIG. 1, 108g of TiO was taken2And 36g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose to dissolve, adding a proper amount of deionized water to ensure that the mass fraction of the mixed solution is 240mg/g, stirring for 12 hours, uniformly mixing, and performing ultrasonic dispersion for 0.5-1 hour to obtain a white water-based flame-retardant coating; respectively dripping red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain a red water-based flame-retardant coating, a yellow water-based flame-retardant coating and a blue water-based flame-retardant coating; the prepared water-based flame-retardant coatings with different colors are coated on the surface of a cotton fabric in a brush way, a conductive electrode is embedded at the bottom of the cotton fabric, the cotton fabric is uniformly coated and then is placed into a drying oven for drying at 50 ℃, and the coating and the drying are carried out for 15 times in total, so that a white modified cotton fabric composite material, a red modified cotton fabric composite material, a yellow modified cotton fabric composite material and a blue modified cotton fabric composite material are respectively prepared.
Example 3
As shown in FIG. 1, 115.2g of TiO was taken2And 28.8g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solutionMixing and adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose to dissolve, adding a proper amount of deionized water to enable the mass fraction of the mixed solution to be 240mg/g, stirring for 12 hours, uniformly mixing, and performing ultrasonic dispersion for 0.5-1 hour to obtain a white water-based flame-retardant coating; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in a 50 ℃ drying oven, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Example 4
As shown in FIG. 1, 72g of TiO was taken2And 72g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 48g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 48g of hydroxymethyl cellulose to dissolve, stirring for 12 hours, uniformly mixing, performing ultrasonic dispersion for 0.5-1 hour, and volatilizing part of water to obtain a white water-based flame-retardant coating with the mass fraction of 240 mg/g; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in a 50 ℃ drying oven, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Example 5
As shown in FIG. 1, 108g of TiO was taken2And 36g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 48g of functional nano-fiber film-forming auxiliary agent cellulose nano-fiber (CNF) and 48g of hydroxymethyl cellulose for dissolving, adding a proper amount of deionized water to ensure that the mass fraction of the mixed solution is 240mg/g, stirring for 12h, and uniformly mixingThen carrying out ultrasonic dispersion for 0.5-1 h to obtain a white water-based flame retardant coating; respectively dripping red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain a red water-based flame-retardant coating, a yellow water-based flame-retardant coating and a blue water-based flame-retardant coating; the prepared water-based flame-retardant coatings with different colors are coated on the surface of a cotton fabric in a brush way, a conductive electrode is embedded at the bottom of the cotton fabric, the cotton fabric is uniformly coated and then is placed into a drying oven for drying at 50 ℃, and the coating and the drying are carried out for 15 times in total, so that a white modified cotton fabric composite material, a red modified cotton fabric composite material, a yellow modified cotton fabric composite material and a blue modified cotton fabric composite material are respectively prepared.
Example 6
As shown in FIG. 1, 115.2g of TiO was taken2And 28.8g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 48g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 48g of hydroxymethyl cellulose to dissolve, adding a proper amount of deionized water to enable the mass fraction of the mixed solution to be 240mg/g, stirring for 12 hours, uniformly mixing, and performing ultrasonic dispersion for 0.5-1 hour to obtain a white water-based flame-retardant coating; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in a 50 ℃ drying oven, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Example 7
As shown in FIG. 1, 72g of TiO was taken2And 72g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose for dissolving, stirring for 3h, uniformly mixing, performing ultrasonic dispersion for 0.5-1 h, and volatilizing part of water to obtain white water with the mass fraction of 240mg/gA colored water-based flame retardant coating; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in a 50 ℃ drying oven, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Example 8
As shown in FIG. 1, 108g of TiO was taken2And 36g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose to dissolve, adding a proper amount of deionized water to enable the mass fraction of the mixed solution to be 240mg/g, stirring for 3 hours, uniformly mixing, and performing ultrasonic dispersion for 0.5-1 hour to obtain a white water-based flame-retardant coating; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in a 50 ℃ drying oven, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Example 9
As shown in FIG. 1, 115.2g of TiO was taken2And 28.8g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose to dissolve, adding a proper amount of deionized water to enable the mass fraction of the mixed solution to be 240mg/g, stirring for 3 hours, uniformly mixing, and performing ultrasonic dispersion for 0.5-1 hour to obtain a white water-based flame-retardant coating; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; will make intoThe obtained water-based flame retardant coatings with different colors are coated on the surface of the cotton fabric in a brush way, the bottom of the cotton fabric is embedded with a conductive electrode, the cotton fabric is uniformly coated and then is dried in a drying oven at 50 ℃, and the coating and the drying are carried out for 15 times in total, so that the modified cotton fabric composite material is prepared.
Example 10
As shown in FIG. 1, 72g of TiO was taken2And 72g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose to dissolve, stirring for 12 hours, uniformly mixing, performing ultrasonic dispersion for 0.5-1 hour, and volatilizing part of water to obtain a white water-based flame-retardant coating with the mass fraction of 240 mg/g; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in an oven at 80 ℃, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Example 11
As shown in FIG. 1, 108g of TiO was taken2And 36g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose to dissolve, adding a proper amount of deionized water to ensure that the mass fraction of the mixed solution is 240mg/g, stirring for 12 hours, uniformly mixing, and performing ultrasonic dispersion for 0.5-1 hour to obtain a white water-based flame-retardant coating; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in an oven at 80 ℃, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Example 12
As shown in FIG. 1, 115.2g of TiO was taken2And 28.8g of MMT are respectively added with a proper amount of deionized water to prepare TiO with the mass fraction of 400mg/g2Respectively ultrasonically dispersing the aqueous solution and the MMT aqueous solution of 60mg/g for 0.5-2 h; adding TiO into the mixture2Mixing the aqueous solution and the MMT aqueous solution, adding 76.8g of functional nanofiber film-forming auxiliary agent Cellulose Nanofiber (CNF) and 19.2g of hydroxymethyl cellulose to dissolve, adding a proper amount of deionized water to ensure that the mass fraction of the mixed solution is 240mg/g, stirring for 12 hours, uniformly mixing, and performing ultrasonic dispersion for 0.5-1 hour to obtain a white water-based flame-retardant coating; respectively dropwise adding red, yellow and blue pigments into the white water-based flame-retardant coating, and uniformly stirring to obtain water-based flame-retardant coatings with different colors; and (3) coating the prepared water-based flame-retardant coatings with different colors on the surface of the cotton fabric, burying a conductive electrode at the bottom of the cotton fabric, uniformly coating, drying in an oven at 80 ℃, and coating and drying for 15 times to obtain the modified cotton fabric composite material.
Comparative example
The commercial water-based paint (Nippon Baodili B7000 water-based general ready mixed paint, titanium dioxide is more than or equal to 20% -30%) purchased in the market is coated on the surface of the cotton fabric, a conductive electrode is embedded at the bottom of the cotton fabric, the cotton fabric is uniformly coated and then placed into a 50 ℃ drying oven for drying, and the coating and the drying are carried out for 15 times to prepare the modified cotton fabric composite material coated with the commercial water-based paint.
Test example
Pure cotton fabrics and the white modified cotton fabric composite material, the red modified cotton fabric composite material, the yellow modified cotton fabric composite material and the blue modified cotton fabric composite material of the embodiment 2 are ignited, as shown in figures 2 a-2 e, the pure cotton fabrics are inflammable, and the white modified cotton fabric composite material, the red modified cotton fabric composite material, the yellow modified cotton fabric composite material and the blue modified cotton fabric composite material of the embodiment 2 have better flame retardance and can still keep a certain shape under the attack of flame.
Application example
As shown in fig. 3a, 3b, and 3c, the blue modified cotton fabric composite material of example 2, the cotton fabric coated with the commercial aqueous coating, and the pure cotton fabric of the comparative example were subjected to a fire alarm experiment, respectively, and a power source (including an ammeter), an alarm lamp, and a sample were connected by a wire to form a series circuit. As shown in fig. 3c, when pure cotton fabric is connected to the circuit, there is no circular alarm phenomenon and the fabric is blown; as shown in fig. 3b, when the cotton fabric coated with the commercial water-based paint of the comparative example is connected into a circuit, when flame attacks, the cotton fabric will be burnt violently first, and when the flame continuously attacks for 22s, the alarm lamp will generate discontinuous weak early warning phenomenon, but after the early warning time is 2s, the alarm signal disappears, and then the alarm phenomenon will not occur again under the continuous flame attack; as shown in fig. 3a, when the blue modified cotton fabric composite material of example 2 is respectively connected to a circuit, the circuit is turned off, and the alarm lamp is turned off; flame attack, the resistance value of the coating is rapidly reduced on the original basis, the current in the circuit is rapidly increased within 3-5 s, and devices such as an alarm lamp and the like are triggered; after the flame is removed, the circuit is immediately disconnected, and the alarm signal disappears, so that the conversion between the conductor and the insulator can be realized. When the flame attacks again, the circuit is switched on again, and after the flame is removed, the circuit is switched off immediately, so that stable cyclic fire early warning is realized.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. The color-adjustable water-based flame-retardant coating with the fire circulation early warning function is characterized by comprising TiO as raw materials2MMT, functional nanofiber film-forming auxiliaries and thickeners;
the TiO is2The mass ratio of the TiO to the MMT is 1-9: 1, and the mass ratio of the TiO to the MMT is2The mass sum of the MMT and the water-based flame-retardant coating accounts for 10-20% of the total mass of the water-based flame-retardant coating;
the functional nano-fiber film-forming auxiliary agent is cellulose nano-fiber.
2. The aqueous flame retardant coating according to claim 1, wherein the functional nanofiber film forming aid accounts for 4-15% of the total mass of the aqueous flame retardant coating.
3. The aqueous flame retardant coating of claim 1 wherein the thickener is a hydroxymethyl cellulose;
the thickening agent accounts for 1-5% of the total mass of the water-based flame-retardant coating.
4. The aqueous flame retardant coating of claim 1, wherein the TiO is selected from the group consisting of2And the mass ratio of MMT to MMT is 2-4: 1.
5. The aqueous flame retardant coating of claim 1 wherein the raw material composition further comprises a pigment.
6. The preparation method of the water-based flame retardant coating according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) adding TiO into the mixture2Respectively preparing the aqueous solution and the MMT into aqueous solution, and respectively carrying out ultrasonic treatment to obtain TiO2Solutions and MMT solutions;
(2) subjecting the TiO to a reaction2And mixing the solution and the MMT solution, adding the functional nanofiber film-forming auxiliary agent and the thickening agent for dissolving, uniformly stirring, and performing ultrasonic dispersion to obtain the water-based flame-retardant coating with the fire circulation early warning function and adjustable color.
7. The method according to claim 6, wherein in the step (1), the TiO is2The concentration of the solution is 350-450 mg/g, the concentration of the MMT solution is 50-100 mg/g, and the ultrasonic time is 0.5-2 h;
in the step (2), the stirring time is 3-12 hours, and the ultrasonic dispersion time is 0.5-1 hour.
8. The method of claim 6, further comprising the steps of:
(3) and (3) adding a pigment into the water-based flame-retardant coating obtained in the step (2), and uniformly stirring to obtain the water-based flame-retardant coating with the corresponding color.
9. The use of the aqueous flame retardant coating according to any one of claims 1 to 5 in fire cycle forewarning.
10. The use according to claim 9, wherein the aqueous flame retardant coating is applied to a wall surface or a surface of a combustible material, dried to form a coating layer, and electrically connected to an alarm device.
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