CN115584206A - Water-based inorganic nano ceramic flame-retardant coating and preparation method thereof - Google Patents

Abstract

The invention discloses a water-based inorganic nano-ceramic flame-retardant coating and a preparation method thereof, and relates to the technical field of coatings. The present invention first mixes terephthalonitrile and 3-bromo-1,2-diaminobenzene to form imidazoline to prepare a self-made antibacterial additive; Mix oxane to form quaternary ammonium salt and benzothiophene to obtain antibacterial film-forming sol; then modify carbon nanotubes with hydrated diphenyliodic acid to obtain modified carbon nanotubes; finally combine antibacterial film-forming sol and modified 1,4-bis(2-arylthiophenyl)-1,3-butadiyne compound and 1,2,4-triazole are mixed to produce water-based inorganic nano ceramic flame retardant coating. The water-based inorganic nano-ceramic flame-retardant coating prepared by the invention has good antibacterial properties, anti-ultraviolet properties and anti-cracking properties.

Description

A kind of water-based inorganic nano-ceramic flame retardant coating and preparation method thereof

technical field

The invention relates to the technical field of coatings, in particular to a water-based inorganic nano-ceramic flame-retardant coating and a preparation method thereof.

Background technique

Traditional coatings generally use low-toxic organic solvents as dispersants, and the cleaning of coating tools after use also consumes a large amount of organic detergents, so traditional coatings are not only harmful to people’s health, but also produce many substances harmful to the environment during use; and Water-based paints use water as a dispersant, and are non-toxic. At the same time, coating tools can be washed directly with water. Today, with more and more emphasis on environmental protection and health, water-based paints are gradually attracting people's attention.

Water-based inorganic nano-ceramic coatings, as a large category of water-based coatings, generally use polysiloxane as a film-forming agent, which shrinks greatly during curing and is easy to crack; and the surface of polysiloxane materials is extremely easy to grow and reproduce various harmful microorganisms , cause surface pollution, when exposed to sunlight, the coating is easy to age and fall off, which affects the service life of the coating, thereby limiting the scope of use of water-based inorganic nano-ceramic coatings. Cracking water-based inorganic nano ceramic flame retardant coating.

Contents of the invention

The purpose of the present invention is to provide a water-based inorganic nano-ceramic flame-retardant coating and a preparation method thereof, so as to solve the problems existing in the prior art.

In order to solve the above technical problems, the present invention provides the following technical solutions:

A water-based inorganic nano-ceramic flame-retardant coating, the water-based inorganic nano-ceramic flame-retardant coating includes antibacterial film-forming sol and modified carbon nanotubes.

Further, the antibacterial film-forming sol is prepared by mixing tripropylamino azidophenylisothiocyanate siloxane and self-made antibacterial additives.

Further, the self-made antibacterial additive is prepared by mixing terephthalonitrile and 3-bromo-1,2-diaminobenzene.

Further, the modified carbon nanotubes are obtained by modifying carbon nanotubes with hydrated diphenyliodic acid.

Further, the method of using the inorganic nano-ceramic flame-retardant coating is as follows: spray the water-based nano-ceramic flame-retardant coating on the substrate, control the spraying thickness to 25-30 μm, place it for 1-2 hours, and blow it at 3-5 m/s After curing with hot air at 50-70°C for 5-6 minutes, blow hot air at 90-120°C at 5-8m/s to continue curing for 18-22 minutes.

Further, a method for preparing a water-based inorganic nano-ceramic flame-retardant coating, the preparation method of the water-based inorganic nano-ceramic flame-retardant coating mainly includes the following preparation steps:

(1) Mix self-made antibacterial additives, tripropylamino azidophenylisothiocyanate siloxane and xylene according to the mass ratio of 1:0.9:6~1:1.1:8, heat to 142~144°C, and heat at 50 Stir at ~80r/min for 8~10h, add mixture A which is 0.1~0.2 times the mass of self-made antibacterial additive, the mass ratio of sodium hydride and dimethyl sulfoxide in mixture A is 1:2~1:3, continue stirring for 25~37min , after heating up to 80-100°C, add mixed solution A with 3-5 times the mass of self-made antibacterial additive, continue stirring for 5-7 minutes, add ketone iodide with 0.1-0.3 times the mass of self-made antibacterial additive, and continue stirring for 4-6 hours, Then add ethanol with 1.5-2 times the mass of self-made antibacterial additive and deionized water with 4-6 times the mass of self-made antibacterial additive, stir at 3000-5000r/min for 20-30min, let it stand for 1-2h, then add 0.3 mass of self-made antibacterial additive ~0.5 times of sodium chloride, continue to stir for 20~30min, add hydrochloric acid solution to adjust the pH to 6.9~7.1, at 30~32℃, continue to stir for 2~3h, then ultrasonically shake at 45000~50000Hz for 18~24min to obtain Antibacterial film-forming sol;

(2) Mix carbon nanotubes and hydrated diphenyliodic acid at a mass ratio of 1:3 to 1:5, stir at 60 to 70 r/min for 4 to 6 minutes, heat up to 90 to 100°C, continue to stir for 2 to 4 hours, and filter , washed with deionized water for 3 to 5 times, filtered, dried at 59 to 61°C and a vacuum of 0.01 to 0.02 MPa for 4 to 6 hours, then added hydrated diphenyliodic acid 1 to 1.5 times the mass of carbon nanotubes, and continued Stir for 20 to 30 minutes, add anhydrous sodium sulfate 0.1 to 0.3 times the mass of carbon nanotubes, heat up to 120 to 125°C, and stir at 500 to 600 r/min for 2 to 5 hours to prepare modified carbon nanotubes;

(3) At 128-132°C, mix antibacterial film-forming sol, modified carbon nanotubes and trifluoromethanesulfonic acid at a mass ratio of 1:0.5:3-1:1:4, and stir at 80-100r/min 3 to 5 minutes, add ketone iodide 0.1 to 0.2 times the mass of the antibacterial film-forming sol, continue to stir for 30 to 40 minutes, cool to room temperature, add 80 to 90% ethanol solution with a mass fraction of 7 to 8 times the mass of the antibacterial film-forming sol After continuing to stir for 7 to 9 minutes, drop in the mixed solution B of 0.2 to 0.4 times the mass of the antibacterial film-forming sol at 15 to 20 ml/min, and stir at 45 to 75 r/min for 2 to 3 hours, then add 0.1 to 0.1 times the mass of the antibacterial film-forming sol 0.2 times the mass of triethylamine and 0.05-0.1 times the mass of iodobenzenediethyl ester of antibacterial film-forming sol, and continue stirring for 30-50 minutes to prepare a water-based inorganic nano-ceramic flame-retardant coating.

Further, the preparation method of the self-made antibacterial additive described in step (1) is: terephthalonitrile, 3-bromo-1,2-diaminobenzene and indole-3-copper acetate in a mass ratio of 1:0.7:0.1 ～1:0.9:0.2 mixing, stirring at 150～200r/min for 8～10min, microwave irradiation under the condition of 10～20W/m ² for 1～3h, to prepare self-made antibacterial additive.

Further, the preparation method of the tripropylaminoazidophenylisothiocyanate siloxane in step (1) is as follows: 3-chloropropylamine and 4-azidophenylisothiocyanate are mixed in a mass ratio of 1:0.9 ～1:1.1 mixing, stirring at 20～25r/min for 3～5min, adding anhydrous aluminum trichloride 0.1～0.2 times the mass of 3-chloropropylamine, raising the temperature to 80～90℃, continuing stirring for 10～15min, adding 3 - 3-glycidoxypropyltrimethoxysilane whose mass is 1.2 to 1.4 times that of chloropropylamine, continue to stir for 0.5 to 2 hours, heat up to 140 to 160°C, and feed ³ -chloropropylamine with a mass of 5 ~10 times the amount of hydrogen, and continue to stir for 34~38h to obtain tripropylamino azidophenylisothiocyanate siloxane.

Further, the mixed solution A described in the step (1) is a palladium chloride solution with a mass fraction of 8 to 12% and a tetrabutylammonium bromide solution with a mass fraction of 15 to 25% in a mass ratio of 1:0.5 to 1 : 0.6 mixed preparation.

Further, the mixed solution B in step (3) is prepared by mixing sodium ethylate and 60-80% ethanol solution at a mass ratio of 1:0.1-1:0.2.

Compared with the prior art, the beneficial effects achieved by the present invention are:

A water-based inorganic nano-ceramic flame-retardant coating includes antibacterial film-forming sol and modified carbon nanotubes; the antibacterial film-forming sol is prepared by mixing tripropylamine azidophenylisothiocyanate siloxane and self-made antibacterial additives; self-made The antibacterial additive is prepared by mixing terephthalonitrile and 3-bromo-1,2-diaminobenzene; the modified carbon nanotube is prepared by modifying the carbon nanotube with hydrated diphenyliodic acid.

First, the nitrile group on terephthalonitrile reacts with the amino group on 3-bromo-1,2-diaminobenzene to form imidazoline, which makes the self-made antibacterial additive have antibacterial effect; the bromine atom and tripropylamine group on the self-made antibacterial additive The propylamine group on the azidophenylisothiocyanate siloxane reacts to form a quaternary ammonium salt, and the self-made antibacterial additive is firmly grafted on the tripropylamine azidophenylisothiocyanate siloxane, which strengthens the antibacterial film formation The antibacterial properties of the sol; at the same time, the benzonitrile on the self-made antibacterial additive and the isothiocyanate on the tripropylamino azide phenylisothiocyanate siloxane react to generate benzothiophene, which enhances the antibacterial properties of the antibacterial film-forming sol sex.

Secondly, under the action of hydrated diphenyliodic acid, a large number of hydroxyl hydrophilic groups are formed on the surface of carbon nanotubes, and at the same time, the carboxyl groups on the hydrated diphenyliodic acid react with the hydroxyl groups on the surface of carbon nanotubes, and through the diphenyl The reaction between iodic acid and benzothiophene of the antibacterial film-forming sol uniformly disperses the modified carbon nanotubes in the antibacterial film-forming sol to generate 1,4-bis(2-arylthiophenyl)-1,3 -Butadiyne compound, when illuminated, 1,4-bis(2-arylthiophenyl)-1,3-butadiyne compound quickly absorbs ultraviolet rays and performs electron transfer, thereby releasing energy and enhancing the water-based inorganic UV resistance of nano-ceramic flame-retardant coatings; condensation copolymerization of silicon-oxygen bonds in inorganic nano-ceramic emulsions, azido and 1,4-bis(2-arylthiophenyl)-1,3-butane in inorganic nano-ceramic emulsions The reaction and cross-linking on the diyne compound generate 1,2,4-triazole, and the modified carbon nanotubes are firmly dispersed in the inorganic nano-ceramic emulsion, which enhances the cross-linking density of the water-based inorganic nano-ceramic flame retardant coating, Thus, the cracking resistance of the waterborne inorganic nano-ceramic flame-retardant coating is enhanced.

detailed description

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

In order to more clearly illustrate that the method provided by the present invention is described in detail by the following examples, each index test method of the water-based inorganic nano-ceramic flame-retardant coating made in the following examples is as follows:

Take the water-based inorganic nano-ceramic flame retardant coating prepared in the same quality example and comparative example, spray it on the surface of the substrate with the same size and material, control the spraying thickness to 27.5μm, and after standing for 1.5h, blow it at 4m/s at 60°C After curing with hot air for 5.5 minutes, blow hot air at 105°C at 6.5 m/s to continue curing for 20 minutes to obtain a water-based inorganic nano-ceramic flame-retardant coating.

Antibacterial property: According to the standard GB/T21866, test the antibacterial rate of the treated water-based inorganic nano-ceramic flame retardant coating.

UV resistance: Place the water-based inorganic nano-ceramic flame-retardant coating under the conditions of 135°C and 270W ultraviolet radiation for artificial accelerated aging experiment, and test the aging time.

Crack resistance: According to the standard JG/T298, test the initial dry crack resistance of the water-based inorganic nano-ceramic flame retardant coating.

Example 1

(1) Mix terephthalonitrile, 3-bromo-1,2-diaminobenzene and copper indole-3-acetate at a mass ratio of 1:0.7:0.1, stir at 150r/min for 8min, and heat at 10W/ ^m2 Under the conditions of microwave irradiation for 1h, self-made antibacterial additives were prepared; 3-chloropropylamine and 4-azidophenylisothiocyanate were mixed at a mass ratio of 1:0.9, stirred at 20r/min for 3min, and 3-chloropropylamine was added 0.1 times the mass of anhydrous aluminum trichloride, heat up to 80 ° C, continue to stir for 10 minutes, add 3-glycidoxypropyltrimethoxysilane with 1.2 times the mass of 3-chloropropylamine, continue to stir for 0.5 hours, and heat up to 140 ℃, 5 times the mass of 3-chloropropylamine was introduced into hydrogen gas at 2m ³ /min, and the stirring was continued for 34 hours to obtain tripropylamino azidophenylisothiocyanate siloxane; self-made antibacterial additives, tripropylamino azide Mix phenylisothiocyanate siloxane and xylene according to the mass ratio of 1:0.9:6, heat to 142°C, stir at 50r/min for 8h, add mixture A which is 0.1 times the mass of self-made antibacterial additive, and sodium hydride in mixture A The mass ratio to dimethyl sulfoxide is 1:2, continue to stir for 25 minutes, and after heating up to 80°C, add a mixed solution A that is 3 times the mass of the self-made antibacterial additive. The mixed solution A is palladium chloride with a mass fraction of 8%. solution and tetrabutylammonium bromide solution with a mass fraction of 15% were prepared by mixing at a mass ratio of 1:0.5; continue stirring for 5 minutes, add ketone iodide with a mass fraction of 0.1 times the mass of the self-made antibacterial additive, continue stirring for 4 hours, and then add the self-made antibacterial Add ethanol with 1.5 times the weight of the additive and deionized water with 4 times the weight of the self-made antibacterial additive, stir at 3000r/min for 20min, let it stand for 1h, then add sodium chloride with 0.3 times the quality of the self-made antibacterial additive, continue stirring for 20min, add hydrochloric acid solution to adjust The pH is 6.9, after stirring for 2 hours at 30°C, ultrasonic vibration at 45000 Hz for 18 minutes to obtain an antibacterial film-forming sol;

(2) Mix carbon nanotubes and hydrated diphenyliodic acid in a mass ratio of 1:3, stir at 60r/min for 4min, heat up to 90°C, continue stirring for 2h, filter, wash with deionized water 3 times, filter, and Dry at 59°C and a vacuum of 0.01MPa for 4 hours, then add hydrated diphenyliodic acid with 1 times the mass of carbon nanotubes, continue stirring for 20 minutes, add anhydrous sodium sulfate with 0.1 times the mass of carbon nanotubes, and heat up to 120°C to Stir at 500r/min for 2h to prepare modified carbon nanotubes;

(3) At 128°C, mix the antibacterial film-forming sol, modified carbon nanotubes and trifluoromethanesulfonic acid at a mass ratio of 1:0.5:3, stir at 80r/min for 3min, and add 0.1 times the mass of the antibacterial film-forming sol ketone iodide, continue to stir for 30min, cool to room temperature, add 80% ethanol solution with a mass fraction of 7 times the mass of the antibacterial film-forming sol, continue stirring for 7min, drop 0.2 times the mass of the antibacterial film-forming sol at 15ml/min Mixed solution B, mixed solution B is prepared by mixing sodium ethylate and 60% ethanol solution at a mass ratio of 1:0.1, after stirring at 45r/min for 2h, add 0.1 times the mass of antibacterial film-forming sol triethylamine and antibacterial film-forming The mass of the sol was 0.05 times that of iodobenzenediethyl ester, and the stirring was continued for 30 minutes to obtain a water-based inorganic nano-ceramic flame-retardant coating.

Example 2

(1) Mix terephthalonitrile, 3-bromo-1,2-diaminobenzene and copper indole-3-acetate at a mass ratio of 1:0.8:0.15, stir at 175r/min for 9min, and heat at 15W/ ^m2 Under the conditions of microwave irradiation for 2 hours, self-made antibacterial additives were prepared; 3-chloropropylamine and 4-azidophenylisothiocyanate were mixed at a mass ratio of 1:1, stirred at 22.5/min for 4 minutes, and 3-chloropropylamine was added 0.15 times the mass of anhydrous aluminum trichloride, heated to 85 ° C, continued to stir for 12.5 minutes, added 3-glycidoxypropyltrimethoxysilane with 1.3 times the mass of 3-chloropropylamine, continued to stir for 1.25 hours, and heated to At 150°C, inject hydrogen gas 7.5 times the mass of 3-chloropropylamine at 3m ³ /min, and continue stirring for 36 hours to obtain tripropylamine azidophenylisothiocyanate siloxane; self-made antibacterial additives, tripropylamine azide Nitrobenzene isothiocyanate siloxane and xylene are mixed according to the mass ratio of 1:1:7, heated to 143°C, stirred at 65r/min for 9h, and mixed with self-made antibacterial additive 0.15 times the mass of mixture A, hydrogenated in mixture A The mass ratio of sodium to dimethyl sulfoxide is 1:2.5, continue to stir for 31 minutes, and after heating up to 90°C, add a mixed solution A that is 4 times the mass of the self-made antibacterial additive. The mixed solution A is a 10% mass fraction of chlorinated The palladium solution and the tetrabutylammonium bromide solution with a mass fraction of 20% are mixed according to the mass ratio of 1:0.55, continue to stir for 6 minutes, add ketone iodide with a mass fraction of 0.2 times the mass of the self-made antibacterial additive, continue to stir for 5 hours, and then add the self-made Ethanol with 1.75 times the mass of antibacterial additive and deionized water with 5 times the mass of self-made antibacterial additive, stirred at 4000r/min for 25min, let stand for 1.5h, then added sodium chloride with 0.4 times the mass of self-made antibacterial additive, continued to stir for 25min, added hydrochloric acid Adjust the pH of the solution to 7, continue to stir for 2.5 hours at 31°C, and then oscillate ultrasonically at 47500 Hz for 21 minutes to obtain an antibacterial film-forming sol;

(2) Mix carbon nanotubes and hydrated diphenyliodic acid in a mass ratio of 1:4, stir at 65r/min for 5min, heat up to 95°C, continue stirring for 3h, filter, wash with deionized water 4 times, filter, and Dry at 60°C and a vacuum of 0.015MPa for 5 hours, then add hydrated diphenyliodic acid with 1.25 times the mass of carbon nanotubes, continue stirring for 25 minutes, add anhydrous sodium sulfate with 0.2 times the mass of carbon nanotubes, raise the temperature to 122.5°C, and /min stirred for 3.5h to prepare modified carbon nanotubes;

(3) At 130°C, mix the antibacterial film-forming sol, modified carbon nanotubes and trifluoromethanesulfonic acid at a mass ratio of 1:0.75:3.5, stir at 90r/min for 4min, and add 0.15 times the mass of the antibacterial film-forming sol ketone iodide, continue to stir for 35min, cool to room temperature, add 85% ethanol solution with a mass fraction of 7.5 times the mass of the antibacterial film-forming sol, continue stirring for 8min, drop in 0.3 times the mass of the antibacterial film-forming sol at 17.5ml/min Mixed solution B, mixed solution B is prepared by mixing sodium ethylate and 70% ethanol solution at a mass ratio of 1:0.15, and after stirring at 60r/min for 2.5h, add 0.15 times the mass of antibacterial film-forming colloidal triethylamine and antibacterial The mass of the film-forming sol was 0.075 times that of iodobenzenediethyl ester, and the stirring was continued for 40 minutes to obtain a water-based inorganic nano-ceramic flame-retardant coating.

Example 3

(1) Mix terephthalonitrile, 3-bromo-1,2-diaminobenzene and copper indole-3-acetate in a mass ratio of 1:0.9:0.2, stir at 200r/min for 10min, and heat at 20W/ ^m2 Under the conditions of microwave irradiation for 3 hours, a self-made antibacterial additive was prepared; 3-chloropropylamine and 4-azidophenylisothiocyanate were mixed in a mass ratio of 1:1.1, stirred at 25r/min for 5min, and 3-chloropropylamine was added 0.2 times the mass of anhydrous aluminum trichloride, heat up to 90°C, continue to stir for 15 minutes, add 3-glycidoxypropyltrimethoxysilane with 1.4 times the mass of 3-chloropropylamine, continue to stir for 2 hours, and heat up to 160°C , with 4m ³ /min into the hydrogen gas 10 times the quality of 3-chloropropylamine, continue to stir for 38h, obtained tripropylamino azide phenyl isothiocyanate siloxane; self-made antibacterial additive, tripropylamino azide Mix isothiocyanate siloxane and xylene according to the mass ratio of 1:1.1:8, heat to 144°C, stir at 80r/min for 10h, add mixture A with 0.2 times the mass of self-made antibacterial additive, sodium hydride and The mass ratio of dimethyl sulfoxide is 1:3, continue to stir for 37 minutes, and after heating up to 100°C, add a mixed solution A that is 5 times the mass of the self-made antibacterial additive. The mixed solution A is a palladium chloride solution with a mass fraction of 12%. It is prepared by mixing tetrabutylammonium bromide solution with a mass fraction of 25% at a mass ratio of 1:0.6, continue stirring for 7 minutes, add ketone iodide with a mass fraction of 0.3 times the mass of the self-made antibacterial additive, continue stirring for 6 hours, and then add the self-made antibacterial additive Ethanol with 2 times the mass and deionized water with 6 times the mass of self-made antibacterial additive, stirred at 5000r/min for 30min, let stand for 2h, then added sodium chloride with 0.5 times the mass of self-made antibacterial additive, continued to stir for 30min, added hydrochloric acid solution to adjust pH 7.1, at 32°C, continue to stir for 3 hours, then ultrasonically oscillate at 50000 Hz for 24 minutes to prepare an antibacterial film-forming sol;

(2) Mix carbon nanotubes and hydrated diphenyliodic acid at a mass ratio of 1:5, stir at 70r/min for 6min, heat up to 100°C, continue to stir for 4h, filter, wash 5 times with deionized water, filter, and Dry at 61°C and a vacuum of 0.02MPa for 6 hours, then add hydrated diphenyliodic acid 1.5 times the mass of carbon nanotubes, continue stirring for 30 minutes, add anhydrous sodium sulfate 0.3 times the mass of carbon nanotubes, heat up to 125°C, and /min stirred for 5h to prepare modified carbon nanotubes;

(3) At 132°C, mix the antibacterial film-forming sol, modified carbon nanotubes and trifluoromethanesulfonic acid in a mass ratio of 1:1:4, stir at 100r/min for 5min, and add 0.2 times the mass of the antibacterial film-forming sol ketone iodide, stirred at 100r/min for 40min, cooled to room temperature, added 90% ethanol solution with a mass fraction of 8 times the mass of the antibacterial film-forming sol, continued to stir for 9min, then dripped the mass fraction of the antibacterial film-forming sol at 20ml/min 0.4 times the mixed solution B, the mixed solution B is prepared by mixing sodium ethylate and 80% ethanol solution at a mass ratio of 1:0.2, after stirring for 3 hours at 75r/min, add 0.2 times the mass of antibacterial film-forming colloid triethylamine and The mass of the antibacterial film-forming sol is 0.1 times that of iodobenzenediethyl ester, and the stirring is continued for 50 minutes to prepare a water-based inorganic nano-ceramic flame-retardant coating.

Comparative example 1

The difference between Comparative Example 1 and Example 2 is that in step (1), only 3-bromo-1,2-diaminobenzene is used to prepare a self-made antibacterial additive, and the rest of the preparation steps are the same as in Example 2.

Comparative example 2

The difference between Comparative Example 2 and Example 2 is that in step (1), only terephthalonitrile is used to prepare the self-made antibacterial additive, and all the other preparation steps are the same as in Example 2.

Comparative example 3

The difference between Comparative Example 3 and Example 2 is that step (1) does not prepare self-made antibacterial additives, and only uses tripropylamino azidophenylisothiocyanate siloxane to prepare antibacterial film-forming sol, and the rest of the preparation steps are the same as in Example 2 .

Comparative example 4

The difference between Comparative Example 4 and Example 2 lies in step (1), using trimethoxysilane and self-made antibacterial additives to prepare antibacterial film-forming sol, and the rest of the preparation steps are the same as in Example 2.

Comparative example 5

The difference between Comparative Example 5 and Example 2 is that in step (3), only the antibacterial film-forming sol is used to prepare the water-based inorganic nano-ceramic flame-retardant coating, and the remaining steps are the same as in Example 2.

Effect example

Table 1 below shows the performance analysis results of the antibacterial, UV resistance and cracking resistance of the water-based inorganic nano-ceramic flame retardant coatings prepared by using Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

Table 1

From Table 1, it can be found that the antibacterial properties, UV resistance and crack resistance of the water-based inorganic nano-ceramic flame retardant coating prepared by embodiment 1, 2, 3 are stronger; from the experiments of embodiment 1, 2, 3 and comparative example 1 Data comparison shows that using terephthalonitrile to prepare self-made antibacterial additives can form imidazoline, and subsequent preparation of antibacterial film-forming sol can form benzothiophene, and can form 1,4-di(2 -arylthiophenyl)-1,3-butadiyne compound and 1,2,4-triazole, the prepared water-based inorganic nano-ceramic flame retardant coating has strong antibacterial properties, UV resistance and crack resistance; from Comparing the experimental data of Examples 1, 2, 3 and Comparative Example 2, it can be found that using 3-bromo-1,2-diaminobenzene to prepare self-made antibacterial additives can form imidazolines, and subsequent preparation of antibacterial film-forming sols can form quaternary ammonium Salt, the prepared water-based inorganic nano-ceramic flame-retardant coating has stronger antibacterial properties; from the experimental data of Examples 1, 2, 3 and Comparative Example 3, it can be found that using self-made antibacterial additives to prepare antibacterial film-forming sols can form quaternary ammonium Salt and benzothiophene, the subsequent preparation of water-based inorganic nano-ceramic flame retardant coatings can form 1,4-bis(2-arylthiophenyl)-1,3-butadiyne compounds and 1,2,4-triazoles, The prepared water-based inorganic nano-ceramic flame-retardant coating has strong antibacterial properties, anti-ultraviolet and crack resistance; from the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4, it can be found that using tripropylamine azide phenyliso Thiocyanate siloxane is used to prepare antibacterial film-forming sol, which can form quaternary ammonium salt and benzothiophene, and the subsequent preparation of water-based inorganic nano-ceramic flame-retardant coating can form 1,4-bis(2-arylthiophenyl)-1 , 3-butadiyne compound and 1,2,4-triazole, the water-based inorganic nano-ceramic flame retardant coating that prepares is stronger in antibacterial property, anti-ultraviolet and anti-cracking property; From embodiment 1,2,3 and pair Comparison of the experimental data of ratio 5 shows that the use of modified carbon nanotubes to prepare water-based inorganic nano-ceramic flame-retardant coatings can form 1,4-bis(2-arylthiophenyl)-1,3-butadiyne compounds and 1 , 2,4-triazole, the prepared water-based inorganic nano-ceramic flame retardant coating has strong UV resistance and crack resistance.

It will be apparent to those skilled in the art that the invention is not limited to the details of the above-described exemplary embodiments, but that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Accordingly, the embodiments should be regarded in all points of view as exemplary and not restrictive, the scope of the invention being defined by the appended claims rather than the foregoing description, and it is therefore intended that the scope of the invention be defined by the appended claims rather than by the foregoing description. All changes within the meaning and range of equivalents of the elements are embraced in the present invention. Any sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. A water-based inorganic nano-ceramic flame-retardant coating, characterized in that, the water-based inorganic nano-ceramic flame-retardant coating comprises antibacterial film-forming sol and modified carbon nanotubes. 2. a kind of water-based inorganic nano-ceramic flame retardant coating according to claim 1, it is characterized in that, described antibacterial film-forming sol is mixed by tripropylamine azidophenylisothiocyanate siloxane and self-made antibacterial additive be made of. 3. A kind of water-based inorganic nano-ceramic flame retardant coating according to claim 2, characterized in that, said self-made antibacterial additive is prepared by mixing terephthalonitrile and 3-bromo-1,2-diaminobenzene. 4. A kind of water-based inorganic nano-ceramic flame retardant coating according to claim 1, characterized in that, the modified carbon nanotubes are obtained by modifying carbon nanotubes with hydrated diphenyliodic acid. 5. a kind of water-based inorganic nano-ceramic flame-retardant coating according to claim 1, is characterized in that, the using method of described inorganic nano-ceramic flame-retardant coating is: water-based nano-ceramic flame-retardant coating is sprayed on the base material, controls The thickness of spraying is 25-30μm. After standing for 1-2 hours, blow hot air at 50-70℃ at 3-5m/s to cure for 5-6min, and then blow hot air at 90-120℃ at 5-8m/s to continue curing for 18- 22min. 6. A preparation method of water-based inorganic nano-ceramic fire-retardant coating, is characterized in that, mainly comprises following preparation steps: (1) Mix self-made antibacterial additives, tripropylamino azidophenylisothiocyanate siloxane and xylene according to the mass ratio of 1:0.9:6~1:1.1:8, heat to 142~144°C, and heat at 50 Stir at ~80r/min for 8~10h, add mixture A which is 0.1~0.2 times the mass of self-made antibacterial additive, the mass ratio of sodium hydride and dimethyl sulfoxide in mixture A is 1:2~1:3, continue stirring for 25~37min , after heating up to 80-100°C, add mixed solution A with 3-5 times the mass of self-made antibacterial additive, continue stirring for 5-7 minutes, add ketone iodide with 0.1-0.3 times the mass of self-made antibacterial additive, and continue stirring for 4-6 hours, Then add ethanol with 1.5-2 times the mass of self-made antibacterial additive and deionized water with 4-6 times the mass of self-made antibacterial additive, stir at 3000-5000r/min for 20-30min, let it stand for 1-2h, then add 0.3 mass of self-made antibacterial additive ~0.5 times of sodium chloride, continue to stir for 20~30min, add hydrochloric acid solution to adjust the pH to 6.9~7.1, at 30~32℃, continue to stir for 2~3h, then ultrasonically shake at 45000~50000Hz for 18~24min to obtain Antibacterial film-forming sol; (2) Mix carbon nanotubes and hydrated diphenyliodic acid at a mass ratio of 1:3 to 1:5, stir at 60 to 70 r/min for 4 to 6 minutes, heat up to 90 to 100°C, continue to stir for 2 to 4 hours, and filter , washed with deionized water for 3 to 5 times, filtered, dried at 59 to 61°C and a vacuum of 0.01 to 0.02 MPa for 4 to 6 hours, then added hydrated diphenyliodic acid 1 to 1.5 times the mass of carbon nanotubes, and continued Stir for 20 to 30 minutes, add anhydrous sodium sulfate 0.1 to 0.3 times the mass of carbon nanotubes, heat up to 120 to 125°C, and stir at 500 to 600 r/min for 2 to 5 hours to prepare modified carbon nanotubes; (3) At 128-132°C, mix antibacterial film-forming sol, modified carbon nanotubes and trifluoromethanesulfonic acid at a mass ratio of 1:0.5:3-1:1:4, and stir at 80-100r/min 3 to 5 minutes, add ketone iodide 0.1 to 0.2 times the mass of the antibacterial film-forming sol, continue to stir for 30 to 40 minutes, cool to room temperature, add 80 to 90% ethanol solution with a mass fraction of 7 to 8 times the mass of the antibacterial film-forming sol After continuing to stir for 7 to 9 minutes, drop in the mixed solution B of 0.2 to 0.4 times the mass of the antibacterial film-forming sol at 15 to 20 ml/min, and stir at 45 to 75 r/min for 2 to 3 hours, then add 0.1 to 0.1 times the mass of the antibacterial film-forming sol 0.2 times the mass of triethylamine and 0.05-0.1 times the mass of iodobenzenediethyl ester of antibacterial film-forming sol, and continue stirring for 30-50 minutes to prepare a water-based inorganic nano-ceramic flame-retardant coating. 7. according to the preparation method of a kind of water-based inorganic nano-ceramic fire retardant coating described in claim 6, it is characterized in that, the preparation method of self-made antibacterial additive described in step (1) is: with terephthalonitrile, 3-bromo-1 , 2-diaminobenzene and indole-3-copper acetate are mixed according to the mass ratio of 1:0.7:0.1～1:0.9:0.2, stirred at 150～200r/min for 8～10min, under the condition of ¹⁰ ～20W/m2 Under microwave irradiation for 1 to 3 hours, a self-made antibacterial additive was prepared. 8. the preparation method of a kind of water-based inorganic nano-ceramic flame retardant coating according to claim 6 is characterized in that, the preparation method of step (1) described tripropylamino azidophenylisothiocyanate siloxane is : Mix 3-chloropropylamine and 4-azidophenylisothiocyanate in a mass ratio of 1:0.9~1:1.1, stir at 20~25r/min for 3~5min, add 0.1~0.2 times the mass of 3-chloropropylamine anhydrous aluminum trichloride, heat up to 80-90°C, continue to stir for 10-15min, add 3-glycidoxypropyltrimethoxysilane whose mass is 1.2-1.4 times that of 3-chloropropylamine, and continue to stir for 0.5-2h , raise the temperature to 140-160°C, pass in hydrogen gas 5-10 times the mass of 3-chloropropylamine at 2-4m ³ /min, and continue stirring for 34-38 hours to prepare tripropylaminoazidophenylisothiocyanate siloxane alkyl. 9. the preparation method of a kind of water-based inorganic nano-ceramic flame retardant coating according to claim 6 is characterized in that, the mixed solution A described in step (1) is that the mass fraction is 8～12% palladium chloride solution and The tetrabutylammonium bromide solution with a mass fraction of 15-25% is prepared by mixing at a mass ratio of 1:0.5-1:0.6. 10. The preparation method of a kind of water-based inorganic nano-ceramic flame-retardant coating according to claim 6, is characterized in that, the mixed solution B described in step (3) is the ethanol solution of sodium ethylate and 60～80% by mass ratio 1:0.1～1:0.2 mixed.