CN113861794B - Nano zirconium phosphate-based flame-retardant bacteriostatic agent, preparation method thereof and prepared intumescent fireproof bacteriostatic coating - Google Patents
Nano zirconium phosphate-based flame-retardant bacteriostatic agent, preparation method thereof and prepared intumescent fireproof bacteriostatic coating Download PDFInfo
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Abstract
The invention discloses a nano zirconium phosphate-based flame-retardant bacteriostatic agent, which is prepared by firstly carrying out intercalation stripping on zirconium phosphate and modifying the zirconium phosphate by using aminoimidazole and chloropropionaldehyde, and can play a synergistic flame-retardant role with an expansion flame-retardant system in a fireproof coating while effectively solving the problems of easy agglomeration of the zirconium phosphate and the like; the film forming property, fire resistance and durability of the fireproof coating can be obviously improved; schiff base and imidazole loaded on the surface of the nano zirconium phosphate sheet layer can be uniformly dispersed in the coating components to play a role in barrier bacteriostasis, and the Schiff base, the nano zirconium phosphate and the imidazole in the flame retardant can effectively improve the bacteriostasis performance of the fireproof coating. The flame retardant provided by the invention integrates flame retardance, smoke suppression, bacteriostasis and enhancement functions, is low in halogen-free cost, good in char formation, environment-friendly and wide in applicability, and the related preparation method is simple in process, simple in reaction conditions and suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of flame-retardant bacteriostatic materials, and particularly relates to a nano zirconium phosphate based flame-retardant bacteriostatic agent and an intumescent fireproof bacteriostatic coating prepared from the same.
Background
The intumescent fire-retardant coating is a substance which is coated on the surface of a base material to improve the fire resistance and slow down the combustion rate, and is prepared by mainly taking macromolecular aqueous emulsion, macromolecular resin and the like as a matrix and adding an intumescent fire-retardant system consisting of an acid source, a gas source, a carbon source and the like, a functional filler and a corresponding auxiliary agent. The components react at high temperature to generate a synergistic effect, and are dehydrated and carbonized to form a uniform and compact cellular expanded carbon layer, so that the air and heat transfer can be effectively isolated, and the excellent fireproof and heat-insulating effects are achieved. However, the traditional fireproof coating generally has the problems of loose carbon layer and the like, so that the flame retardant efficiency is poor, and meanwhile, the antibacterial effect is almost not achieved.
Zirconium phosphate is an artificially synthesized layered solid acid and has the characteristics of excellent thermal stability, chemical stability, strong acid and alkali resistance and the like. The zirconium phosphate layers are mainly superposed by hydrogen bonding and Van der Waals force, and the HP0 of the zirconium phosphate layers4 2-H in the radical+The interlayer space has large free activity, and the interlayer crystal water molecules can be replaced by polar organic molecules. Although the flame retardance of the flame retardant can be obviously improved based on the layered barrier effect and the catalytic carbonization effect of the solid acid of the zirconium phosphate, the problems of poor thermal stability, low flame retardant efficiency and the like of the flame retardant are caused because the carbon layer of the traditional flame retardant system is loose and the zirconium phosphate is easy to agglomerate.
To solve the above technical problems, organic surface modification of zirconium phosphate is a common and effective method. In patent CN108203519A, methylamine is adopted to intercalate zirconium phosphate, the intercalated zirconium phosphate is stripped into lamellar zirconium phosphate after mechanical ball milling, the lamellar zirconium phosphate is mixed with macromolecular flame retardant MCA, and the zirconium phosphate is used as a synergist modified flame retardant and applied to a PA6 flame-retardant composite material, but in the patent, only the zirconium phosphate is used as a synergist and only aiming at a PA6 material, the problems of large compounding amount, limited application field, poor flame-retardant effect and the like exist. In patent CN109810545A, zirconium phosphate is stripped into nanosheets and added into a flame-retardant system, and the catalysis of the zirconium phosphate nanosheets is utilized to improve the carbonization effect of polymers, so that the flame-retardant efficiency is improved. In addition, the bacteriostatic effect of zirconium phosphate on the coating is rarely reported.
Therefore, the method has great research and application significance in the application fields of further optimizing the modification means of the zirconium phosphate compound and improving the related performance of the zirconium phosphate compound.
Disclosure of Invention
The invention mainly aims to solve the problems of poor char forming quality, loose char layer, low flame retardant efficiency and the like of the existing flame retardant, and provides a nano zirconium phosphate-based flame retardant bacteriostatic agent and an intumescent fire-proof bacteriostatic coating prepared by using the same; modifying the stripped zirconium phosphate nanosheets by using aminoimidazole and chloropropanal to synthesize a flame-retardant bacteriostatic agent based on nano zirconium phosphate, wherein the bacteriostatic performance of the fireproof coating is remarkably improved by using Schiff base groups formed by the reaction of the aminoimidazole and chloropropanal and the specific synergistic antibacterial effect of the zirconium phosphate and imidazole; meanwhile, the grafted imidazole group and zirconium phosphate have excellent flame-retardant synergistic effect, and the fireproof performance of the fireproof coating can be effectively improved; the obtained flame retardant integrates the flame-retardant, smoke-inhibiting and bacteriostatic properties and the enhancement function, and the related preparation method is simple, low in cost, environment-friendly, wide in applicability and suitable for popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a nanometer zirconium phosphate-based flame-retardant bacteriostatic agent comprises the following steps:
1) exfoliated zirconium phosphate (ZrP): dropwise adding tetrabutyl ammonium hydroxide (TBA can weaken the acting force between zirconium phosphate layers, peeling zirconium phosphate and exposing hydroxyl groups between the layers) into the zirconium phosphate dispersion liquid, carrying out ultrasonic stirring reaction, then dropwise adding concentrated acid to carry out secondary reaction (removing the TBA solution), and carrying out solid-liquid separation to obtain semitransparent gel precipitate;
2) grafting chloropropionaldehyde: mixing the semitransparent gel precipitate obtained in the step 1) with chloropropanal, stirring for reaction, centrifugally washing, and drying to obtain a light yellow liquid;
3) synthesizing Schiff base: mixing the faint yellow liquid obtained in the step 2) with aminoimidazole, mechanically stirring at a certain temperature, heating to reflux, cooling to room temperature after the reaction is finished, filtering, and washing to obtain the flame-retardant bacteriostatic agent based on the nano zirconium phosphate.
In the above scheme, the zirconium phosphate is alpha-zirconium phosphate.
In the scheme, the concentrated acid is one or more of concentrated phosphoric acid, concentrated hydrochloric acid, concentrated nitric acid and concentrated sulfuric acid; the concentration is 3-18 mol/L; the dropping time is 30-90 min.
In the scheme, the concentration of the tetrabutylammonium hydroxide solution is 0.05-10 mol/L; the dripping time is 30-90 min; the reaction temperature is 0-20 ℃; the ultrasonic stirring reaction time is 0.5-2 h.
In the scheme, the molar ratio of zirconium phosphate to tetrabutylammonium hydroxide introduced in the step 1) is 5: 1-1: 6.
In the above scheme, the tetrabutylammonium hydroxide is mixed with a concentrated acid-introduced acid component (H)3PO4、HCl、HNO3、H2SO4One or more of) is 2:1 to 1: 8.
In the scheme, the secondary reaction time in the step 1) is 0.5-3 h.
In the scheme, the molar ratio of the zirconium phosphate introduced in the step 1), the chloropropionaldehyde introduced in the step 2) and the aminoimidazole introduced in the step 3) is 1 (1-8) to (0.5-8).
In the scheme, the stirring reaction temperature in the step 2) is 30-100 ℃, and the stirring time is 12-24 hours.
In the scheme, the aminoimidazole in the step 3) is an imidazole derivative containing amino, and can be one or more of 2-aminoimidazole, 4-aminoimidazole, 1- (3-aminopropyl) imidazole, 2-aminobenzimidazole and the like.
In the scheme, the mechanical stirring temperature in the step 3) is 60-120 ℃, the mechanical stirring time is 30-120min, and the reflux reaction time is 12-24 h.
The nanometer zirconium phosphate-based flame-retardant bacteriostatic agent prepared according to the scheme is a faint yellow powder crystal.
The nanometer zirconium phosphate-based flame-retardant bacteriostatic agent obtained by the scheme is applied to preparation of an intumescent fire-retardant coating, and comprises the following components in percentage by mass: 20-30% of methacrylic acid modified acrylate core-shell emulsion, 30-36% of ammonium polyphosphate, 10-20% of pentaerythritol, 10-15% of melamine, 1-5% of titanium dioxide, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octyl alcohol, 1-10% of nano zirconium phosphate based flame retardant bacteriostatic agent and the balance of water.
The intumescent fire-retardant coating prepared according to the scheme has the advantages of excellent fire resistance, good bacteriostatic effect, low halogen-free cost, environmental protection and wide applicability.
The principle of the invention is as follows:
according to the invention, firstly tetrabutylammonium hydroxide is used for stripping zirconium phosphate to expose hydroxyl groups among zirconium phosphate layers, then chloropropionaldehyde is used for carrying out a chemical reaction with the stripped zirconium phosphate, and finally, aminoimidazole and aldehyde groups in the chloropropionaldehyde react to form Schiff base, so that the nano zirconium phosphate-based flame-retardant bacteriostatic agent is prepared, and when the nano zirconium phosphate-based flame-retardant bacteriostatic agent is applied to an intumescent fire-retardant coating system, the fireproof performance and the durability of the nano zirconium phosphate-based flame-retardant bacteriostatic agent can be obviously improved, and meanwhile, the nano zirconium phosphate-based flame-retardant bacteriostatic agent has an excellent bacteriostatic effect:
1) flame retardant and durability properties; when a fire disaster occurs, ammonium polyphosphate decomposes at high temperature to release acidic substances, ammonia gas and other non-combustible gases, catalyzes pentaerythritol to dehydrate and carbonize to form a carbon layer skeleton, finally melamine is heated to decompose to release non-combustible gases, and a carbon layer is blown to form a honeycomb porous carbon layer to play a role in flame retardance; the nano zirconium phosphate-based flame-retardant bacteriostatic agent can quickly form carbon on the surface of a base material while playing a flame-retardant role, fill gaps between sheet layers to form more and dense microscopic carbon cages, block oxygen and heat transfer in the air, and seal a large amount of degradation products, meanwhile, introduced Schiff base and aminoimidazole can act on the microscopic carbon cages, zirconium phosphate, chloropropionaldehyde and aminoimidazole react and can be crosslinked to generate a crosslinked net structure with high thermal stability, so that the graphitization degree of a combustion carbon layer is improved, a P-N-C synergistic effect can be realized, meanwhile, the strength of the carbon layer of the carbon cages can be effectively improved, the compactness of the carbon layer is enhanced, a flame-retardant role is further played on the aspect of the microstructure, and the flame-retardant role is played in cooperation with an expansion flame-retardant system in a fireproof coating; in addition, the obtained organic modified nano zirconium phosphate is beneficial to synchronously improving the durability of the fireproof coating.
2) According to the invention, the bacteriostatic ability of high-valence metal zirconium ions of nano zirconium phosphate is utilized, and in addition, the nano zirconium phosphate nanoparticle diameter and the zirconium ions in the nano zirconium phosphate nanoparticle can destroy cell walls of microorganisms, so that groups such as Schiff base and imidazole loaded on a nano zirconium phosphate sheet layer can be promoted to perform an effect in a cell interior, the bacteriostatic effect of the Schiff base can be effectively improved, the imidazole groups and the Schiff base can perform a good bacteriostatic synergistic effect, and multiple mechanisms act together, so that the bacteriostatic performance of the obtained coating can be remarkably improved.
Compared with the prior art, the invention has the beneficial effects that:
1) the nanometer zirconium phosphate-based flame-retardant bacteriostatic agent has high-efficiency flame retardance and excellent char formation, can play a synergistic flame-retardant role with an expansion fireproof system consisting of ammonium polyphosphate, pentaerythritol and melamine in a fireproof coating, promotes the fireproof coating to form a carbon layer with higher quality and strength, and further realizes high-efficiency flame retardance; meanwhile, based on the Schiff base group in the flame-retardant bacteriostatic agent and the specific synergistic antibacterial effect between zirconium phosphate and imidazole, the bacteriostatic effect of the fireproof coating can be synchronously improved; the obtained flame retardant integrates the functions of flame retardance, smoke suppression, bacteriostasis and enhancement, can give consideration to good chemical stability, and can effectively expand the application field of the fireproof coating.
2) The zirconium phosphate sheet layer is subjected to graft modification by the chloropropionaldehyde and the aminoimidazole, so that the surface polarity of the zirconium phosphate can be effectively reduced, the components of the fireproof coating are effectively simplified, the compatibility and the dispersibility among the components of the coating are better, the film-forming property, the fire resistance, the durability and the practicability of the coating can be effectively improved, and the fireproof performance of the obtained fireproof coating is further effectively improved.
3) The nanometer zirconium phosphate-based flame-retardant bacteriostatic agent provided by the invention utilizes a contact reaction mechanism and an active oxygen mechanism to destroy the replication capacity of DNA molecules of bacteria, so that the normal replication of genetic materials and the propagation of organisms are influenced; microorganisms can be killed by further oxidizing the outer cell membrane by generating free radicals; the micro-particle size of the nano zirconium phosphate can load imidazole and Schiff base groups to easily attack microorganisms, and the nano zirconium phosphate is combined with sulfydryl of enzyme protein in cells, so that certain enzymes containing sulfydryl groups lose activity, cell walls of the microorganisms are damaged, growth and reproduction of the microorganisms are controlled, and an excellent antibacterial effect is achieved.
4) The flame retardant disclosed by the invention is low in halogen-free cost, good in char formation, environment-friendly and wide in applicability, and the related preparation method is simple and convenient in process, mild in reaction conditions, wide in application field and suitable for industrialization, popularization and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following 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.
In the following examples, the preparation of zirconium phosphate (α -zirconium phosphate) used comprises the following steps: 50mL of concentrated phosphoric acid with a molar concentration of 1mo1/L was prepared, and added to a 250mL three-necked flask, and 5.00g of zirconium oxychloride (ZrOCl) was added2- 8H20) Heating to 95 deg.CMechanically stirring at 20min to disperse zirconium oxychloride, stopping stirring, reacting at reflux temperature for 24 hr, separating solid from liquid, washing with deionized water until the pH of the supernatant meets the requirement>And 5, drying the washed solid product in an oven at the temperature of 80 ℃ for 12 hours, and grinding to obtain white zirconium phosphate powder.
In the following examples, the dispersant used was wetting dispersant 5040 and the defoamer was silicone defoamer 470.
In the following examples, the preparation method of the methacrylic acid modified acrylate emulsion used comprises the following steps:
1) 2.0g of alkylphenol polyoxyethylene and 4.0g of lauryl sodium sulfate are dissolved in 90ml of deionized water to prepare an emulsifier aqueous solution, and the emulsifier aqueous solution is divided into three parts of 35ml, 30ml and 25 ml; adding 100g of n-butyl acrylate and 20g of methyl methacrylate into 35ml of emulsifier aqueous solution, stirring and mixing at room temperature, and pre-emulsifying for 1h to prepare a nuclear pre-emulsion; adding 20g of n-butyl acrylate, 60g of methyl methacrylate and 4.8g of methacrylic acid into 30ml of emulsifier aqueous solution, stirring and mixing at room temperature, and pre-emulsifying for 2h to prepare a shell pre-emulsion; dissolving 0.6g of sodium bicarbonate in 25ml of emulsifier water solution, stirring and dissolving to prepare a buffer water solution; adding 1.0g of potassium persulfate into 30ml of deionized water, stirring and dissolving to prepare an initiator aqueous solution;
2) preparing a seed emulsion: sequentially adding a buffer aqueous solution, an initiator aqueous solution with the volume of 1/3 and a nuclear pre-emulsion with the volume of 1/2 in a reaction vessel while stirring, heating to 70 ℃, and preserving heat for 0.5h when a large amount of blue light appears in the emulsion to obtain a seed emulsion;
3) polymerization of the core layer: slowly dripping the rest nuclear pre-emulsion and 1/3 initiator aqueous solution into the seed emulsion after the heat preservation of the seed emulsion is finished, controlling the temperature to 80 ℃ and preserving the heat for 0.5h after finishing dripping within 1h to obtain nuclear layer emulsion;
4) shell polymerization: and (3) when the heat preservation of the core emulsion is finished, dropwise adding the rest initiator aqueous solution and the shell pre-emulsion, finishing dropping within 1.5h, then heating to 85 ℃, preserving the heat for 0.5h, then naturally cooling to 40 ℃, adjusting the pH value to 8, and sieving by using a 200-mesh sieve to obtain the methacrylic acid modified acrylate core-shell emulsion.
Example 1
A nanometer zirconium phosphate-based flame-retardant bacteriostatic agent and a preparation method thereof comprise the following steps:
1) exfoliated zirconium phosphate (ZrP): in a 500ml four-mouth flask, 0.01mol of zirconium phosphate and 300ml of deionized water are fully dispersed by mechanical stirring and ultrasonic action, the process lasts for 30min, the temperature is kept at 5 ℃, then 100ml of tetrabutyl ammonium hydroxide solution (TBA concentration is 0.1 mol/L) is dripped into the four-mouth flask at a constant speed within 30min, ultrasonic stirring reaction is continued for 2h after dripping, 20ml of concentrated phosphoric acid with the concentration of 14.5mol/L is dripped into the flask at a constant speed within 30min, and after the reaction is finished (2h), the mixed solution is centrifuged to carry out solid-liquid separation, so as to obtain semitransparent gel precipitate and is washed by distilled water;
2) grafting chloropropionaldehyde: dispersing the product obtained in the step 1) and 0.01mol of chloropropionaldehyde in DMSO, carrying out mechanical stirring reaction for 16h at 50 ℃, centrifuging, washing, and drying to obtain light yellow liquid;
3) synthesizing Schiff base: dispersing the product obtained in the step 2) and 0.01mol of aminoimidazole in DMSO, mechanically stirring for 60min at 80 ℃, then heating to reflux reaction for 24h, cooling to room temperature after the reaction is finished, filtering, and washing to obtain the flame-retardant bacteriostatic agent based on the nano zirconium phosphate.
Example 2
A nanometer zirconium phosphate-based flame-retardant bacteriostatic agent and a preparation method thereof comprise the following steps:
1) exfoliated zirconium phosphate (ZrP): in a 500ml four-mouth flask, 0.01mol of zirconium phosphate and 300ml of deionized water are fully dispersed by mechanical stirring and ultrasonic action, the process lasts for 30min, the temperature is kept at 5 ℃, then 100ml of tetrabutyl ammonium hydroxide solution (TBA concentration is 0.1 mol/L) is dripped into the four-mouth flask at a constant speed within 30min, ultrasonic stirring reaction is continued for 2h after dripping, 20ml of concentrated phosphoric acid with the concentration of 14.5mol/L is dripped into the flask at a constant speed within 30min, and after the reaction is finished (2h), the mixed solution is centrifuged to carry out solid-liquid separation, so as to obtain semitransparent gel precipitate and is washed by distilled water;
2) grafting chloropropionaldehyde: dispersing the product obtained in the step 1) and 0.03mol of chloropropionaldehyde in DMSO, carrying out mechanical stirring reaction at 80 ℃ for 18h, centrifugally washing, and drying to obtain a light yellow liquid;
3) synthesizing Schiff base: dispersing the product obtained in the step 2) and 0.01mol of aminoimidazole in DMSO, mechanically stirring for 90min at 70 ℃, heating to reflux reaction for 18h, cooling to room temperature after the reaction is finished, filtering, and washing to obtain the flame-retardant bacteriostatic agent based on the nano zirconium phosphate.
Application example 1
The nanometer zirconium phosphate-based flame-retardant bacteriostatic agent obtained in the embodiment 1 is applied to the preparation of the intumescent fire-retardant coating, and comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersant, 0.5% of defoamer, 0.5% of n-octanol, 10% of water and 5% of flame retardant and bacteriostatic agent based on nano zirconium phosphate; grinding the weighed flame-retardant bacteriostatic agent based on the nano zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide and hydroxyethyl cellulose into powder, and then adding water, fully grinding and uniformly mixing; adding the defoaming agent and the dispersing agent, and continuously and fully grinding; and finally, adding methacrylic acid modified acrylate emulsion and n-octanol, fully grinding and uniformly mixing to obtain the fireproof coating.
Application example 2
The nanometer zirconium phosphate-based flame-retardant bacteriostatic agent obtained in the embodiment 1 is applied to the preparation of the intumescent fire-retardant coating, and comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersant, 0.5% of defoamer, 0.5% of n-octanol, 12% of water and 3% of flame retardant bacteriostatic agent based on nano zirconium phosphate; grinding the weighed flame-retardant bacteriostatic agent based on the nano zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide and hydroxyethyl cellulose into powder, and then adding water, fully grinding and uniformly mixing; adding the defoaming agent and the dispersing agent, and continuously and fully grinding; and finally, adding methacrylic acid modified acrylate emulsion and n-octanol, fully grinding and uniformly mixing to obtain the fireproof coating.
Application example 3
The nanometer zirconium phosphate-based flame-retardant bacteriostatic agent obtained in the embodiment 1 is applied to the preparation of the intumescent fire-retardant coating, and comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersant, 0.5% of defoamer, 0.5% of n-octanol, 13% of water and 2% of flame retardant and bacteriostatic agent based on nano zirconium phosphate; grinding the weighed flame-retardant bacteriostatic agent based on nano zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide and hydroxyethyl cellulose into powder, and then adding water, fully grinding and uniformly mixing; adding the defoaming agent and the dispersing agent, and continuously and fully grinding; and finally, adding methacrylic acid modified acrylate emulsion and n-octanol, fully grinding and uniformly mixing to obtain the fireproof coating.
Comparative example 1
The preparation method of the fireproof coating in the comparative example 1 is substantially the same as that in the application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol and 15% of water.
Comparative example 2
The preparation method of the fireproof coating in the comparative example 2 is substantially the same as that in the application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 10% of water and 5% of zirconium phosphate.
Comparative example 3
The preparation method of the fireproof coating in the comparative example 3 is substantially the same as that in the application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 10% of water and 5% of 2-aminoimidazole.
Comparative example 4
The preparation method of the fireproof coating of comparative example 4 is substantially the same as that of application example 1, except that the components and the mass percentages thereof are as follows: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersant, 0.5% of defoamer, 0.5% of n-octanol, 10% of water and 5% of zirconium phosphate and 2-aminoimidazole mixture (3% of zirconium phosphate and 2% of 2-aminoimidazole).
The intumescent fire-retardant coatings obtained in application examples 1-3 and comparative examples 1-4 were respectively subjected to fire resistance tests, and the results are shown in table 1.
TABLE 1 relevant Performance test of the intumescent coatings obtained in application examples 1-3 and comparative examples 1-4
| Application example 1 | Application example 2 | Application example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Morphology of coating preparation process | Uniform and fine without particles Attachment of | Uniform and fine without particles Attachment of | Uniform and fine without particles Attachment of | Uniform and fine without particles Attachment of | With a small amount of fine particles Attachment of | With a trace of fine particles Attachment of | With a small amount of fine particles Attachment of |
| Limit of fire resistance/min | 142.3 | 118.2 | 106.5 | 75.0 | 98.6 | 89.1 | 99.8 |
| Surface topography | Uniform and fine without caking | Uniform and fine without caking | Uniform and fine without caking | Uniform and fine without caking | Uniform and fine without caking | Uniform and fine without caking | Uniform and fine without caking |
| Storage time/month | ＞7 | ＞7 | ＞7 | ＜6 | ＜6 | ＜6 | ＜6 |
| Thickness of carbon layer/mm | 20.3 | 15.7 | 12.3 | 5.3 | 7.4 | 8.7 | 9.0 |
| Degree of densification of carbon layer | The carbon layer is more compact and has higher strength Height of | The carbon layer is more compact and has higher strength Height of | The carbon layer is more compact and has higher strength Height of | The carbon layer is more loose and has higher strength Is lower than | Loose carbon layer and higher strength Is low in | Compact carbon layer and high strength | Compact carbon layer and high strength |
| (ATCC 25923) inactivation time- min | 3 | 20 | 46 | / | 80 | 68 | 49 |
| (ATCC 25922) inactivation time- min | 2 | 18 | 40 | / | 75 | 62 | 53 |
The above results show that: the flame-retardant bacteriostatic agent based on the nano zirconium phosphate has the advantages of higher flame-retardant efficiency, excellent bacteriostatic effect, environmental protection, no pollution, good compatibility with resin, base materials and the like, and can effectively give consideration to other properties of the material, and the flame-retardant bacteriostatic agent can show the advantages of excellent fire resistance, better bacteriostatic property, good char formation, high carbon layer strength, good stability (long storage time) and the like when being applied to the preparation of the intumescent fire-retardant coating, and the related preparation method is simple and has wide application fields.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention. The invention can be realized by all the raw materials listed in the invention, and the invention can be realized by the upper and lower limit values and interval values of all the raw materials, and the examples are not listed. Further, the applicant intends to point out that modifications and variations may be made in accordance with the above teachings while remaining within the spirit and principles of the present invention, and all such modifications and variations are intended to fall within the scope of the appended claims.
Claims (9)
1. A preparation method of a nanometer zirconium phosphate-based flame-retardant bacteriostatic agent is characterized by comprising the following steps:
1) stripping zirconium phosphate: dropwise adding tetrabutyl ammonium hydroxide into the zirconium phosphate dispersion liquid, carrying out ultrasonic stirring reaction, then dropwise adding concentrated acid to carry out secondary reaction, and carrying out solid-liquid separation to obtain semitransparent gel precipitate;
2) grafting chloropropionaldehyde: mixing the semitransparent gel precipitate obtained in the step 1) with chloropropanal, stirring for reaction, centrifugally washing, and drying to obtain a light yellow liquid;
3) synthesizing Schiff base: mixing the light yellow liquid obtained in the step 2) with aminoimidazole, mechanically stirring, carrying out reflux reaction, cooling to room temperature, filtering, and washing to obtain the flame retardant bacteriostatic agent based on the nano zirconium phosphate;
the molar ratio of the zirconium phosphate introduced in the step 1), the chloropropionaldehyde introduced in the step 2) and the aminoimidazole introduced in the step 3) is 1 (1-8) to (0.5-8).
2. The method according to claim 1, wherein the concentration of the tetrabutylammonium hydroxide solution is 0.05 to 10 mol/L; the dripping time is 30-90 min; the reaction temperature is 0-20 ℃, and the ultrasonic stirring reaction time is 0.5-2 h.
3. The method according to claim 1, wherein the molar ratio of zirconium phosphate to tetrabutylammonium hydroxide introduced in step 1) is 5:1 to 1: 6.
4. The preparation method according to claim 1, wherein the secondary reaction time in the step 1) is 0.5-3 h.
5. The preparation method of claim 1, wherein the stirring reaction temperature in the step 2) is 30-100 ℃, and the stirring time is 12-24 hours.
6. The preparation method according to claim 1, wherein the aminoimidazole in step 3) is an imidazole derivative containing an amino group.
7. The preparation method of claim 1, wherein the mechanical stirring temperature in the step 3) is 60-120 ℃, the mechanical stirring time is 30-120min, and the reflux reaction time is 12-24 h.
8. The nanometer zirconium phosphate-based flame-retardant bacteriostatic agent prepared by the preparation method of any one of claims 1 to 7.
9. An intumescent fire retardant coating prepared by the nanometer zirconium phosphate-based flame retardant bacteriostatic agent of claim 8, which is characterized in that the components and the mass percentages thereof comprise: 20-30% of methacrylic acid modified acrylate core-shell emulsion, 30-36% of ammonium polyphosphate, 10-20% of pentaerythritol, 10-15% of melamine, 1-5% of titanium dioxide, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octyl alcohol, 1-10% of nano zirconium phosphate based flame retardant bacteriostatic agent and the balance of water.
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| CN202111101288.8A CN113861794B (en) | 2021-09-18 | 2021-09-18 | Nano zirconium phosphate-based flame-retardant bacteriostatic agent, preparation method thereof and prepared intumescent fireproof bacteriostatic coating |
| PCT/CN2021/120989 WO2023039939A1 (en) | 2021-09-18 | 2021-09-27 | Nano zirconium phosphate-based flame-retardant bacteriostatic agent and intumescent fireproof antibacterial coating prepared therefrom |
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| CN116554757B (en) * | 2023-05-24 | 2024-01-05 | 成都大学 | Preparation method of organic solid acid modified boron nitride water-based intumescent fireproof coating |
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