CN111117407A - Super-hydrophobic coating with flame retardant effect and preparation method thereof - Google Patents
Super-hydrophobic coating with flame retardant effect and preparation method thereof Download PDFInfo
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- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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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
- C09D5/185—Intumescent 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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Abstract
The invention discloses a super-hydrophobic coating with a flame retardant effect and a preparation method thereof, and relates to the technical field of high polymer materials. Firstly treating cholesterol with succinic anhydride and thionyl chloride to prepare pretreated cholesterol, then mixing the pretreated cholesterol with glucan for reaction to prepare modified glucan, mixing the modified glucan with polylactic acid, dialyzing in water, a gadolinium chloride solution and an ammonium polyphosphate solution in sequence to prepare flame-retardant microspheres, then calcining graphene oxide and silicon dioxide together, etching by hydrofluoric acid to prepare modified graphene, mixing and grinding the modified graphene and the modified glucan, and mixing with a silicone-acrylic emulsion and a dispersing agent to prepare the super-hydrophobic coating with a flame-retardant effect. The super-hydrophobic coating with the flame retardant effect has excellent flame retardance and hydrophobicity.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a super-hydrophobic coating with a flame retardant effect and a preparation method thereof.
Background
With the continuous development and utilization of super-hydrophobic material technology, in recent years, the following preparation technology of super-hydrophobic surface is developed: wet/reactive ion etching, embossing, machining, laser ablation, chemical/electrochemical oxidation, chemical/electrochemical deposition, sol-gel, hydrothermal synthesis, thermal spraying, and the like. However, expensive equipment and harsh process conditions make these techniques for preparing superhydrophobic coatings/thin films difficult to scale for industrial production and risk of being easily damaged. In order to solve these problems, a technology of uniformly spraying the prepared super-hydrophobic coating on the surface of the substrate by a spray coating method to form a super-hydrophobic coating has been developed as a novel method for constructing a super-hydrophobic film layer and has been widely used.
However, the currently used superhydrophobic coatings all adopt flammable organic solvents such as ethanol, isopropanol, petroleum hydrocarbon, acetone and the like as dispersing agents or dissolving agents, so that the superhydrophobic coatings have great potential safety hazards in the processes of preparation, production, transportation and the like, and the scale production, construction environment and batch transportation of the superhydrophobic coatings are greatly limited. Secondly, the additive of the super-hydrophobic coating often contains some combustible particles, such as carbon nano tubes, organic powder and the like, so that the super-hydrophobic coating has potential safety hazard in practical application. Therefore, the invention aims to provide the super-hydrophobic coating with the flame retardant effect and the preparation method thereof.
Disclosure of Invention
The invention aims to provide a super-hydrophobic coating with a flame retardant effect and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the super-hydrophobic coating with the flame retardant effect is characterized by mainly comprising the following raw material components in parts by weight: 20-40 parts of silicone-acrylic emulsion, 5-8 parts of modified graphene, 3-5 parts of dispersing agent and 15-20 parts of solvent.
The super-hydrophobic coating with the flame retardant effect is characterized by further comprising the following raw material components in parts by weight: 5-10 parts of flame-retardant microspheres.
Preferably, the silicone acrylic emulsion is BF-400B type silicone acrylic emulsion with the solid content of 50% or SD-528 type silicone acrylic emulsion with the solid content of 46%.
As optimization, the modified graphene is obtained by calcining graphene oxide and silicon dioxide together and then etching by hydrofluoric acid; the dispersing agent is any one of polyethylene glycol 200 or polyethylene glycol 400; the solvent is an ethanol solution with the mass fraction of 60%.
Preferably, the flame-retardant microspheres are prepared by modifying glucan with cholesterol, then reacting with polylactic acid, and mixing and dialyzing with an ammonium polyphosphate aqueous solution.
As optimization, the super-hydrophobic coating with the flame retardant effect mainly comprises the following raw material components in parts by weight: 30 parts of BF-400B type silicone-acrylate emulsion, 5 parts of modified graphene, 3 parts of polyethylene glycol 200, 15 parts of solvent and 6 parts of flame-retardant microspheres.
As optimization, the preparation method of the super-hydrophobic coating with the flame retardant effect mainly comprises the following preparation steps:
(1) mixing dextran with pretreated cholesterol, adding ethylenediamine, stirring under nitrogen atmosphere for reaction, dialyzing, and freeze drying to obtain modified dextran;
(2) mixing the modified glucan obtained in the step (1) with polylactic acid, dialyzing in water, dialyzing in gadolinium chloride solution, finally dialyzing in ammonium polyphosphate solution, and freeze-drying to obtain flame-retardant microspheres;
(3) mixing graphene oxide and nano silicon dioxide, freezing and drying, calcining in a nitrogen atmosphere to obtain pretreated graphene, mixing the pretreated graphene with hydrofluoric acid, washing with water and drying to obtain modified graphene;
(4) mixing and grinding the flame-retardant microspheres obtained in the step (2) and the modified graphene obtained in the step (3), mixing the flame-retardant microspheres with the silicone-acrylic emulsion, the solvent and the dispersant, and stirring and dispersing to obtain the super-hydrophobic coating with the flame-retardant effect;
(5) and (4) carrying out index analysis on the super-hydrophobic coating with the flame retardant effect obtained in the step (4).
As optimization, the preparation method of the super-hydrophobic coating with the flame retardant effect mainly comprises the following preparation steps:
(1) mixing glucan and dimethyl sulfoxide according to a mass ratio of 1: 250, adding ethylenediamine with the mass of 1-2 times of that of the glucan, stirring and mixing to obtain a glucan solution, and mixing the glucan solution and the pretreated cholesterol according to a mass ratio of 200: 1-300: 1, mixing, controlling the adding rate of pretreated cholesterol to be 2-3 mL/min, stirring and reacting under the nitrogen atmosphere to obtain a modified glucan compound, dialyzing the modified glucan compound in water for 24 hours, and freeze-drying to obtain modified glucan;
(2) mixing the modified glucan obtained in the step (1) with polylactic acid according to a mass ratio of 1: 1, adding dimethyl sulfoxide with the mass 50-80 times of that of the modified glucan obtained in the step (1), stirring and mixing to obtain a mixed dispersion liquid, placing the mixed dispersion liquid into a dialysis bag with the molecular weight cutoff of 1400, placing the dialysis bag into water for dialysis for 4 hours, taking out the dialysis bag, placing the dialysis bag into a gadolinium chloride solution with the mass fraction of 2% for dialysis for 48 hours, taking out the dialysis bag again, placing the dialysis bag into an ammonium polyphosphate solution with the mass fraction of 10% for dialysis for 4 hours, and freeze-drying substances in the dialysis bag to obtain flame-retardant microspheres;
(3) mixing graphene oxide and water according to a mass ratio of 1: 150, performing ultrasonic dispersion for 30min under the condition that the frequency is 55kHz to obtain a graphene oxide suspension, and mixing nano silicon dioxide and water according to the mass ratio of 1: 80, performing ultrasonic dispersion for 25min under the condition that the frequency is 45kHz to obtain a nano silicon dioxide suspension, and mixing the graphene oxide suspension and the nano silicon dioxide suspension according to the volume ratio of 1: 2, mixing, freeze-drying to obtain a graphene mixture, placing the graphene mixture in a carbonization furnace, introducing nitrogen into the carbonization furnace at a speed of 80-200 mL/min, carrying out heat treatment at 1000 ℃ for 30min, cooling, discharging to obtain a modified graphene blank, and mixing the modified graphene blank with hydrofluoric acid according to a mass ratio of 1: 8, mixing, soaking for 10min, filtering to obtain a filter cake, and washing the filter cake with deionized water for 3 times to obtain modified graphene;
(4) the flame-retardant microspheres obtained in the step (2) and the modified graphene obtained in the step (3) are mixed according to a mass ratio of 1.2: 1, mixing and grinding to obtain a flame retardant additive, and mixing the flame retardant additive with BF-400B type silicone-acrylic emulsion according to a mass ratio of 11: 30, adding polyethylene glycol 200 accounting for 0.1 time of the mass of the BF-400B silicone acrylic emulsion and 60% ethanol solution accounting for 0.5 time of the mass of the BF-400B silicone acrylic emulsion, and stirring and mixing to obtain the super-hydrophobic coating with the flame retardant effect;
(5) and (4) carrying out index analysis on the super-hydrophobic coating with the flame retardant effect obtained in the step (4).
Preferably, the preparation method of the pretreated cholesterol in the step (1) comprises the following steps of mixing cholesterol and pyridine according to a mass ratio of 1: 100, adding succinic anhydride with the mass being 1 time of that of cholesterol, stirring for reaction, then carrying out reduced pressure distillation to obtain a crude product, mixing the crude product with an ethanol solution with the mass fraction being 90%, filtering at the temperature of 50-80 ℃ to obtain a filtrate, recrystallizing the filtrate in ice water to obtain cholesterol-succinate, and mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1: 80, adding thionyl chloride with the mass 10 times that of the cholesterol-succinate, controlling the adding speed of the thionyl chloride to be 5-8 mL/min, stirring for reaction, and performing rotary evaporation and concentration to obtain the pretreated cholesterol.
Preferably, the polylactic acid in the step (2) is polylactic acid with a relative molecular weight of 3 × 104.
Compared with the prior art, the invention has the beneficial effects that:
the invention adds the flame-retardant microspheres and the modified graphene when preparing the super-hydrophobic coating with the flame-retardant effect, firstly, the graphene is changed from a simple lamellar structure into a corrugated lamellar structure after being modified, and after the product is used, a bionic gully structure can be formed on the surface of a paint film, so that the water contact angle is improved, and further, the hydrophobic property of the product is improved, secondly, the flame-retardant microspheres added in the process of preparing the super-hydrophobic coating with the flame-retardant effect are prepared from cholesterol-modified glucan and polylactic acid, the microspheres formed by the cholesterol-modified glucan and the polylactic acid can absorb ammonium polyphosphate inside the microspheres after being dialyzed, so that the problem of performance reduction of the product caused by directly adding the ammonium polyphosphate in the product is effectively solved, and because the ammonium polyphosphate is an intumescent flame retardant, after the product is heated, the ammonium polyphosphate can promote the carbonization of the microspheres, the method has the advantages that the microspheres are subjected to swelling cracking, and the wrinkled graphene is extruded, so that after a product is heated, a compact flame-retardant layer is formed on the surface of a paint film formed on the product, and the flame-retardant performance of the product is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to illustrate the method for testing each index of the superhydrophobic coating with flame retardant effect, which is prepared in the following examples, as follows:
hydrophobic property: and (3) applying the super-hydrophobic coating with the flame retardant effect obtained in each example and a comparative product on the surface of a glass sheet, and after the coating is cured, placing the glass sheet in a checking water contact angle.
Flame retardant property: the super-hydrophobic coating with the flame retardant effect obtained in each example and a comparative product are coated on the surface of a glass sheet, and after the coating is cured, the glass sheet is placed in a position for checking the limit oxygen index.
Example 1
A super-hydrophobic coating with a flame retardant effect mainly comprises the following components in parts by weight: 30 parts of BF-400B type silicone-acrylate emulsion, 5 parts of modified graphene, 3 parts of polyethylene glycol 200 and 6 parts of flame-retardant microspheres.
A preparation method of a super-hydrophobic coating with a flame retardant effect mainly comprises the following preparation steps:
(1) mixing glucan and dimethyl sulfoxide according to a mass ratio of 1: 250, adding ethylenediamine with the mass of 1 time of that of the glucan into a beaker, stirring and mixing for 30min at the temperature of 45 ℃ and the rotating speed of 400r/min to obtain a glucan solution, and mixing the glucan solution and the pretreated cholesterol according to the mass ratio of 250: 1, mixing the mixture in a flask, controlling the adding rate of pretreated cholesterol to be 3mL/min, introducing nitrogen into the flask at the rate of 25mL/min, stirring and reacting for 7 hours at the temperature of 70 ℃ to obtain a modified glucan compound, dialyzing the modified glucan compound in water for 24 hours, and freeze-drying to obtain modified glucan;
(2) mixing the modified glucan obtained in the step (1) with polylactic acid according to a mass ratio of 1: 1, adding dimethyl sulfoxide with the mass 80 times of that of the modified glucan obtained in the step (1) into a stirrer, stirring and mixing for 30min at the temperature of 40 ℃ and the rotating speed of 300r/min to obtain a mixed dispersion, placing the mixed dispersion into a dialysis bag with the molecular weight cutoff of 1400, placing the dialysis bag into water for dialysis for 4h, taking out the dialysis bag, placing the dialysis bag into a gadolinium chloride solution with the mass fraction of 2% for dialysis for 48h, taking out the dialysis bag again, placing the dialysis bag into an ammonium polyphosphate solution with the mass fraction of 10% for dialysis for 4h, and freeze-drying substances in the dialysis bag to obtain flame-retardant microspheres;
(3) mixing graphene oxide and water according to a mass ratio of 1: 150, performing ultrasonic dispersion for 30min under the condition that the frequency is 55kHz to obtain a graphene oxide suspension, and mixing nano silicon dioxide and water according to the mass ratio of 1: 80, performing ultrasonic dispersion for 25min under the condition that the frequency is 45kHz to obtain a nano silicon dioxide suspension, and mixing the graphene oxide suspension and the nano silicon dioxide suspension according to the volume ratio of 1: 2, mixing, freeze-drying to obtain a graphene mixture, placing the graphene mixture in a carbonization furnace, introducing nitrogen into the carbonization furnace at a rate of 150mL/min, carrying out heat treatment at 1000 ℃ for 30min, cooling to room temperature, discharging to obtain a modified graphene blank, and mixing the modified graphene blank with hydrofluoric acid according to a mass ratio of 1: 8, mixing, soaking for 10min, filtering to obtain a filter cake, and washing the filter cake with deionized water for 3 times to obtain modified graphene;
(4) the flame-retardant microspheres obtained in the step (2) and the modified graphene obtained in the step (3) are mixed according to a mass ratio of 1.2: 1, mixing and grinding to obtain a flame retardant additive, and mixing the flame retardant additive with BF-400B type silicone-acrylic emulsion according to a mass ratio of 11: 30, adding polyethylene glycol 200 accounting for 0.1 time of the mass of the BF-400B silicone acrylic emulsion and 60% ethanol solution accounting for 0.5 time of the mass of the BF-400B silicone acrylic emulsion, and stirring and mixing to obtain the super-hydrophobic coating with the flame retardant effect;
(5) and (4) carrying out index analysis on the super-hydrophobic coating with the flame retardant effect obtained in the step (4).
Preferably, the preparation method of the pretreated cholesterol in the step (1) comprises the following steps of mixing cholesterol and pyridine according to a mass ratio of 1: 100, adding succinic anhydride with the mass being 1 time of that of cholesterol, stirring for reaction, then carrying out reduced pressure distillation to obtain a crude product, mixing the crude product with an ethanol solution with the mass fraction being 90%, filtering at the temperature of 60 ℃ to obtain a filtrate, recrystallizing the filtrate in ice water to obtain cholesterol-succinate, and mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1: 80, adding thionyl chloride with the mass 10 times that of the cholesterol-succinate, controlling the adding speed of the thionyl chloride to be 8mL/min, stirring for reaction, and performing rotary evaporation and concentration to obtain the pretreated cholesterol.
Preferably, the polylactic acid in the step (2) has a relative molecular weight of 3 × 104The polylactic acid of (1).
Example 2
A super-hydrophobic coating with a flame retardant effect mainly comprises the following components in parts by weight: 30 parts of BF-400B type silicone-acrylate emulsion, 5 parts of modified graphene, 3 parts of polyethylene glycol 200 and 6 parts of flame-retardant microspheres.
A preparation method of a super-hydrophobic coating with a flame retardant effect mainly comprises the following preparation steps:
(1) mixing glucan and polylactic acid according to a mass ratio of 1: 1, adding dimethyl sulfoxide with the mass 80 times of that of glucan into a stirrer, stirring and mixing for 30min at the temperature of 40 ℃ and the rotating speed of 300r/min to obtain mixed dispersion, placing the mixed dispersion into a dialysis bag with the molecular weight cutoff of 1400, placing the dialysis bag into water for dialysis for 4h, taking out the dialysis bag, placing the dialysis bag into a gadolinium chloride solution with the mass fraction of 2% for dialysis for 48h, taking out the dialysis bag again, placing the dialysis bag into an ammonium polyphosphate solution with the mass fraction of 10% for dialysis for 4h, and freeze-drying substances in the dialysis bag to obtain the flame-retardant microspheres;
(2) mixing graphene oxide and water according to a mass ratio of 1: 150, performing ultrasonic dispersion for 30min under the condition that the frequency is 55kHz to obtain a graphene oxide suspension, and mixing nano silicon dioxide and water according to the mass ratio of 1: 80, performing ultrasonic dispersion for 25min under the condition that the frequency is 45kHz to obtain a nano silicon dioxide suspension, and mixing the graphene oxide suspension and the nano silicon dioxide suspension according to the volume ratio of 1: 2, mixing, freeze-drying to obtain a graphene mixture, placing the graphene mixture in a carbonization furnace, introducing nitrogen into the carbonization furnace at a rate of 150mL/min, carrying out heat treatment at 1000 ℃ for 30min, cooling to room temperature, discharging to obtain a modified graphene blank, and mixing the modified graphene blank with hydrofluoric acid according to a mass ratio of 1: 8, mixing, soaking for 10min, filtering to obtain a filter cake, and washing the filter cake with deionized water for 3 times to obtain modified graphene;
(3) the flame-retardant microspheres obtained in the step (1) and the modified graphene obtained in the step (2) are mixed according to a mass ratio of 1.2: 1, mixing and grinding to obtain a flame retardant additive, and mixing the flame retardant additive with BF-400B type silicone-acrylic emulsion according to a mass ratio of 11: 30, adding polyethylene glycol 200 accounting for 0.1 time of the mass of the BF-400B silicone acrylic emulsion and 60% ethanol solution accounting for 0.5 time of the mass of the BF-400B silicone acrylic emulsion, and stirring and mixing to obtain the super-hydrophobic coating with the flame retardant effect;
(4) and (4) carrying out index analysis on the super-hydrophobic coating with the flame retardant effect obtained in the step (3).
Preferably, the polylactic acid in the step (1) has a relative molecular weight of 3 × 104The polylactic acid of (1).
Example 3
A super-hydrophobic coating with a flame retardant effect mainly comprises the following components in parts by weight: 30 parts of BF-400B type silicone-acrylate emulsion, 5 parts of graphene, 3 parts of polyethylene glycol 200 and 6 parts of flame-retardant microspheres.
A preparation method of a super-hydrophobic coating with a flame retardant effect mainly comprises the following preparation steps:
(1) mixing glucan and dimethyl sulfoxide according to a mass ratio of 1: 250, adding ethylenediamine with the mass of 1 time of that of the glucan into a beaker, stirring and mixing for 30min at the temperature of 45 ℃ and the rotating speed of 400r/min to obtain a glucan solution, and mixing the glucan solution and the pretreated cholesterol according to the mass ratio of 250: 1, mixing the mixture in a flask, controlling the adding rate of pretreated cholesterol to be 3mL/min, introducing nitrogen into the flask at the rate of 25mL/min, stirring and reacting for 7 hours at the temperature of 70 ℃ to obtain a modified glucan compound, dialyzing the modified glucan compound in water for 24 hours, and freeze-drying to obtain modified glucan;
(2) mixing the modified glucan obtained in the step (1) with polylactic acid according to a mass ratio of 1: 1, adding dimethyl sulfoxide with the mass 80 times of that of the modified glucan obtained in the step (1) into a stirrer, stirring and mixing for 30min at the temperature of 40 ℃ and the rotating speed of 300r/min to obtain a mixed dispersion, placing the mixed dispersion into a dialysis bag with the molecular weight cutoff of 1400, placing the dialysis bag into water for dialysis for 4h, taking out the dialysis bag, placing the dialysis bag into a gadolinium chloride solution with the mass fraction of 2% for dialysis for 48h, taking out the dialysis bag again, placing the dialysis bag into an ammonium polyphosphate solution with the mass fraction of 10% for dialysis for 4h, and freeze-drying substances in the dialysis bag to obtain flame-retardant microspheres;
(3) the flame-retardant microspheres obtained in the step (2) and graphene are mixed according to a mass ratio of 1.2: 1, mixing and grinding to obtain a flame retardant additive, and mixing the flame retardant additive with BF-400B type silicone-acrylic emulsion according to a mass ratio of 11: 30, adding polyethylene glycol 200 accounting for 0.1 time of the mass of the BF-400B silicone acrylic emulsion and 60% ethanol solution accounting for 0.5 time of the mass of the BF-400B silicone acrylic emulsion, and stirring and mixing to obtain the super-hydrophobic coating with the flame retardant effect;
(4) and (4) carrying out index analysis on the super-hydrophobic coating with the flame retardant effect obtained in the step (3).
Preferably, the preparation method of the pretreated cholesterol in the step (1) comprises the following steps of mixing cholesterol and pyridine according to a mass ratio of 1: 100, adding succinic anhydride with the mass being 1 time of that of cholesterol, stirring for reaction, then carrying out reduced pressure distillation to obtain a crude product, mixing the crude product with an ethanol solution with the mass fraction being 90%, filtering at the temperature of 60 ℃ to obtain a filtrate, recrystallizing the filtrate in ice water to obtain cholesterol-succinate, and mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1: 80, adding thionyl chloride with the mass 10 times that of the cholesterol-succinate, controlling the adding speed of the thionyl chloride to be 8mL/min, stirring for reaction, and performing rotary evaporation and concentration to obtain the pretreated cholesterol.
Preferably, the polylactic acid in the step (2) has a relative molecular weight of 3 × 104The polylactic acid of (1).
Comparative example
A super-hydrophobic coating with a flame retardant effect mainly comprises the following components in parts by weight: 30 parts of BF-400B type silicone-acrylate emulsion, 5 parts of graphene, 3 parts of polyethylene glycol 200 and 6 parts of flame-retardant microspheres.
A preparation method of a super-hydrophobic coating with a flame retardant effect mainly comprises the following preparation steps:
(1) mixing glucan and polylactic acid according to a mass ratio of 1: 1, adding dimethyl sulfoxide with the mass 80 times of that of glucan into a stirrer, stirring and mixing for 30min at the temperature of 40 ℃ and the rotating speed of 300r/min to obtain mixed dispersion, placing the mixed dispersion into a dialysis bag with the molecular weight cutoff of 1400, placing the dialysis bag into water for dialysis for 4h, taking out the dialysis bag, placing the dialysis bag into a gadolinium chloride solution with the mass fraction of 2% for dialysis for 48h, taking out the dialysis bag again, placing the dialysis bag into an ammonium polyphosphate solution with the mass fraction of 10% for dialysis for 4h, and freeze-drying substances in the dialysis bag to obtain the flame-retardant microspheres;
(2) the flame-retardant microspheres obtained in the step (1) and graphene are mixed according to a mass ratio of 1.2: 1, mixing and grinding to obtain a flame retardant additive, and mixing the flame retardant additive with BF-400B type silicone-acrylic emulsion according to a mass ratio of 11: 30, adding polyethylene glycol 200 accounting for 0.1 time of the mass of the BF-400B silicone acrylic emulsion and 60% ethanol solution accounting for 0.5 time of the mass of the BF-400B silicone acrylic emulsion, and stirring and mixing to obtain the super-hydrophobic coating with the flame retardant effect;
(3) and (3) carrying out index analysis on the super-hydrophobic coating with the flame retardant effect obtained in the step (2).
Preferably, the polylactic acid in the step (1) has a relative molecular weight of 3 × 104The polylactic acid of (1).
Examples of effects
The following table 1 shows the results of performance analysis of the superhydrophobic coating having flame retardant effect using examples 1 to 3 of the present invention and a comparative example.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Water contact Angle (°) | 155.6 | 130.1 | 121.2 | 106.8 |
| Limiting oxygen index (%) | 26.8 | 24.3 | 21.6 | 19.2 |
Compared with the experimental data of the comparative example and the example 1 in the table 1, the flame retardant microspheres and the modified graphene can be added to effectively improve the hydrophobic property and the flame retardant property of the product when the super-hydrophobic coating with the flame retardant effect is prepared; from the comparison of the experimental data of the embodiment 1 and the embodiment 2, it can be found that the flame retardant property of the product can be effectively improved by using the microspheres prepared from the pretreated cholesterol-modified glucan and the polylactic acid when preparing the superhydrophobic coating with the flame retardant effect, and probably because the ammonium polyphosphate can be coated in the microspheres in the dialysis process after the pretreated cholesterol-modified glucan is mixed with the polylactic acid, so that after the dextran is added into the product, the carbonization of the polylactic acid microspheres can be promoted when the product is combusted, a compact flame retardant layer is formed with the graphene, and the flame retardant property of the product is further improved; from the comparison of the experimental data of the embodiment 1 and the embodiment 3, it can be found that when the super-hydrophobic coating with the flame retardant effect is prepared, graphene is not modified, and the surface of the graphene does not have a wrinkle structure, so that a bionic structure cannot be formed on the surface of a film after the film is formed, and the hydrophobic property of the product is reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The super-hydrophobic coating with the flame retardant effect is characterized by mainly comprising the following raw material components in parts by weight: 20-40 parts of silicone-acrylic emulsion, 5-8 parts of modified graphene, 3-5 parts of dispersing agent and 15-20 parts of solvent.
2. The super-hydrophobic coating with the flame retardant effect as claimed in claim 1, wherein the super-hydrophobic coating with the flame retardant effect further comprises the following raw material components in parts by weight: 5-10 parts of flame-retardant microspheres.
3. The super-hydrophobic paint with flame retardant effect as claimed in claim 2, wherein the silicone acrylic emulsion is BF-400B type silicone acrylic emulsion with 50% solid content or SD-528 type silicone acrylic emulsion with 46% solid content.
4. The super-hydrophobic coating with the flame retardant effect as claimed in claim 3, wherein the modified graphene is obtained by co-calcining graphene oxide and silicon dioxide and then etching with hydrofluoric acid; the dispersing agent is any one of polyethylene glycol 200 or polyethylene glycol 400; the solvent is an ethanol solution with the mass fraction of 60%.
5. The super-hydrophobic coating with the flame retardant effect as claimed in claim 4, wherein the flame retardant microspheres are prepared by modifying dextran with cholesterol, then reacting with polylactic acid, mixing with ammonium polyphosphate water solution, and dialyzing.
6. The super-hydrophobic coating with the flame retardant effect as claimed in claim 5, wherein the super-hydrophobic coating with the flame retardant effect mainly comprises the following raw material components in parts by weight: 30 parts of BF-400B type silicone-acrylate emulsion, 5 parts of modified graphene, 3 parts of polyethylene glycol 200, 15 parts of solvent and 6 parts of flame-retardant microspheres.
7. A preparation method of a super-hydrophobic coating with a flame retardant effect is characterized by mainly comprising the following preparation steps:
(1) mixing dextran with pretreated cholesterol, adding ethylenediamine, stirring under nitrogen atmosphere for reaction, dialyzing, and freeze drying to obtain modified dextran;
(2) mixing the modified glucan obtained in the step (1) with polylactic acid, dialyzing in water, dialyzing in gadolinium chloride solution, finally dialyzing in ammonium polyphosphate solution, and freeze-drying to obtain flame-retardant microspheres;
(3) mixing graphene oxide and nano silicon dioxide, freezing and drying, calcining in a nitrogen atmosphere to obtain pretreated graphene, mixing the pretreated graphene with hydrofluoric acid, washing with water and drying to obtain modified graphene;
(4) mixing and grinding the flame-retardant microspheres obtained in the step (2) and the modified graphene obtained in the step (3), mixing the flame-retardant microspheres with the silicone-acrylic emulsion, the solvent and the dispersant, and stirring and dispersing to obtain the super-hydrophobic coating with the flame-retardant effect;
(5) and (4) carrying out index analysis on the super-hydrophobic coating with the flame retardant effect obtained in the step (4).
8. The preparation method of the flame-retardant superhydrophobic coating according to claim 6, characterized by mainly comprising the following preparation steps:
(1) mixing glucan and dimethyl sulfoxide according to a mass ratio of 1: 250, adding ethylenediamine with the mass of 1-2 times of that of the glucan, stirring and mixing to obtain a glucan solution, and mixing the glucan solution and the pretreated cholesterol according to a mass ratio of 200: 1-300: 1, mixing, controlling the adding rate of pretreated cholesterol to be 2-3 mL/min, stirring and reacting under the nitrogen atmosphere to obtain a modified glucan compound, dialyzing the modified glucan compound in water for 24 hours, and freeze-drying to obtain modified glucan;
(2) mixing the modified glucan obtained in the step (1) with polylactic acid according to a mass ratio of 1: 1, adding dimethyl sulfoxide with the mass 50-80 times of that of the modified glucan obtained in the step (1), stirring and mixing to obtain a mixed dispersion liquid, placing the mixed dispersion liquid into a dialysis bag with the molecular weight cutoff of 1400, placing the dialysis bag into water for dialysis for 4 hours, taking out the dialysis bag, placing the dialysis bag into a gadolinium chloride solution with the mass fraction of 2% for dialysis for 48 hours, taking out the dialysis bag again, placing the dialysis bag into an ammonium polyphosphate solution with the mass fraction of 10% for dialysis for 4 hours, and freeze-drying substances in the dialysis bag to obtain flame-retardant microspheres;
(3) mixing graphene oxide and water according to a mass ratio of 1: 150, performing ultrasonic dispersion for 30min under the condition that the frequency is 55kHz to obtain a graphene oxide suspension, and mixing nano silicon dioxide and water according to the mass ratio of 1: 80, performing ultrasonic dispersion for 25min under the condition that the frequency is 45kHz to obtain a nano silicon dioxide suspension, and mixing the graphene oxide suspension and the nano silicon dioxide suspension according to the volume ratio of 1: 2, mixing, freeze-drying to obtain a graphene mixture, placing the graphene mixture in a carbonization furnace, introducing nitrogen into the carbonization furnace at a speed of 80-200 mL/min, carrying out heat treatment at 1000 ℃ for 30min, cooling, discharging to obtain a modified graphene blank, and mixing the modified graphene blank with hydrofluoric acid according to a mass ratio of 1: 8, mixing, soaking for 10min, filtering to obtain a filter cake, and washing the filter cake with deionized water for 3 times to obtain modified graphene;
(4) the flame-retardant microspheres obtained in the step (2) and the modified graphene obtained in the step (3) are mixed according to a mass ratio of 1.2: 1, mixing and grinding to obtain a flame retardant additive, and mixing the flame retardant additive with BF-400B type silicone-acrylic emulsion according to a mass ratio of 11: 30, adding polyethylene glycol 200 accounting for 0.1 time of the mass of the BF-400B silicone acrylic emulsion and 60% ethanol solution accounting for 0.5 time of the mass of the BF-400B silicone acrylic emulsion, and stirring and mixing to obtain the super-hydrophobic coating with the flame retardant effect;
(5) and (4) carrying out index analysis on the super-hydrophobic coating with the flame retardant effect obtained in the step (4).
9. The method for preparing the superhydrophobic coating with the flame retardant effect according to claim 7, wherein the step (1) of preparing the pretreated cholesterol is to mix the cholesterol and the pyridine in a mass ratio of 1: 100, adding succinic anhydride with the mass being 1 time of that of cholesterol, stirring for reaction, then carrying out reduced pressure distillation to obtain a crude product, mixing the crude product with an ethanol solution with the mass fraction being 90%, filtering at the temperature of 50-80 ℃ to obtain a filtrate, recrystallizing the filtrate in ice water to obtain cholesterol-succinate, and mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1: 80, adding thionyl chloride with the mass 10 times that of the cholesterol-succinate, controlling the adding speed of the thionyl chloride to be 5-8 mL/min, stirring for reaction, and performing rotary evaporation and concentration to obtain the pretreated cholesterol.
10. The method for preparing the flame-retardant superhydrophobic coating according to claim 7, wherein the polylactic acid of the step (2) has a relative molecular weight of 3 x 104The polylactic acid of (1).
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