Halogen-free flame-retardant silane water-based paint and preparation and application thereof
Technical Field
The invention relates to the technical field of paint preparation, in particular to a halogen-free flame-retardant silane water-based paint.
Background
In recent years, with the increasing strictness of fire safety regulations, people pay more attention to the reduction of fire hazards caused by highly flammable materials such as wood, plastics, textiles and the like. A suitable flame retardant may retard the ignition time or inhibit the spread of flame of these materials, thereby eliminating the potential for fire hazards and reducing life and property damage. People have long invested great efforts to improve the fire-retardant properties of wood, plastics, textiles, etc., and there are three fire-retardant methods that have been widely used so far: the first method is a low-cost rapid mixing technique, i.e. mechanically blending the flame retardant into the polymer matrix, however, an effective flame retardant effect requires a large amount of flame retardant to be loaded, which will have a significant impact on the strength and elastic modulus of the material; the second method is to modify a functional group with flame-retardant effect on a material matrix through chemical modification, so as to reduce the flammability of the material, change a flame-retardant element into a component of a polymer chain, generally have higher flame-retardant efficiency and longer durable flame-retardant effect, but the method can change the form and physical properties of most polymers, such as melting point, density, glass transition temperature and the like, and cause troubles to the industrial production of certain materials; the third method is surface treatment, i.e. using fire retardant and fire retardant coatings, which has become the most convenient, economical and effective method.
The common flame-retardant coating contains halogen, and when the halogen-containing material is combusted, a large amount of toxic smoke, carbon monoxide and hydrogen halide gas are released, so that evacuation and fire extinguishing work of people is prevented in a fire, secondary pollution is caused after the fire occurs, and life and property are seriously lost. Halogen-free flame retardant coatings have become the development trend of coatings, but the flame retardant additives used in common halogen-free flame retardant coatings are conventional aluminum hydroxide, magnesium hydroxide, silicate and expanded graphite systems, when the conventional magnesium hydroxide is used as an additive, the flame retardant rate is low, the required filling amount is large, and the flame retardant effect can be achieved only when the total weight of the coating is more than 50%. Therefore, the development of a halogen-free flame retardant coating with relatively low addition of a flame retardant and good flame retardant effect is urgently needed to meet the needs of social development.
Disclosure of Invention
In order to solve the technical problems, the invention provides a halogen-free flame-retardant silane water-based paint and preparation and application thereof, and aims to provide the halogen-free flame-retardant silane water-based paint which adopts a halogen-free formula, does not generate secondary pollution during combustion, adopts a water-based fluorine-containing silane base material, has good elasticity, tough and wear-resistant surface, excellent high and low temperature performance, water resistance, ultraviolet resistance, medium resistance, irradiation resistance and other characteristics, has proper viscosity, is easy to adopt various operation modes such as spraying, dip coating, brush coating or pouring coating and the like, and is a widely applied and ideal protective material.
The invention provides a halogen-free flame-retardant silane water-based paint which is prepared from the following raw materials in parts by weight: 70-90 parts of tridecafluorooctyl trimethoxy silane, 10-20 parts of aluminum oxide modified graphene oxide flame retardant, 10-20 parts of emulsifier, 20-30 parts of hydrotalcite, 1-10 parts of coupling agent, 1-10 parts of dispersant, 0.01-5 parts of reinforcing agent, 0.1-5 parts of inorganic pigment and 220 parts of deionized water 150-;
the emulsifier is selected from one or more of polyvinyl benzene sulfonic acid, sodium polyvinyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide and dioctyl sodium sulfosuccinate;
the inorganic pigment is selected from one or more of titanium white, chrome yellow, iron blue, cadmium red, cadmium yellow, lithopone, carbon black, iron oxide red and iron oxide yellow;
the coupling agent is selected from silane coupling agent and is selected from one of KH550, KH560, KH570, KH792, DL602 and DL 171;
the dispersing agent is selected from one or more of liquid paraffin, microcrystalline paraffin, barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate, copper stearate, polyethylene glycol 200 and polyethylene glycol 400;
the reinforcing agent is selected from one or more of silicon carbide fiber, nano titanium carbide, ceramic powder, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, polyacrylamide, polyvinylamine, carboxymethyl cellulose-polyvinyl alcohol, sodium polyacrylate, sodium caseinate, hydroxyapatite and sodium carboxymethyl cellulose.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 60-70 parts of tridecafluorooctyl trimethoxy silane, 12-17 parts of aluminum oxide modified graphene oxide flame retardant, 12-17 parts of emulsifier, 22-27 parts of hydrotalcite, 2-7 parts of coupling agent, 2-7 parts of dispersant, 0.1-3 parts of reinforcing agent, 0.5-3 parts of inorganic pigment and 200 parts of deionized water 170.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 65 parts of tridecafluorooctyl trimethoxy silane, 15 parts of aluminum oxide modified graphene oxide flame retardant, 16 parts of emulsifier, 25 parts of hydrotalcite, 5 parts of coupling agent, 5 parts of dispersing agent, 1 part of reinforcing agent, 2 parts of inorganic pigment and 185 parts of deionized water.
As a further improvement of the invention, the aluminum oxide modified graphene oxide flame retardant is prepared by the following steps:
preparing graphene oxide by adopting an improved Hummers method;
step two, ultrasonically dispersing graphene oxide in absolute ethyl alcohol, heating to 50 ℃, adding a silane coupling agent KH570 into the absolute ethyl alcohol, dropwise adding an acetic acid solution to enable the pH value of the solution to be 4.0-5.0 to obtain a prehydrolysis silane coupling agent solution, slowly dropwise adding the prehydrolysis silane coupling agent solution into the graphene oxide ethanol solution, continuously adding aluminum oxide, heating in a water bath at 80-90 ℃, stirring for reacting for 2-4h, performing suction filtration after the reaction is finished, and washing the solid with ethanol for multiple times to obtain the aluminum oxide modified graphene oxide flame retardant.
As a further improvement of the invention, the ultrasonic condition is 700W ultrasonic for 30-50 min.
As a further improvement of the invention, the mass ratio of the graphene oxide to the silane coupling agent KH570 to the aluminum oxide is 10 to (0.5-1) to (2-5).
The invention further provides a preparation method of the halogen-free flame-retardant silane water-based paint, which comprises the following steps:
step one, adding tridecafluorooctyltrimethoxysilane into a reaction kettle, uniformly stirring, adding 1/2 deionized water and an emulsifier, carrying out ultrasonic treatment for 30min, and then carrying out open stirring reaction at room temperature for 4-6h to obtain emulsion A;
step two, heating the aluminum oxide modified graphene oxide flame retardant, the hydrotalcite, the coupling agent, the dispersing agent, the reinforcing agent and the remaining 1/2 deionized water in a water bath at the temperature of 30-50 ℃, stirring for 3-4h, cooling and discharging, adding the inorganic pigment, and uniformly mixing to obtain a component B;
and step three, uniformly mixing the emulsion A and the component B by using an electronic stirrer to obtain the emulsion.
As a further improvement of the invention, the ultrasonic power is 400-600W.
The invention further protects the application of the halogen-free flame-retardant silane water-based paint in the field of building materials.
The invention has the following beneficial effects:
1. the aluminum oxide modified graphene oxide flame retardant prepared by the invention adopts a halogen-free formula, does not generate secondary pollution during combustion, and has a flame retardant effect equivalent to or even better than that of a common flame retardant when the addition amount of the flame retardant is only 3-5%;
2. the halogen-free flame-retardant silane water-based paint prepared by the invention adopts a water-based fluorine-containing silane base material, has good elasticity, a tough and wear-resistant surface, and has excellent characteristics of high and low temperature performance, water resistance, ultraviolet resistance, medium resistance, irradiation resistance and the like, and in addition, the paint has proper viscosity, is easy to adopt various operation modes such as spraying, dip coating, brush coating or flow coating and the like, and is a widely-applied and very ideal protective material;
3. according to the invention, various inorganic pigments are added, and water-based paint with different colors can be prepared by selecting different colors and controlling the addition amount, so that the attractiveness is enhanced.
Drawings
FIG. 1 is a preparation process diagram of a halogen-free flame-retardant silane water-based paint.
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, and it is obvious that the embodiments described are only some representative embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
Example 1 preparation of a halogen-free flame retardant silane waterborne coating:
the raw materials comprise:
70 parts of tridecafluorooctyl trimethoxy silane, 10 parts of aluminum oxide modified graphene oxide flame retardant, 10 parts of polyvinyl benzene sulfonic acid, 20 parts of hydrotalcite, 1711 parts of coupling agent DL, 1 part of barium stearate, 0.01 part of nano titanium carbide, 0.1 part of titanium white and 150 parts of deionized water;
the aluminum oxide modified graphene oxide flame retardant is prepared by the following steps;
the raw materials comprise: the mass ratio of the graphene oxide to the silane coupling agent KH570 to the aluminum oxide is 10: 0.5: 2;
preparing graphene oxide by adopting an improved Hummers method;
step two, dispersing graphene oxide in absolute ethyl alcohol by ultrasonic waves (ultrasonic conditions are 700W ultrasonic waves for 30min), heating to 50 ℃, adding a silane coupling agent KH570 into the absolute ethyl alcohol, dropwise adding an acetic acid solution to enable the pH value of the solution to be 4.0 to obtain a prehydrolysis silane coupling agent solution, slowly dropwise adding the prehydrolysis silane coupling agent solution into the graphene oxide ethanol solution, continuously adding aluminum oxide, heating in a water bath at 80 ℃, stirring and reacting for 2 hours, performing suction filtration after the reaction is finished, and washing the solid with ethanol for multiple times to obtain the aluminum oxide modified graphene oxide flame retardant.
Preparing a halogen-free flame-retardant silane water-based paint:
step one, adding tridecafluorooctyl trimethoxy silane into a reaction kettle, uniformly stirring, adding 1/2 deionized water and polyvinyl benzene sulfonic acid, performing ultrasonic treatment for 30min at the ultrasonic power of 400W, and then performing open stirring reaction for 4h at room temperature to obtain emulsion A;
step two, heating the aluminum oxide modified graphene oxide flame retardant, hydrotalcite, a coupling agent DL171, barium stearate, nano titanium carbide and the remaining 1/2 deionized water in a water bath at 30 ℃, stirring for 3 hours, cooling and discharging, adding titanium white, and uniformly mixing to obtain a component B;
and step three, uniformly mixing the emulsion A and the component B by using an electronic stirrer to obtain the halogen-free flame-retardant silane water-based paint.
Example 2 preparation of a halogen-free flame retardant silane waterborne coating:
the raw materials comprise:
90 parts of tridecafluorooctyl trimethoxy silane, 20 parts of aluminum oxide modified graphene oxide flame retardant, 20 parts of hexadecyl trimethyl ammonium bromide, 30 parts of hydrotalcite, 10 parts of coupling agent KH 57010, 10 parts of cadmium stearate, 5 parts of ceramic powder, 5 parts of iron oxide red and 220 parts of deionized water;
the aluminum oxide modified graphene oxide flame retardant is prepared by the following steps;
the raw materials comprise: the mass ratio of the graphene oxide to the silane coupling agent KH570 to the aluminum oxide is 10: 1: 5;
preparing graphene oxide by adopting an improved Hummers method;
step two, dispersing graphene oxide in absolute ethyl alcohol by ultrasonic waves (ultrasonic conditions are 700W for 50min), heating to 50 ℃, adding a silane coupling agent KH570 into the absolute ethyl alcohol, dropwise adding an acetic acid solution to enable the pH value of the solution to be 5.0 to obtain a prehydrolysis silane coupling agent solution, slowly dropwise adding the prehydrolysis silane coupling agent solution into the graphene oxide ethanol solution, continuously adding aluminum oxide, heating in a water bath at 80-90 ℃, stirring and reacting for 2-4h, performing suction filtration after the reaction is finished, and washing solids with ethanol for multiple times to obtain the aluminum oxide modified graphene oxide flame retardant.
Preparing a halogen-free flame-retardant silane water-based paint:
step one, adding tridecafluorooctyltrimethoxysilane into a reaction kettle, stirring uniformly, adding 1/2 deionized water and hexadecyl trimethyl ammonium bromide, performing ultrasonic treatment for 30min at the ultrasonic power of 600W, and then performing open stirring reaction for 6h at room temperature to obtain emulsion A;
step two, heating the aluminum oxide modified graphene oxide flame retardant, hydrotalcite, a coupling agent KH570, cadmium stearate, ceramic powder and the remaining 1/2 deionized water in a water bath at 50 ℃, stirring for 4 hours, cooling and discharging, adding iron oxide red, and uniformly mixing to obtain a component B;
and step three, uniformly mixing the emulsion A and the component B by using an electronic stirrer to obtain the halogen-free flame-retardant silane water-based paint.
Example 3 preparation of a halogen-free flame retardant silane waterborne coating:
the raw materials comprise:
65 parts of tridecafluorooctyl trimethoxysilane, 15 parts of an aluminum oxide modified graphene oxide flame retardant, 16 parts of dioctyl sodium sulfosuccinate, 25 parts of hydrotalcite, 5 parts of a coupling agent KH 5505, 2005 parts of polyethylene glycol, 1 part of sodium polyacrylate, 1 part of chrome yellow, 1 part of iron blue and 185 parts of deionized water;
the aluminum oxide modified graphene oxide flame retardant is prepared by the following steps:
the raw materials comprise: the mass ratio of the graphene oxide to the silane coupling agent KH570 to the aluminum oxide is 10: 0.7: 3.5;
preparing graphene oxide by adopting an improved Hummers method;
step two, dispersing graphene oxide in absolute ethyl alcohol by ultrasonic waves (ultrasonic conditions are 700W and ultrasonic for 40min), heating to 50 ℃, adding a silane coupling agent KH570 into the absolute ethyl alcohol, dropwise adding an acetic acid solution to enable the pH value of the solution to be 4.5 to obtain a prehydrolysis silane coupling agent solution, slowly dropwise adding the prehydrolysis silane coupling agent solution into the graphene oxide ethanol solution, continuously adding aluminum oxide, heating in a water bath at 85 ℃, stirring and reacting for 3 hours, performing suction filtration after the reaction is finished, and washing the solid with ethanol for multiple times to obtain the aluminum oxide modified graphene oxide flame retardant.
Preparing a halogen-free flame-retardant silane water-based paint:
step one, adding tridecafluorooctyltrimethoxysilane into a reaction kettle, uniformly stirring, adding 1/2 deionized water and dioctyl sodium sulfosuccinate, performing ultrasonic treatment for 30min at the ultrasonic power of 500W, and then stirring and reacting for 5h at room temperature to obtain emulsion A;
step two, heating the aluminum oxide modified graphene oxide flame retardant, hydrotalcite, a coupling agent KH550, polyethylene glycol 200, sodium polyacrylate and the remaining 1/2 deionized water in a water bath at 40 ℃, stirring for 3.5 hours, cooling and discharging, adding chrome yellow and iron blue, and uniformly mixing to obtain a component B;
and step three, uniformly mixing the emulsion A and the component B by using an electronic stirrer to obtain the halogen-free flame-retardant silane water-based paint.
Comparative example 1, prepared according to the method of patent ZL 201410008209.2 "a flame retardant coating and its use".
Firstly, 32.14 parts of A1(HDI trimer) and 134.9 parts of A2 (prepolymer of TDI isocyanate and polytetrahydrofuran ether) are added according to the isocyanate molar ratio of 1: 1, 1.2 parts of defoaming agent BYK-141 and 26.7 parts of diluent propylene glycol monomethyl ether acetate are put into a stirring tank, stirred for 5min at the speed of 800r/min, and then discharged. Secondly, 86.4 parts of chain extender polyaspartic acid ester (NHQ640, amine value: 162) and 30.7 parts of melamine modified polyether POP-290 are weighed and added into a stirring tank, 3.4 parts of dispersant BYK-163, 2.9 parts of defoamer BYK-392, 2.6 parts of flatting agent BYK-410 and 2.7 parts of organic bismuth catalyst (BiCAT8108) are added according to the experimental formula and dispersed for 5min at 1000r/min, 46.2 parts of flame retardant filler melamine coated ammonium polyphosphate (ExolitAPP462), 20 parts of expandable graphite, 48.7 parts of diethyl aluminum hypophosphite and 8 parts of aluminum titanate are gradually added until all the components are uniformly mixed, 6.6 parts of carbon black are added, 55.4 parts of diluent 2-butanone, 150# solvent oil and propylene glycol methyl ether mixed solvent (volume ratio is 3: 1) are added, and the mixture is mixed and stirred for 10 min, and the stirring speed is set to 2400 r/min. And then, moving the system into a sand mill to grind for 5 minutes, and then filtering and discharging with 1500-mesh gauze to obtain the flame-retardant coating.
Comparative example 2 was prepared according to the method of patent ZL 201110206283.1 "a room temperature curable phenyl silicone conformal coating".
220g of phenyltrimethoxysilane, 64g of methylphenyldimethoxysilane and 295g of toluene are added into a 1L three-necked flask, 73.3g of hydrochloric acid aqueous solution with the mass fraction of 0.01% is dropwise added into the flask under normal temperature and rapid stirring, the dropwise adding time is controlled to be about 20min, the temperature is raised to 75 ℃ after the hydrochloric acid aqueous solution is dropwise added, the reflux reaction is carried out for 4.5h, the temperature is reduced to 50 ℃ after the reflux reaction is finished, 1.29g of hexamethyldisilazane is added, the reaction is stopped after the reaction is cooled and stood, the reaction solution after filtration is heated to 120-130 ℃, and 325g of semitransparent phenyl silicone resin is obtained after by-products methanol and partial solvent are distilled out under normal pressure, wherein the solid content of the resin is about 55%. 210g of the prepared methyl phenyl silicone resin, 70.4g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 80mpa.s and 265g of toluene are added into a 1L three-neck flask provided with a nitrogen protection and water distribution device, copolycondensation reaction is carried out at 110 ℃ in the presence of a catalyst under the protection of nitrogen, water generated by the polycondensation reaction is collected by a water distributor in the reaction process, partial solvent is distilled out under reduced pressure after continuous reaction for 6 hours, the reactant is adjusted to certain solid content, and finally the transparent and uniform block copolymer of the methyl phenyl silicone resin and the linear polysiloxane with the viscosity of 350mpa.s is obtained. And (2) taking 100 parts of the obtained copolymer of the methyl phenyl silicone resin and the linear polysiloxane, adding 5 parts of methyl trimethoxy silane, 2 parts of gamma-aminopropyl triethoxysilane, 0.1 part of tricresyl phosphate, 0.5 part of isopropyl titanate and 30 parts of toluene, and uniformly mixing to obtain the phenyl silicone resin conformal coating II capable of being cured at room temperature.
Test example 1
The test method comprises the following steps:
fatigue test: according to GB/T13934-2006;
and (3) testing the adhesive force: according to GB/T9286-1998;
the heat release rate and smoke toxicity and smoke density of the flame-retardant coating are as follows: according to EN 45545.
The results are shown in Table 1.
Table 1 results of paint property testing for each group
Note: a number of deflections of the coating first developing cracks
According to the data in the table, the material coated with the flame-retardant coating has the advantages that the heat release rate is obviously reduced, the smoke toxicity and the smoke density are greatly reduced, and the flame-retardant material has a very good flame-retardant effect. Meanwhile, as can be seen from table 1, the material coated with the halogen-free flame retardant silane water-based paint prepared by the invention has good adhesive force and fatigue resistance. Compared with the prior art, the maximum average heat release rate is reduced under the condition of ensuring that the material has lower smoke density and toxicity, the fatigue resistance is greatly improved, and the comprehensive performance is better.
Various modifications may be made to the above without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is therefore intended to be limited not by the above description, but rather by the scope of the appended claims.