CN110903513A - Silicon dioxide core-shell antibacterial flame retardant and preparation method thereof - Google Patents
Silicon dioxide core-shell antibacterial flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the fields of environmental protection, fire protection and new materials, in particular to a silicon dioxide core-shell antibacterial flame retardant and a preparation method thereof. Uniformly mixing an inorganic flame retardant, an alkali solution and absolute ethyl alcohol, adding ethyl orthosilicate, dispersing a silicon dioxide flame retardant in an ethanol water solution, adding a silane coupling agent, and adding alkyl dimethyl tertiary amine to obtain the silicon dioxide core-shell antibacterial flame retardant. The silicon dioxide core-shell antibacterial flame retardant prepared by the invention has the advantages of controllable structure, high flame retardant efficiency, excellent smoke suppression effect, effective molten drop prevention, capability of improving inorganic particle dispersibility, antibacterial property, suitability for being used as efficient antibacterial flame retardants of polyester, polyvinyl chloride, polypropylene, polyethylene, epoxy resin and unsaturated resin, strong functionality, no toxicity, environmental protection and wide application prospect.
Description
Technical Field
The invention relates to the fields of environmental protection, fire protection and new materials, in particular to a silicon dioxide core-shell antibacterial flame retardant and a preparation method thereof.
Background
The inorganic flame retardant such as aluminum hydroxide, magnesium hydroxide, zinc stannate, zinc hydroxystannate and the like is a nontoxic inorganic flame retardant with good flame retardance and high efficiency for smoke suppression, and has very wide application and development prospects. But its application is limited due to its own structural disadvantages such as large specific surface area, phase separation from polymer molecules, etc. In recent years, with the gradual increase of the requirements of flame retardants, some new inorganic flame retardant varieties are successively introduced in foreign markets, and the flame retardant with the core-shell structure has potential application value as a novel flame retardant with a functional structure, and the research of the flame retardant with the core-shell structure is more and more focused by people. By preparing the flame retardant with the core-shell structure, functional composition between the shell material and the core material can be realized, the original properties of the core particles are kept, and meanwhile, the properties of the shell material can be introduced, so that further grafting and modification of the core particles are facilitated, the modification cost can be reduced, and a good synergistic effect can be obtained. The silicon flame retardant has the advantages of high flame retardant efficiency, low toxicity, anti-dripping, environmental friendliness and the like, and the inorganic silicon flame retardant can form SiO when the material is combusted2The covering has double functions of heat insulation and shielding, is a carbon-forming smoke suppressant, can endow a high polymer with excellent flame retardance and smoke suppression, and can improve the processing performance of the material and the mechanical property of the material.
Because simple composite flame retardants can not meet social requirements, multifunctional core-shell structure materials need to be developed, the development of the materials is advanced with the society, and the materials have important significance for further expanding the application field and filling and perfecting a novel antibacterial flame-retardant smoke suppressant system.
Disclosure of Invention
The purpose of the invention is as follows: in order to provide a silica core-shell antibacterial flame retardant with better effect and a preparation method thereof, the specific purpose is seen in a plurality of substantial technical effects of the specific implementation part.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a silicon dioxide core-shell antibacterial flame retardant is characterized by comprising the following steps:
firstly, uniformly mixing an inorganic flame retardant, an alkali solution and absolute ethyl alcohol, mechanically stirring for 10 min-10 h at room temperature, slowly adding tetraethoxysilane, reacting for 8-24 h at room temperature, centrifuging the mixed solution, pouring out clear liquid, adding absolute ethyl alcohol, performing ultrasonic dispersion, centrifuging again, washing and drying to obtain a silicon dioxide flame retardant; and finally, dispersing the silicon dioxide flame retardant into 60-95% ethanol water, after ultrasonic dispersion, slowly adding a silane coupling agent, reacting for 3-7 h at 70-90 ℃, filtering, washing, drying, dispersing into a solvent, adding alkyl dimethyl tertiary amine, reacting for 3-7 h at 70-90 ℃, filtering, washing, and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
The invention further adopts the technical scheme that the inorganic flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, zinc stannate and zinc hydroxystannate.
The further technical scheme of the invention is that the alkali solution is one or more of sodium hydroxide, potassium hydroxide and ammonia water; the concentration of the ethanol aqueous solution is 60 to 95 percent; the solvent is one or more of tetrahydrofuran, toluene, acetonitrile and acetone; the alkyl dimethyl tertiary amine is one or more of dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine and octadecyl dimethyl tertiary amine.
The silicon dioxide core-shell antibacterial flame retardant is characterized in that the nanometer core-shell particle structure is that a core material is an inorganic flame retardant, a shell material is silicon dioxide, and a grafting layer is alkyl dimethyl tertiary amine.
Use of an alkyldimethyl tertiary amine and/or silica in the preparation of a material which is synergistically flame retardant and which prevents afterburning.
Compared with the prior art, the invention adopting the technical scheme has the following beneficial effects:
① the nanometer nuclear shell antibacterial flame retardant has large selection space, meets the material use performance according to the functionality, and the nanometer surface grafting antibacterial agent can improve the even dispersibility of the nanometer particles in the matrix, also improves the antibacterial performance of the material, and resists precipitation, namely the permanent antibacterial agent.
② the nanometer nuclear shell antibacterial flame retardant has stable physical and chemical properties, is synergistic in flame retarding and smoke suppression, forms a compact carbon layer structure in the combustion process, avoids degradation of internal materials, greatly enhances the flame retarding performance, reduces the cost of the flame retardant, improves the water resistance of the flame retardant, and is easier to store.
③ the nanometer nuclear shell particle of the invention does not need to add catalyst and the like in the preparation, does not introduce impurity elements, reduces the complexity of production equipment, has wide application prospect and is suitable for industrialized production.
④ the nanometer nuclear shell antibacterial flame retardant of the invention uses a chemical method to coat inorganic particles (aluminum hydroxide, magnesium hydroxide, zinc stannate, zinc hydroxystannate) with silicon dioxide to prepare a nuclear shell structure, then a shell layer is chemically grafted with an antibacterial agent, and the antibacterial agent and the silicon dioxide are cooperated to prevent corrosion and pollution, and the nanometer nuclear shell antibacterial flame retardant is white inorganic powder, has good adaptability with pigment, wide application field and good application and development prospect.
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To further illustrate the present invention, further description is provided below with reference to the accompanying drawings:
FIG. 1 is Table 1; FIG. 2 is Table 2.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention. In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", "top", "bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, as they may be fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The patent provides a plurality of parallel schemes, and different expressions belong to an improved scheme based on a basic scheme or a parallel scheme. Each solution has its own unique features.
The invention aims to provide a preparation method of a silicon dioxide core-shell antibacterial flame retardant, which has the advantages of high flame retardant efficiency, excellent smoke suppression, good antibacterial property and dispersibility, improved mechanical property, no toxicity, environmental protection, easily obtained raw materials, easiness in industrial production and capability of solving the difficulties in the prior art.
Firstly, uniformly mixing an inorganic flame retardant, an alkali solution and absolute ethyl alcohol, mechanically stirring for 10 min-10 h at room temperature, then slowly adding tetraethoxysilane, reacting for 8 h-24 h at room temperature, centrifuging the mixed solution, pouring out clear liquid, adding absolute ethyl alcohol, ultrasonically dispersing, centrifuging again, washing and drying. And finally, dispersing the silicon dioxide flame retardant in an ethanol water solution, performing ultrasonic dispersion, slowly adding a silane coupling agent, reacting for 3-7 h at 70-90 ℃, filtering, washing, drying, dispersing in a solvent, adding alkyl dimethyl tertiary amine, reacting for 3-7 h at 70-90 ℃, filtering, washing, and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Inorganic flame retardants as described above are commercially available, inorganic flame retardants (e.g., aluminum hydroxide, magnesium hydroxide, zinc stannate, zinc hydroxystannate).
The silane coupling agents as described above, such as gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-chloropropyltriethoxysilane, gamma-chloropropyltrimethoxysilane, are commercially available.
The alkali solution, sodium hydroxide, potassium hydroxide, and aqueous ammonia as described above can be commercially available.
The ethanol aqueous solution has a concentration of 60% to 95%, and is commercially available.
The solvents mentioned above, tetrahydrofuran, toluene, acetonitrile, acetone, are commercially available.
The above-mentioned alkyldimethyl tertiary amine, dodecyldimethyl tertiary amine, tetradecyldimethyl tertiary amine, hexadecyldimethyl tertiary amine, and octadecyldimethyl tertiary amine are commercially available.
The nano core-shell particles have excellent flame retardance, smoke suppression, antibacterial property and dispersibility. It is suitable for being used as efficient antibacterial flame retardant for polyester, polyvinyl chloride, polypropylene, polyethylene, epoxy resin, unsaturated resin and the like.
The nanometer nuclear shell particle structure of the invention is that the core material is inorganic fire retardant, the shell material is silicon dioxide, and the grafting layer is alkyl dimethyl tertiary amine.
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 7.5kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 8.2kg of ethyl orthosilicate is slowly added, after reaction for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 7.5kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; and finally, dispersing the silicon dioxide flame retardant into 8.0kg of 95% ethanol water solution, performing ultrasonic dispersion, slowly adding 6.5kg of gamma-chloropropyltrimethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 24.5kg of dodecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Example 2 firstly, 50kg of zinc hydroxystannate, 6.6kg of ammonia water and 7.5kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 21.4kg of tetraethoxysilane is slowly added, after reaction for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 7.5kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; and finally, dispersing the silicon dioxide flame retardant into 8.0kg of 95% ethanol water solution, performing ultrasonic dispersion, slowly adding 6.5kg of gamma-chloropropyltrimethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 24.5kg of dodecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Example 3 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 10kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 49.2kg of tetraethoxysilane is slowly added, after reaction for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 10kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; and finally, dispersing the silicon dioxide flame retardant into 20.0kg of 95% ethanol water solution, performing ultrasonic dispersion, slowly adding 6.5kg of gamma-chloropropyltrimethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 24.5kg of dodecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Example 4, 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 10kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 49.2kg of tetraethoxysilane is slowly added, after the reaction is carried out for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 10kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; and finally, dispersing the silicon dioxide flame retardant into 20.0kg of 95% ethanol water solution, performing ultrasonic dispersion, slowly adding 8.5kg of gamma-methacryloxypropyltrimethoxysilane, reacting for 6 hours at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 40.5kg of dodecyl dimethyl tertiary amine, reacting for 4 hours at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Example 5 50kg of zinc hydroxystannate, 6.6kg of ammonia water and 15kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 27.4kg of tetraethoxysilane is slowly added, after reaction for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 15kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; and finally, dispersing the silicon dioxide flame retardant into 20kg of 95% ethanol water solution, performing ultrasonic dispersion, slowly adding 6.5kg of gamma-aminopropyltriethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 22.3kg of hexadecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Example 6 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 25kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 35.1kg of tetraethoxysilane is slowly added, after reaction for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 25kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; and finally, dispersing the silicon dioxide flame retardant into 8.0kg of 95% ethanol water solution, performing ultrasonic dispersion, slowly adding 7.2kg of 3-chloropropyltriethoxysilane, reacting for 6 hours at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 25.5kg of tetradecyl dimethyl tertiary amine, reacting for 4 hours at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Example 7 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 7.5kg of absolute ethanol are mixed uniformly, mechanically stirred for 10min at room temperature, then 7.2kg of tetraethoxysilane is slowly added, after reaction for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 7.5kg of absolute ethanol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; and finally, dispersing the silicon dioxide flame retardant into 8.0kg of 95% ethanol water solution, performing ultrasonic dispersion, slowly adding 6.5kg of 3-chloropropyltriethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 19.1kg of octadecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Comparative example 1 Ammonia water and absolute ethyl alcohol are mixed evenly, mechanical stirring is carried out for 10min at room temperature, then 43.3kg of ethyl orthosilicate is slowly added, after reaction is carried out for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, the absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out. And finally, dispersing the silicon dioxide flame retardant in a 95% ethanol water solution, performing ultrasonic dispersion, adding gamma-chloropropyltrimethoxysilane, reacting for 6 hours at 80 ℃, filtering, washing, drying, dispersing in an acetonitrile solvent, adding 13.9kg of dodecyl dimethyl tertiary amine, reacting for 4 hours at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Comparative example 2 ammonia water and absolute ethyl alcohol were mixed uniformly, mechanically stirred for 10min at room temperature, then 43.3kg of ethyl orthosilicate was slowly added, after reaction for 10h at room temperature, the mixture was centrifuged, the clear solution was poured out and absolute ethyl alcohol was added, ultrasonically dispersed, centrifuged again, washed and dried. And finally, dispersing the silicon dioxide flame retardant in a 95% ethanol water solution, performing ultrasonic dispersion, adding gamma-chloropropyltrimethoxysilane, reacting for 6 hours at 80 ℃, filtering, washing, drying, dispersing in an acetonitrile solvent, adding 53.6kg of dodecyl dimethyl tertiary amine, reacting for 4 hours at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
Comparative example 3 Ammonia water and absolute ethyl alcohol are mixed evenly, mechanical stirring is carried out for 10min at room temperature, then 43.3kg of ethyl orthosilicate is slowly added, after reaction is carried out for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, the absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out. And finally, dispersing the silicon dioxide flame retardant in a 95% ethanol water solution, performing ultrasonic dispersion, adding gamma-chloropropyltrimethoxysilane, reacting for 6 hours at 80 ℃, filtering, washing, drying, dispersing in an acetonitrile solvent, adding 125kg of dodecyl dimethyl tertiary amine, reacting for 4 hours at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
The core-shell proportions of the silicon dioxide core-shell antibacterial flame retardant are different, and the flame retardant, smoke suppression and antibacterial performances of the silicon dioxide core-shell antibacterial flame retardant are different in degree. Therefore, the inventor of the scheme adopts the prepared silicon dioxide core-shell antibacterial flame retardant (examples 1-7) and the silicon dioxide core-shell antibacterial flame retardant (comparative examples 1-3) to apply the silicon dioxide core-shell antibacterial flame retardant to a polyvinyl chloride (PVC) film material. Reference is made to: the combustion behavior of the plastic GB/T2406.2-2009 measured by the oxygen index method is part 2: the greenhouse test is carried out by a method provided by a non-support material (film) in the greenhouse; the smoke density test method for combustion or decomposition of the building material is more than or equal to that provided by GB/T8627-2007; flame retardant material rating test method provided in American Standard ANSI/UL 94-1985; evaluation part 3 of antibacterial performance of textile with GB/T20944.3-2008 being not more than or equal to: the oscillation method is not less than the provided method for carrying out the antibacterial performance test. The flame retardant, 50g of diisononyl phthalate (DINP) as a plasticizer, 2.5g of barium-zinc stabilizer and 100g of polyvinyl chloride resin were mixed uniformly according to the formulation, and then the mixture was calendered by a flat vulcanizer to prepare a sample having a thickness of 0.5mm, and part of the test results are shown in tables 1 and 2:
table 1 shows the flame retardant property, smoke suppression property and antibacterial property data of comparative examples 1-3 of the silicon dioxide core-shell antibacterial flame retardant on PVC (polyvinyl chloride) film material
Table 2 shows the flame retardant property, smoke suppression property and antibacterial property data of the silicon dioxide core-shell antibacterial flame retardant of examples 1 to 7 on PVC film material
As can be seen from tables 1 and 2, the silica core-shell antibacterial flame retardant disclosed by the invention has improved smoke suppression and flame retardant properties and better uniform dispersion performance on polyvinyl chloride film materials. And the silica particles and the silica core-shell particles have excellent antibacterial performance after being grafted with the antibacterial agent. Meanwhile, the mechanical property damage of the flame retardant to the polyvinyl chloride film material is found to be smaller than that of inorganic compound filling in the experiment, the polyvinyl chloride film material can be used as an environment-friendly flame retardant and an antibacterial agent, namely can be used as a permanent antibacterial flame retardant, and the application field is wide.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to illustrate the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and the invention is to be limited to the embodiments described above.
Claims (10)
1. The preparation method of the silicon dioxide core-shell antibacterial flame retardant is characterized by comprising the following steps:
firstly, uniformly mixing an inorganic flame retardant, an alkali solution and absolute ethyl alcohol, mechanically stirring for 10 min-10 h at room temperature, then adding tetraethoxysilane, reacting for 8 h-24 h at room temperature, centrifuging the mixed solution, pouring out clear liquid, adding absolute ethyl alcohol, ultrasonically dispersing, centrifuging again, washing and drying to obtain a silicon dioxide flame retardant; finally, dispersing the silicon dioxide flame retardant into 60-95% ethanol water, adding a silane coupling agent after ultrasonic dispersion, reacting for 3-7 h at 70-90 ℃, filtering, washing, drying, and dispersing in a solvent; and adding alkyl dimethyl tertiary amine, reacting for 3-7 h at 70-90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
2. The method for preparing silica core-shell antibacterial flame retardant according to claim 1, wherein the inorganic flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, zinc stannate and zinc hydroxystannate.
3. The method for preparing the silica core-shell antibacterial flame retardant according to claim 1, wherein the alkali solution is one or more of sodium hydroxide, potassium hydroxide and ammonia water; the mass ratio of the alkali solution to the inorganic flame retardant is 1: 1-1: 9; the mass ratio of the ethyl orthosilicate to the inorganic flame retardant is 1: 1-1: 9.
4. the preparation method of the silica core-shell antibacterial flame retardant according to claim 1, wherein the mass ratio of the absolute ethyl alcohol to the inorganic flame retardant is 1: 1-1: 9; the ethanol water solution accounts for 10-50% of the inorganic flame retardant by mass.
5. The method for preparing the silica core-shell antibacterial flame retardant according to claim 1, wherein the silane coupling agent is one or more of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-chloropropyltriethoxysilane and gamma-chloropropyltrimethoxysilane, and the mass ratio of the silane coupling agent to the inorganic flame retardant is 1: 5-1: 9.
6. the preparation method of the silica core-shell antibacterial flame retardant according to claim 1, wherein the solvent is one or more of tetrahydrofuran, toluene, acetonitrile and acetone; the mass ratio of the solvent to the inorganic flame retardant is 1: 1-1: 9.
7. the method for preparing silica core-shell antibacterial flame retardant according to claim 1, wherein the alkyl dimethyl tertiary amine is one or more of dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine and octadecyl dimethyl tertiary amine; the mass ratio of the alkyl dimethyl tertiary amine to the silane coupling agent is 3: 1-9: 1.
8. the silicon dioxide core-shell antibacterial flame retardant is characterized in that the nanometer core-shell particle structure is that a core material is an inorganic flame retardant, a shell material is silicon dioxide, and a grafting layer is alkyl dimethyl tertiary amine.
9. Use of an alkyldimethyl tertiary amine and silica in the preparation of a material which is synergistically flame retardant and which prevents afterburning.
10. The preparation method of the silicon dioxide core-shell antibacterial flame retardant is characterized by comprising any one of the following schemes:
the method comprises the following steps of 1, uniformly mixing 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 7.5kg of absolute ethyl alcohol, mechanically stirring for 10min at room temperature, slowly adding 8.2kg of ethyl orthosilicate, reacting for 10h at room temperature, centrifuging a mixed solution, pouring out a clear solution, adding 7.5kg of absolute ethyl alcohol, ultrasonically dispersing, centrifuging again, washing, and drying to obtain a silicon dioxide flame retardant; finally, dispersing the silicon dioxide flame retardant in 8.0kg of 95% ethanol water solution, after ultrasonic dispersion, slowly adding 6.5kg of gamma-chloropropyltrimethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing in 10.0kg of acetonitrile solvent, adding 24.5kg of dodecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant;
the technical scheme 2 is that 50kg of zinc hydroxystannate, 6.6kg of ammonia water and 7.5kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 21.4kg of tetraethoxysilane is slowly added, after reaction for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 7.5kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; finally, dispersing the silicon dioxide flame retardant in 8.0kg of 95% ethanol water solution, after ultrasonic dispersion, slowly adding 6.5kg of gamma-chloropropyltrimethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing in 10.0kg of acetonitrile solvent, adding 24.5kg of dodecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant;
the technical scheme 3 is that 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 10kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 49.2kg of tetraethoxysilane is slowly added, after the reaction is carried out for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 10kg of absolute ethyl alcohol is added, the ultrasonic dispersion is carried out, the centrifugation is carried out again, the washing and the drying are carried out, and the silicon dioxide flame retardant is obtained; finally, dispersing the silicon dioxide flame retardant in 20.0kg of 95% ethanol water solution, after ultrasonic dispersion, slowly adding 6.5kg of gamma-chloropropyltrimethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing in 10.0kg of acetonitrile solvent, adding 24.5kg of dodecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant;
according to the technical scheme 4, 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 10kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 49.2kg of tetraethoxysilane is slowly added, after the reaction is carried out for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 10kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; finally, dispersing the silicon dioxide flame retardant into 20.0kg of 95% ethanol water solution, after ultrasonic dispersion, slowly adding 8.5kg of gamma-methacryloxypropyltrimethoxysilane, reacting for 6 hours at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 40.5kg of dodecyl dimethyl tertiary amine, reacting for 4 hours at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant;
the technical scheme 5 is that 50kg of zinc hydroxystannate, 6.6kg of ammonia water and 15kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, 27.4kg of tetraethoxysilane is slowly added, after the reaction is carried out for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 15kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; finally, dispersing the silicon dioxide flame retardant in 20kg of 95% ethanol water solution, after ultrasonic dispersion, slowly adding 6.5kg of gamma-aminopropyltriethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing in 10.0kg of acetonitrile solvent, adding 22.3kg of hexadecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant;
the technical scheme 6 is that 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 25kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 35.1kg of tetraethoxysilane is slowly added, after the reaction is carried out for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 25kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; finally, dispersing the silicon dioxide flame retardant in 8.0kg of 95% ethanol water solution, after ultrasonic dispersion, slowly adding 7.2kg of 3-chloropropyltriethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing in 10.0kg of acetonitrile solvent, adding 25.5kg of tetradecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant;
according to the technical scheme 7, 50kg of zinc hydroxystannate, 5.6kg of ammonia water and 7.5kg of absolute ethyl alcohol are uniformly mixed, mechanically stirred for 10min at room temperature, then 7.2kg of ethyl orthosilicate is slowly added, after reaction is carried out for 10h at room temperature, the mixed solution is centrifuged, the clear solution is poured out, 7.5kg of absolute ethyl alcohol is added, ultrasonic dispersion is carried out, centrifugation is carried out again, washing and drying are carried out, and the silicon dioxide flame retardant is obtained; and finally, dispersing the silicon dioxide flame retardant into 8.0kg of 95% ethanol water solution, performing ultrasonic dispersion, slowly adding 6.5kg of 3-chloropropyltriethoxysilane, reacting for 6h at 80 ℃, filtering, washing, drying, dispersing into 10.0kg of acetonitrile solvent, adding 19.1kg of octadecyl dimethyl tertiary amine, reacting for 4h at 90 ℃, filtering, washing and drying to obtain the silicon dioxide core-shell antibacterial flame retardant.
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