CN114702769B - Reinforced flame-retardant microcapsule composite material and preparation method thereof - Google Patents
Reinforced flame-retardant microcapsule composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an enhanced flame-retardant microcapsule composite material and a preparation method thereof, wherein the composite material takes a modified thermoplastic polymer as a core, a synergistic flame retardant layer is coated on the outer side surface of the modified thermoplastic polymer, and finally a modified filling flame retardant layer is coated on the outer side of a graphene layer to form a compact three-layer core-shell structure; the modified thermoplastic polymer is modified thermoplastic resin, the modified filling flame retardant is modified zinc stannate, the synergistic flame retardant layer is graphene, and the mass percentages of the modified thermoplastic resin, the modified filling flame retardant and the graphene are as follows: 80% of modified thermoplastic resin, 10-19% of modified filling flame retardant and 1-10% of synergistic flame retardant graphene. The three layers of compact core-shell structures formed by the three components and the synergistic effect of the three layers of compact core-shell structures enable the mechanical properties of the modified thermoplastic polymer to be improved, and the smoke suppression performance and the flame retardant performance of the composite material to be simultaneously improved.
Description
Technical Field
The invention relates to the technical field of new flame-retardant materials, in particular to an enhanced flame-retardant microcapsule composite material prepared from modified zinc stannate/graphene/thermoplastic resin and a preparation method thereof.
Background
Polyvinyl chloride (PVC) has been attracting attention due to its good flexibility, processability, and mechanical properties, and is often used in flexible pipes, conveyor belts, packaging materials, and other common applications. The chlorine content of the general PVC is higher, the mass fraction reaches 58.7%, and the PVC is more fireproof than most organic polymers. However, the conventional plasticizers used to make flexible PVC greatly reduce their excellent fire resistance, which results in a large amount of dense black smoke after combustion. Therefore, the flame retardant performance and smoke suppression performance of flexible polyvinyl chloride need to be improved.
The Chinese patent application No. CN201711372128.0 discloses a high-flame-retardant soft PVC coated polyester filament polymer composite sunshade material, which obviously improves the flame retardance of the soft PVC coated polyester filament polymer composite sunshade material by the combined action of gas phase and solid phase, so that the limiting oxygen index of the soft PVC coated polyester filament polymer composite sunshade material reaches 32.4%, solves the problem of low limiting oxygen index of the soft PVC coated polyester filament polymer composite sunshade material, obviously improves the flame retardant efficiency of the product, and reduces the fire hazard of the product. However, the high-flame-retardant soft PVC coated polyester yarn polymer composite sun-shading material disclosed by the invention has excellent flame retardant property, but has larger limitation on mechanical property, and meanwhile, has poor smoke suppression effect, so that the high-flame-retardant soft PVC coated polyester yarn polymer composite sun-shading material still has challenges in industrial popularization.
"flame retardant capsule" materials have been developed for several years, i.e., the flame retardant material is encapsulated within a capsule by a capsule shell to improve the physical stability of the flame retardant upon storage. However, a major problem with such flame retardant materials is that although they increase the flame retardancy of the material, they severely affect the mechanical properties of the material. Meanwhile, in the prior art, the flame retardant is usually compounded by adopting a mode of melt blending with a thermoplastic polymer, and the compounding method is not friendly to the mechanical property of the composite material, cannot form a specific microstructure, and is not beneficial to the improvement of the performances such as smoke suppression and the like of the composite material; when the polymer in the material is degraded, the escape of combustible gas cannot be prevented, and heat and mass transfer cannot be hindered.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the reinforced flame-retardant microcapsule composite material, which is provided with a unique three-dimensional microstructure by synchronously improving components, proportions and preparation processes, and particularly by coating graphene on the surface of a modified thermoplastic polymer and then coating a layer of modified zinc stannate to form a compact three-layer core-shell structure, and the addition of the flame retardant improves the physical properties of the polymer and simultaneously improves the smoke suppression performance and the flame retardant performance.
The invention also aims to provide a preparation method of the reinforced flame-retardant microcapsule composite material, which enables the composite material to construct a unique three-dimensional microstructure through synchronous improvement of components, proportions and preparation processes, simplifies the preparation process, and improves the mutual compatibility, bonding strength and comprehensive performance of the materials.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the reinforced flame-retardant microcapsule composite material is characterized in that a modified thermoplastic polymer is taken as a core, a synergistic flame retardant layer is coated on the outer side surface of the modified thermoplastic polymer, and finally a modified filling flame retardant layer is coated on the outer side of a graphene layer to form a compact three-layer core-shell structure; the modified thermoplastic polymer is modified thermoplastic resin, the modified filling flame retardant is modified zinc stannate, the synergistic flame retardant layer is graphene, and the mass percentages of the modified thermoplastic resin, the modified filling flame retardant and the graphene are as follows: 80% of modified thermoplastic resin, 10-19% of modified filling flame retardant and 1-10% of synergistic flame retardant graphene;
the three layers of compact core-shell structures formed by the three components and the synergistic effect of the three layers of compact core-shell structures enable the mechanical properties of the modified thermoplastic polymer to be improved, and the smoke suppression performance and the flame retardant performance of the composite material to be simultaneously improved.
The modified thermoplastic resin is one of PDA modified polyvinyl chloride (PVC) and Polystyrene (PS), or functional PVC/PS particles formed by modifying and modifying the composition of the modified thermoplastic resin with PDA.
The modified zinc stannate may be zinc hydroxystannate.
The preparation method of the reinforced flame-retardant microcapsule composite material is characterized by comprising the following steps:
s1: dispersing a set amount of water-soluble graphene into deionized water, and performing ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
s2: preparing and weighing modified thermoplastic resin particles with required mass according to a proportion, immersing the modified thermoplastic resin particles into the graphene slurry in the step S1, standing for 5 hours, coating a synergistic flame retardant layer on the outer side surface of the modified thermoplastic resin particles, and taking out and drying the modified thermoplastic resin particles to obtain graphene/modified thermoplastic resin particles with a single-layer core-shell structure;
s3: preparing and weighing modified zinc stannate with required mass according to a proportion, and dispersing the modified zinc stannate into deionized water to obtain zinc hydroxystannate slurry;
s4: immersing the graphene/modified thermoplastic resin particles obtained in the step S2 into the zinc hydroxystannate slurry obtained in the step S3, and coating a layer of zinc hydroxystannate on the outer side of a graphene layer of the graphene/modified thermoplastic resin particles to obtain a modified zinc stannate/graphene/thermoplastic resin mixture with a three-layer core-shell structure;
s5: and drying and banburying the modified zinc stannate/graphene/modified thermoplastic resin mixture to obtain the modified zinc stannate/graphene/thermoplastic resin reinforced flame-retardant microcapsule composite material with the three-layer compact core-shell structure.
The PDA modified thermoplastic resin particles are prepared in the step S2, and specifically comprise the following steps:
s21: dissolving a proper amount of Tris powder into deionized water to obtain a 5mmol/L buffer solution, and dropwise adding hydrochloric acid to adjust the pH to 8.5 to obtain a Tris-HCl buffer solution;
s22: weighing a proper amount of dopamine, dissolving in the Tris-HCl buffer solution, and obtaining a PDA-Tris-HCl solution, wherein the concentration of the dopamine is 2.5 mg/ml;
s23: weighing a proper amount of thermoplastic resin powder, adding the PDA-Tris-HCl solution, stirring for 24 hours at the temperature of 70 ℃, and drying for 3 hours to obtain the PDA modified thermoplastic resin particles.
In the step S2, PDA modified thermoplastic resin particles are prepared, wherein the thermoplastic resin powder in the step S23 is PVC/PS mixed powder, and the mass ratio of the PVC to the thermoplastic resin powder is PVC: PS particles = 1: and 1, finally obtaining the PDA modified PVC/PS particles.
The modified zinc stannate with the required mass is prepared in the step S3 and weighed according to the proportion, and specifically comprises the following steps:
s31: weighing proper amount of ZnCl 2 The powder is put into deionized water to prepare ZnCl with the concentration of 2mol/L 2 An aqueous solution;
s32: weighing a proper amount of Na 2 SnO 3 ·3H 2 O is dissolved in deionized water, and the concentration of Na is worth 2mol/L 2 SnO 3 ·3H 2 An aqueous O solution;
s33: weighing a proper amount of ZnCl in the step S31 2 The aqueous solution is directed to Na in step S32 2 SnO 3 ·3H 2 Dropwise adding the O aqueous solution until white precipitation appears in the mixed solution, and reacting for 1h at 60 ℃ to obtain a wet filter cake;
s34: and (3) transferring the wet filter cake in the step (S33) into n-butanol, fully mixing, adopting normal pressure azeotropic distillation, and drying the obtained powder in a 125 ℃ oven to obtain zinc hydroxystannate, namely the modified zinc stannate.
Compared with the prior art, the invention has the advantages that:
1. according to the reinforced flame-retardant microcapsule composite material and the preparation method, the components, the proportion and the preparation process are synchronously improved, so that the composite material is constructed into a unique three-dimensional microstructure, and particularly, the surface of the modified thermoplastic polymer is coated with graphene and then is coated with a layer of modified zinc stannate, so that a compact three-layer core-shell structure is formed, and the mechanical property of the polymer is improved, and the smoke suppression property and the flame retardant property are simultaneously improved by adding the flame retardant. The material has excellent water resistance and weather resistance, is environment-friendly, has simple preparation steps, and is suitable for popularization and application.
2. According to the reinforced flame-retardant microcapsule composite material and the preparation method, a PVC/PS matrix is modified by using PDA, functionalized PVC/PS is blended with graphene dispersion liquid, a solvent is evaporated to coat graphene on the surface of functionalized PVC/PS particles, then modified zinc stannate is coated on the surface, and finally, the reinforced flame-retardant microcapsule composite material with a three-layer core-shell structure is obtained by directly tabletting. The material has a unique core-shell structure, so that the addition of the flame retardant does not influence the mechanical properties of the polymer.
3. According to the flame-retardant microcapsule prepared by the invention, graphene is introduced, so that the composite material is provided with a compact protective carbon layer, and when the polymer nanocomposite is degraded, the escape of combustible gas can be prevented, and heat and mass transfer are hindered.
4. According to the preparation method of the reinforced flame-retardant microcapsule composite material, through synchronous improvement of components, proportions and preparation processes, the composite material is made into a unique three-dimensional microstructure, the preparation process is simplified, and the compatibility, the bonding strength and the comprehensive performance of the materials are improved; the mechanical ball milling modification method is adopted to modify the three materials two by two, so that the preparation process is simplified, and the density and the bonding performance of the materials are improved.
5. According to the invention, the graphene is introduced again to form the flame retardant with a unique microstructure on the basis of the core-shell structure, so that the flame retardant performance of the composite material is improved, and the mechanical performance is not affected. The zinc stannate adopted by the invention is taken as a common inorganic tin flame retardant, has nontoxic and excellent flame retardant performance, is considered as one of high-efficiency green flame retardants, but the single inorganic flame retardant limits the exertion of the flame retardant performance, and the composite material is enabled to obtain a compact protective carbon layer along with the introduction of a core-shell structure and graphene, so that the escape of combustible gas can be prevented and the heat and mass transfer can be hindered when the polymer nanocomposite is degraded.
Drawings
FIG. 1 is a scanning electron microscope image of the reinforced flame retardant microcapsule prepared in this example;
FIG. 2 is a scanning electron microscope image of the reinforced flame retardant microcapsule composite material prepared in the embodiment of the invention.
The present invention will be described in detail with reference to the accompanying drawings and examples.
The specific embodiment is as follows:
examples:
the reinforced flame-retardant microcapsule composite material provided by the embodiment takes a modified thermoplastic polymer as a core, a synergistic flame retardant layer is coated on the outer side surface of the modified thermoplastic polymer, and finally a modified filling flame retardant layer is coated on the outer side of the graphene layer, so that a compact three-layer core-shell structure is formed; the modified thermoplastic polymer is modified thermoplastic resin, the modified filling flame retardant is modified zinc stannate, the synergistic flame retardant layer is graphene, and the mass percentages of the modified thermoplastic resin, the modified filling flame retardant and the graphene are as follows: 80% of modified thermoplastic resin, 10-19% of modified filling flame retardant and 1-10% of synergistic flame retardant graphene; the three layers of compact core-shell structures formed by the three components and the synergistic effect of the three layers of compact core-shell structures enable the mechanical properties of the modified thermoplastic polymer to be improved, and the smoke suppression performance and the flame retardant performance of the composite material to be simultaneously improved.
The modified thermoplastic resin is one of PDA modified polyvinyl chloride (PVC) and Polystyrene (PS), or functional PVC/PS particles formed by modifying and modifying the composition of the modified thermoplastic resin with PDA.
The modified zinc stannate can also be zinc hydroxystannate.
The preparation method of the reinforced flame-retardant microcapsule composite material comprises the following steps:
s1: dispersing a set amount of water-soluble graphene into deionized water, and performing ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
s2: preparing and weighing modified thermoplastic resin particles with required mass according to a proportion, immersing the modified thermoplastic resin particles into the graphene slurry in the step S1, standing for 5 hours, coating a synergistic flame retardant layer on the outer side surface of the modified thermoplastic resin particles, and taking out and drying the modified thermoplastic resin particles to obtain graphene/modified thermoplastic resin particles with a single-layer core-shell structure;
wherein the preparation of PDA modified thermoplastic resin particles specifically comprises the following steps:
s21: dissolving a proper amount of Tris powder into deionized water to obtain a 5mmol/L buffer solution, and dropwise adding hydrochloric acid to adjust the pH to 8.5 to obtain a Tris-HCl buffer solution;
s22: weighing a proper amount of dopamine, dissolving in the Tris-HCl buffer solution, and obtaining a PDA-Tris-HCl solution, wherein the concentration of the dopamine is 2.5 mg/ml;
s23: weighing a proper amount of thermoplastic resin powder, adding the PDA-Tris-HCl solution, stirring for 24 hours at the temperature of 70 ℃, and drying for 3 hours to obtain modified thermoplastic resin particles modified by the PDA;
when the thermoplastic resin powder is PVC/PS mixed powder, the mass ratio of the thermoplastic resin powder to the PVC: PS particles = 1: and 1, finally obtaining the PDA modified PVC/PS particles. In other embodiments, other values may be selected for the mass ratio of the two.
S3: preparing and weighing modified zinc stannate with required mass according to a proportion, and dispersing the modified zinc stannate into deionized water to obtain zinc hydroxystannate slurry;
wherein the preparation and the weighing of the modified zinc stannate with the required mass according to the proportion concretely comprise the following steps:
s31: weighing proper amount of ZnCl 2 The powder is put into deionized water to prepare ZnCl with the concentration of 2mol/L 2 An aqueous solution;
s32: weighing a proper amount of Na 2 SnO 3 ·3H 2 O is dissolved in deionized water, and the concentration of Na is worth 2mol/L 2 SnO 3 ·3H 2 An aqueous O solution;
s33: weighing a proper amount of ZnCl in the step S31 2 The aqueous solution is directed to Na in step S32 2 SnO 3 ·3H 2 Dropwise adding the O aqueous solution until white precipitation appears in the mixed solution, and reacting for 1h at 60 ℃ to obtain a wet filter cake;
s34: and (3) transferring the wet filter cake in the step (S33) into n-butanol, fully mixing, adopting normal pressure azeotropic distillation, and drying the obtained powder in a 125 ℃ oven to obtain zinc hydroxystannate, namely the modified zinc stannate.
S4: immersing the graphene/modified thermoplastic resin particles obtained in the step S2 into the zinc hydroxystannate slurry obtained in the step S3, and coating a layer of zinc hydroxystannate on the outer side of a graphene layer of the graphene/modified thermoplastic resin particles to obtain a modified zinc stannate/graphene/thermoplastic resin mixture with a three-layer core-shell structure;
s5: and drying and banburying the modified zinc stannate/graphene/modified thermoplastic resin mixture to obtain the modified zinc stannate/graphene/thermoplastic resin reinforced flame-retardant microcapsule composite material with the three-layer compact core-shell structure.
Example 1
The embodiment of the invention provides an enhanced flame-retardant microcapsule composite material and a preparation method thereof, which are specific applications of the previous embodiment, in particular to a preparation method of a modified zinc stannate/graphene/PVC enhanced flame-retardant microcapsule composite material, comprising the following steps:
(1) Dispersing 4g of water-soluble graphene into deionized water, and performing ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
(2) Weighing 80g of modified PVC resin, immersing in graphene slurry, standing for 5 hours, taking out and drying to obtain graphene/modified PVC resin;
(3) Weighing 16g of zinc hydroxystannate, and dispersing the zinc hydroxystannate into deionized water to obtain zinc hydroxystannate slurry;
(4) Immersing the obtained graphene/modified PVC resin into zinc hydroxystannate slurry to obtain a modified zinc stannate/graphene/modified PVC resin mixture;
(5) And (3) drying and banburying the obtained modified zinc stannate/graphene/modified PVC resin mixture, and controlling the temperature to be 170-180 ℃ to obtain the modified zinc stannate/graphene/PVC resin reinforced flame-retardant microcapsule composite material.
The standard sample bars were subjected to limiting oxygen index test, flame smoke density test and mechanical property test, and the results are shown in Table 1.
Example 2
The embodiment of the invention provides an enhanced flame-retardant microcapsule composite material and a preparation method thereof, which are specific applications of the previous embodiment, in particular to a preparation method of a modified zinc stannate/graphene/PS enhanced flame-retardant microcapsule composite material, and specifically comprise the following steps:
(1) Dispersing 4g of water-soluble graphene into deionized water, and performing ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
(2) Weighing 80g of modified PS resin, immersing in graphene slurry, standing for 5 hours, taking out and drying to obtain graphene/modified PVC resin;
(3) Weighing 16g of zinc hydroxystannate, and dispersing the zinc hydroxystannate into deionized water to obtain zinc hydroxystannate slurry;
(4) Immersing the obtained graphene/modified PS resin into zinc hydroxystannate slurry to obtain a modified zinc stannate/graphene/modified PS resin mixture;
(5) And (3) drying and banburying the obtained modified zinc stannate/graphene/modified PS resin mixture, and controlling the temperature to be 170-180 ℃ to obtain the modified zinc stannate/graphene/PS resin reinforced flame-retardant microcapsule composite material.
The standard sample bars were subjected to limiting oxygen index test, flame smoke density test and mechanical property test, and the results are shown in Table 1.
Example 3
The embodiment of the invention provides a preparation method of a modified zinc stannate/graphene/PVC reinforced flame-retardant microcapsule composite material, which specifically comprises the following steps:
(1) And dispersing 6g of water-soluble graphene into deionized water, and performing ultrasonic treatment for 5 hours to obtain uniform graphene slurry.
(2) 80g of modified PVC resin is weighed, immersed in graphene slurry, and after standing for 5 hours, taken out and dried to obtain graphene/modified PVC resin.
(3) 14g of zinc hydroxystannate was weighed and dispersed in deionized water to obtain zinc hydroxystannate slurry.
(4) And immersing the obtained graphene/modified PVC resin into zinc hydroxystannate slurry to obtain a modified zinc stannate/graphene/modified PVC resin mixture.
(5) And drying and banburying the obtained modified zinc stannate/graphene/modified PVC resin mixture to obtain the modified zinc stannate/graphene/PVC resin reinforced flame-retardant microcapsule composite material. The temperature is controlled to be 170 ℃ to 180 DEG C
The standard sample bars were subjected to limiting oxygen index test, flame smoke density test and mechanical property test, and the results are shown in Table 1.
Example 4
The embodiment of the invention provides a preparation method of a modified zinc stannate/graphene/PVC/PS reinforced flame-retardant microcapsule composite material, which specifically comprises the following steps: PVC/PS
(1) Dispersing 6g of water-soluble graphene into deionized water, and performing ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
(2) Weighing 40g of modified PVC and PS resin respectively, immersing the modified PVC and PS resin into graphene slurry, standing for 5 hours, taking out and drying to obtain graphene/modified PVC/PS resin;
(3) 14g of zinc hydroxystannate is weighed and dispersed into deionized water to obtain zinc hydroxystannate slurry;
(4) Immersing the obtained graphene/modified PVC/PS resin into zinc hydroxystannate slurry to obtain a modified zinc stannate/graphene/modified PVC/PS resin mixture;
(5) And (3) drying and banburying the obtained modified zinc stannate/graphene/modified PS resin mixture, and controlling the temperature to be 170-180 ℃ to obtain the modified zinc stannate/graphene/PVC/PS resin reinforced flame-retardant microcapsule composite material.
The standard sample bars were subjected to limiting oxygen index test, flame smoke density test and mechanical property test, and the results are shown in Table 1.
Referring to fig. 1, an electron microscope image of the reinforced flame-retardant microcapsule prepared in examples 1-4 clearly shows that the three components are coated and cooperated to form a microscopic three-layer compact core-shell structure, specifically, a modified thermoplastic polymer surface is coated with graphene and then coated with a layer of modified zinc stannate to form a compact three-layer core-shell structure, three layers of materials are coated to form multi-layer blades in a three-dimensional space, a large number of gaps are formed between the blades, the specific surface area is increased, and the addition of the flame-retardant microcapsule improves the polymer mechanical property of the finally prepared composite material, and simultaneously improves the smoke suppression property and the flame retardance.
The reinforced flame-retardant microcapsule composite materials prepared in the examples 1-4 are respectively prepared into standard sample bars, the microstructure of the standard sample bars is shown in the figure 2, and the reinforced flame-retardant microcapsule composite materials have compact and uniform structure and good mechanical properties; the standard bars were subjected to limiting oxygen index test, flame smoke density test and mechanical property test, and the test results are shown in table 1.
As can be seen from Table 1, the core-shell flame retardant composite material with the modified thermoplastic polymer resin surface coated with graphene and zinc stannate according to the embodiments of the invention can obviously improve the flame retardant property and mechanical property of the thermoplastic polymer resin, and when the addition amount of the graphene is 6%, the flame retardant property is optimal, and meanwhile, the mechanical property is optimal, so that both the flame retardant property and the mechanical property are combined.
TABLE 1
Note that: oxygen index test standard: GB/T5454-1997; flame smoke density test standard: astm e662; impact strength test standard GB/T1843-2008; tensile Strength test Standard GB/T16421-1996.
According to the invention, through the combination of specific components, proportions and preparation methods, the constructed microscopic core-shell structure enables the introduction of the flame retardant, so that the flame retardant property of the composite material is improved, and the mechanical property is not affected. Zinc stannate is used as a common inorganic tin flame retardant, has nontoxic and excellent flame retardant performance, is considered as one of high-efficiency green flame retardants, but the single inorganic flame retardant limits the exertion of the flame retardant performance, and along with the introduction of graphene, the composite material obtains a compact protective carbon layer, and can prevent the escape of combustible gas and block heat and mass transfer when the polymer nanocomposite is degraded.
In other embodiments of the present invention, the technical effects described in the present invention may be achieved by selecting different schemes in the ranges of the steps, components, proportions and process parameters described in the present invention, so that the present invention is not listed one by one.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. All equivalent changes of the components, proportions and processes according to the invention are covered in the protection scope of the invention.
Claims (7)
1. The reinforced flame-retardant microcapsule composite material is characterized in that a modified thermoplastic polymer is taken as a core, a synergistic flame retardant layer is coated on the outer side surface of the modified thermoplastic polymer, and finally a modified filling flame retardant layer is coated on the outer side of a graphene layer to form a compact three-layer core-shell structure; the modified thermoplastic polymer is modified thermoplastic resin, the modified filling flame retardant is modified zinc stannate, the synergistic flame retardant layer is graphene, and the mass percentages of the modified thermoplastic resin, the modified filling flame retardant and the graphene are as follows: 80 percent of modified thermoplastic resin, 10 to 19 percent of modified filling flame retardant, 1 to 10 percent of synergistic flame retardant graphene,
the three layers of compact core-shell structures formed by the three components and the synergistic effect of the three layers of compact core-shell structures enable the mechanical properties of the modified thermoplastic polymer to be improved, and the smoke suppression performance and the flame retardant performance of the composite material to be simultaneously improved.
2. The reinforced flame-retardant microcapsule composite material according to claim 1, wherein the modified thermoplastic resin is one of PDA-modified polyvinyl chloride and polystyrene, or functional PVC/PS particles formed by modifying a composition thereof with PDA.
3. The reinforced flame retardant microcapsule composite of claim 1, wherein the modified zinc stannate is zinc hydroxystannate.
4. A method of preparing the reinforced flame retardant microcapsule composite of any of claims 1-3, comprising the steps of:
s1: dispersing a set amount of water-soluble graphene into deionized water, and performing ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
s2: preparing and weighing modified thermoplastic resin particles with required mass according to a proportion, immersing the modified thermoplastic resin particles into the graphene slurry in the step S1, standing for 5 hours, coating a synergistic flame retardant layer on the outer side surface of the modified thermoplastic resin particles, and taking out and drying the modified thermoplastic resin particles to obtain graphene/modified thermoplastic resin particles with a single-layer core-shell structure;
s3: preparing and weighing modified zinc stannate with required mass according to a proportion, and dispersing the modified zinc stannate into deionized water to obtain zinc hydroxystannate slurry;
s4: immersing the graphene/modified thermoplastic resin particles obtained in the step S2 into the zinc hydroxystannate slurry obtained in the step S3, and coating a layer of zinc hydroxystannate on the outer side of a graphene layer of the graphene/modified thermoplastic resin particles to obtain a modified zinc stannate/graphene/thermoplastic resin mixture with a three-layer core-shell structure;
s5: and drying and banburying the modified zinc stannate/graphene/modified thermoplastic resin mixture to obtain the modified zinc stannate/graphene/thermoplastic resin reinforced flame-retardant microcapsule composite material with the three-layer compact core-shell structure.
5. The method according to claim 4, wherein the PDA-modified thermoplastic resin particles are produced in step S2, specifically comprising the steps of:
s21: dissolving a proper amount of Tris powder into deionized water to obtain a 5mmol/L buffer solution, and dropwise adding hydrochloric acid to adjust the pH to 8.5 to obtain a Tris-HCl buffer solution;
s22: weighing a proper amount of dopamine, dissolving in the Tris-HCl buffer solution, and obtaining a PDA-Tris-HCl solution, wherein the concentration of the dopamine is 2.5 mg/ml;
s23: weighing a proper amount of thermoplastic resin powder, adding the PDA-Tris-HCl solution, stirring for 24 hours at the temperature of 70 ℃, and drying for 3 hours to obtain the PDA modified thermoplastic resin particles.
6. The method according to claim 5, wherein PDA modified thermoplastic resin particles are produced in step S2, wherein the thermoplastic resin powder in step S23 is a PVC/PS mixed powder, and the mass ratio of the two is PVC: PS particles = 1: and 1, finally obtaining the PDA modified PVC/PS particles.
7. The preparation method according to claim 4, wherein the modified zinc stannate prepared in the step S3 and weighed according to the proportion has the following specific steps:
s31: weighing proper amount of ZnCl 2 The powder is put into deionized water to prepare ZnCl with the concentration of 2mol/L 2 An aqueous solution;
s32: weighing a proper amount of Na 2 SnO 3 ·3H 2 O is dissolved in deionized water, and the concentration of Na is worth 2mol/L 2 SnO 3 ·3H 2 An aqueous O solution;
s33: weighing a proper amount of ZnCl in the step S31 2 The aqueous solution is directed to Na in step S32 2 SnO 3 ·3H 2 Dropwise adding the O aqueous solution until white precipitation appears in the mixed solution, and reacting for 1h at 60 ℃ to obtain a wet filter cake;
s34: and (3) transferring the wet filter cake in the step (S33) into n-butanol, fully mixing, adopting normal pressure azeotropic distillation, and drying the obtained powder in a 125 ℃ oven to obtain zinc hydroxystannate, namely the modified zinc stannate.
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