CN114702769A - Enhanced flame-retardant microcapsule composite material and preparation method thereof - Google Patents
Enhanced 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 modified filling flame retardant is prepared from the following components in percentage by mass: 80% of modified thermoplastic resin, 10-19% of modified filling flame retardant and 1-10% of synergistic flame retardant graphene. The composite material has a three-layer compact core-shell structure formed by the three components and the synergistic effect of the three components, so that the mechanical property of the modified thermoplastic polymer is improved, and the smoke suppression performance and the flame retardant performance of the composite material are 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 attracted much attention due to its good flexibility, processability, and mechanical properties, and is often used in hoses, conveyor belts, packaging materials, and other common applications. The general PVC has higher chlorine content, the mass fraction reaches 58.7 percent, and the PVC is more fireproof than most organic polymers. However, the conventional plasticizers used to manufacture flexible PVC greatly reduce its excellent fire-retardant property, resulting in a large amount of dense black smoke after burning. Therefore, the flame retardant performance and smoke suppression performance of flexible polyvinyl chloride are in need of improvement.
The Chinese patent application No. CN201711372128.0 discloses a high-flame-retardant polymer composite sun-shading material with soft PVC-coated polyester yarns, which obviously improves the flame retardance of the high-polymer composite sun-shading material with the soft PVC-coated polyester yarns through the combined action of gas phase and solid phase, so that the limit oxygen index of the high-polymer composite sun-shading material reaches 32.4 percent, solves the problem that the limit oxygen index of the high-polymer composite sun-shading material with the soft PVC-coated polyester yarns is low, obviously improves the flame-retardant efficiency of products, and reduces the fire hazard risk of the products. However, although the high-flame-retardant flexible PVC-coated polyester filament polymer composite sun-shading material disclosed by the invention has excellent flame-retardant performance, the mechanical properties of the material have great limitations, and the smoke suppression effect of the material is poor, so that the material still has challenges in industrial popularization.
For a few years, "fire retardant capsule" materials have been developed, i.e., the fire retardant material is encapsulated by a capsule shell to improve the physical stability of the fire retardant during storage. However, the main problem of such flame retardant materials is that they increase the flame retardancy of the materials, but they seriously affect the mechanical properties of the materials. Meanwhile, in the prior art, the flame retardant is usually compounded by adopting a mode of melt blending with thermoplastic polymers, 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 improving the performances of the composite material such as smoke suppression and the like; when the polymer in the material is degraded, the combustible gas can not be prevented from escaping, and the heat transfer and mass transfer can not be hindered.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an enhanced flame-retardant microcapsule composite material, which is characterized in that a unique three-dimensional microstructure is constructed by the composite material through synchronous improvement of components, proportion and a preparation process, specifically, a compact three-layer core-shell structure is formed by coating graphene on the surface of a modified thermoplastic polymer and then coating a layer of modified zinc stannate, and the mechanical property of the polymer is improved by adding a flame retardant, and the smoke suppression property and the flame retardant property are simultaneously improved.
The invention also aims to provide a preparation method of the enhanced flame-retardant microcapsule composite material, which constructs a unique three-dimensional microstructure through synchronous improvement of components, proportion and preparation process, simplifies the preparation process, and improves the compatibility, bonding strength and comprehensive performance of the materials.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
an enhanced 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 modified filling flame retardant is prepared from the following components in percentage by mass: 80% of modified thermoplastic resin, 10-19% of modified filling flame retardant and 1-10% of synergistic flame retardant graphene;
the composite material has a three-layer compact core-shell structure formed by the three components and the synergistic effect of the three components, so that the mechanical property of the modified thermoplastic polymer is improved, and the smoke suppression performance and the flame retardant performance of the composite material are simultaneously improved.
The modified thermoplastic resin is one of PDA modified polyvinyl chloride (PVC) and Polystyrene (PS) or a functionalized PVC/PS particle formed by modifying and modifying a composition of the modified thermoplastic resin and the PDA.
The modified zinc stannate can be zinc hydroxystannate.
The preparation method of the enhanced flame-retardant microcapsule composite material is characterized by comprising the following steps of:
s1: dispersing a set amount of water-soluble graphene into deionized water, and carrying out ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
s2: preparing and weighing modified thermoplastic resin particles with required mass in proportion, immersing the modified thermoplastic resin particles into the graphene slurry obtained 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, taking out and drying 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 the 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 enhanced flame-retardant microcapsule composite material with the three-layer compact core-shell structure.
The preparation of the PDA modified thermoplastic resin particles in step S2 specifically includes the following steps:
s21: dissolving a proper amount of Tris powder into deionized water to obtain 5mmol/L buffer solution, and dropwise adding hydrochloric acid to adjust the pH value to 8.5 to obtain Tris-HCl buffer solution;
s22: weighing a proper amount of dopamine, and dissolving the dopamine in the Tris-HCl buffer solution with the concentration of 2.5mg/ml to obtain a PDA-Tris-HCl solution;
s23: weighing a proper amount of thermoplastic resin powder, adding the thermoplastic resin powder into the PDA-Tris-HCl solution, stirring for 24 hours at the temperature of 70 ℃, and drying for 3 hours to obtain the modified thermoplastic resin particles modified by the PDA.
Preparing PDA modified thermoplastic resin particles in step S2, wherein the thermoplastic resin powder in step S23 is PVC/PS mixed powder, and the mass ratio of the PVC to the PS is as follows: PS particles ═ 1: and 1, finally obtaining the modified PVC/PS particles modified by the PDA.
Step S3, preparing and weighing modified zinc stannate with required mass according to the proportion, which comprises the following steps:
s31: weighing appropriate amount of ZnCl2Putting the powder into deionized water to prepare ZnCl with the concentration of 2mol/L2An aqueous solution;
s32: weighing a proper amount of Na2SnO3·3H2Dissolving O in deionized water to obtain Na with concentration of 2mol/L2SnO3·3H2An aqueous solution of O;
s33: measuring a proper amount of ZnCl in the step S312Introduction of aqueous solution into step S32 by Na2SnO3·3H2Dropwise adding an O aqueous solution until a white precipitate appears in the mixed solution, and reacting at 60 ℃ for 1h to obtain a wet filter cake;
s34: and (4) transferring the wet filter cake obtained in the step (S33) into n-butanol, fully mixing, carrying out azeotropic distillation at normal pressure, and drying the obtained powder in an oven at 125 ℃ to obtain zinc hydroxystannate, namely modified zinc stannate.
Compared with the prior art, the invention has the advantages that:
1. according to the enhanced flame-retardant microcapsule composite material and the preparation method provided by the invention, the components, the proportion and the preparation process are synchronously improved, so that the composite material constructs a unique three-dimensional microstructure, specifically, a layer of modified zinc stannate is coated after graphene is coated on the surface of a modified thermoplastic polymer to form a compact three-layer core-shell structure, the mechanical property of the polymer is improved due to the addition of a flame retardant, and the smoke suppression property and the flame retardant property are simultaneously improved. The material has excellent water resistance and weather resistance, is environment-friendly, has simple preparation steps, and is suitable for popularization and application.
2. The invention provides an enhanced flame-retardant microcapsule composite material and a preparation method thereof. The material has a unique core-shell structure, so that the mechanical property of the polymer is not influenced by the addition of the flame retardant.
3. According to the flame-retardant microcapsule prepared by the invention, the graphene is introduced, so that the composite material obtains a compact protective carbon layer, and when the polymer nano composite material is degraded, the escape of combustible gas can be prevented, and heat and mass transfer is hindered.
4. According to the preparation method of the enhanced flame-retardant microcapsule composite material, provided by the invention, the components, the proportion and the preparation process are synchronously improved, so that the composite material constructs 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 three materials are modified pairwise by adopting a mechanical ball milling modification method, 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 flame retardant with a unique microstructure is formed by introducing graphene on the basis of the core-shell structure, so that the flame retardant property of the composite material is improved, and the mechanical property is not influenced. The zinc stannate adopted by the invention is used as a common inorganic tin flame retardant, has non-toxic and excellent flame retardant property, is considered as one of high-efficiency green flame retardants, but the single inorganic flame retardant limits the exertion of the flame retardant property, and with the introduction of a core-shell structure and graphene, the composite material obtains a compact protective carbon layer, so that when the polymer nano composite material is degraded, the escape of combustible gas can be prevented, and the heat transfer and mass transfer are hindered.
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 by the embodiment of the invention.
The present invention will be described in detail below with reference to the drawings and examples.
The specific implementation mode is as follows:
example (b):
the enhanced 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 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 modified filling flame retardant is prepared from the following components in percentage by mass: 80% of modified thermoplastic resin, 10-19% of modified filling flame retardant and 1-10% of synergistic flame retardant graphene; the composite material has a three-layer compact core-shell structure formed by the three components and the synergistic effect of the three components, so that the mechanical property of the modified thermoplastic polymer is improved, and the smoke suppression performance and the flame retardant performance of the composite material are simultaneously improved.
The modified thermoplastic resin is one of PDA modified polyvinyl chloride (PVC) and Polystyrene (PS) or a functionalized PVC/PS particle formed by modifying and modifying a composition of the modified thermoplastic resin and the PDA.
The modified zinc stannate can also be zinc hydroxystannate.
A preparation method of the enhanced flame-retardant microcapsule composite material comprises the following steps:
s1: dispersing a set amount of water-soluble graphene into deionized water, and carrying out ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
s2: preparing and weighing modified thermoplastic resin particles with required mass in proportion, immersing the modified thermoplastic resin particles into the graphene slurry obtained 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, taking out and drying to obtain graphene/modified thermoplastic resin particles with a single-layer core-shell structure;
the preparation method of the PDA modified thermoplastic resin particles specifically comprises the following steps:
s21: dissolving a proper amount of Tris powder into deionized water to obtain 5mmol/L buffer solution, and dropwise adding hydrochloric acid to adjust the pH value to 8.5 to obtain Tris-HCl buffer solution;
s22: weighing a proper amount of dopamine, and dissolving the dopamine in the Tris-HCl buffer solution with the concentration of 2.5mg/ml to obtain a PDA-Tris-HCl solution;
s23: weighing a proper amount of thermoplastic resin powder, adding the thermoplastic resin powder into 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 PVC to the PS is PVC: PS particles ═ 1: and 1, finally obtaining the modified PVC/PS particles modified by the PDA. In other embodiments, other values of the mass ratio of the two may be selected.
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;
the preparation method comprises the following steps of:
s31: weighing appropriate amount of ZnCl2Putting the powder into deionized water to prepare ZnCl with the concentration of 2mol/L2An aqueous solution;
s32: weighing a proper amount of Na2SnO3·3H2Dissolving O in deionized water to obtain Na with concentration of 2mol/L2SnO3·3H2An aqueous solution of O;
s33: measuring a proper amount of ZnCl in the step S312The aqueous solution is introduced into step S32 with Na2SnO3·3H2Dropwise adding an O aqueous solution until a white precipitate appears in the mixed solution, and reacting at 60 ℃ for 1h to obtain a wet filter cake;
s34: and (4) transferring the wet filter cake obtained in the step (S33) into n-butanol, fully mixing, carrying out azeotropic distillation at normal pressure, and drying the obtained powder in an oven at 125 ℃ to obtain zinc hydroxystannate, namely 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 the 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 enhanced flame-retardant microcapsule composite material with the three-layer compact core-shell structure.
Example 1
The embodiment of the invention provides a reinforced flame-retardant microcapsule composite material and a preparation method thereof, which are specific applications of the embodiment, in particular to a preparation method of a modified zinc stannate/graphene/PVC reinforced 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 the modified PVC resin into the graphene slurry, standing for 5 hours, taking out and drying to obtain graphene/modified PVC resin;
(3) weighing 16g of zinc hydroxystannate, and dispersing 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 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 enhanced flame-retardant microcapsule composite material.
The standard sample strips are subjected to limit oxygen index test, 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 embodiment, in particular to a preparation method of a modified zinc stannate/graphene/PS enhanced flame-retardant microcapsule composite material, and the preparation method comprises 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 the modified PS resin into the graphene slurry, standing for 5 hours, taking out and drying to obtain graphene/modified PVC resin;
(3) weighing 16g of zinc hydroxystannate, and dispersing 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 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 enhanced flame-retardant microcapsule composite material.
The standard sample strips are subjected to limit oxygen index test, smoke density test and mechanical property test, and the results are shown in table 1.
Example 3
The preparation method of the modified zinc stannate/graphene/PVC enhanced flame-retardant microcapsule composite material provided by the embodiment of the invention specifically comprises the following steps:
(1) and 6g of water-soluble graphene is dispersed into deionized water, and ultrasonic treatment is carried out for 5 hours to obtain uniform graphene slurry.
(2) And weighing 80g of modified PVC resin, immersing the modified PVC resin into the graphene slurry, standing for 5 hours, taking out and drying to obtain the graphene/modified PVC resin.
(3) 14g of zinc hydroxystannate was weighed and dispersed in deionized water to obtain a zinc hydroxystannate slurry.
(4) And (3) immersing the obtained graphene/modified PVC resin into the 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 enhanced flame-retardant microcapsule composite material. The temperature is controlled to be 170-180 DEG C
The standard sample strips are subjected to limit oxygen index test, smoke density test and mechanical property test, and the results are shown in table 1.
Example 4
The preparation method of the modified zinc stannate/graphene/PVC/PS enhanced flame-retardant microcapsule composite material provided by the embodiment of the invention 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 the graphene slurry, standing for 5 hours, taking out and drying to obtain graphene/modified PVC/PS resin;
(3) weighing 14g of zinc hydroxystannate, and dispersing 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 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 enhanced flame-retardant microcapsule composite material.
The standard sample strips are subjected to limit oxygen index test, smoke density test and mechanical property test, and the results are shown in table 1.
Referring to the attached drawing 1, which is an electron microscope image of the enhanced flame-retardant microcapsule prepared in examples 1 to 4, clearly shows a microscopic three-layer compact core-shell structure formed by coating and cooperating the three components, specifically, a layer of modified zinc stannate is coated after graphene is coated on the surface of a modified thermoplastic polymer to form a compact three-layer core-shell structure, after the three-layer material is coated, multi-layer blades are formed in a three-dimensional space, a large number of gaps are formed among the blades, the specific surface area is increased, and the addition of the flame-retardant microcapsule promotes the mechanical properties of the polymer of the finally prepared composite material, and the smoke suppression performance and the flame retardant performance are simultaneously improved.
The enhanced flame-retardant microcapsule composite materials prepared in the embodiments 1 to 4 are respectively prepared into standard sample strips, the microstructure of the standard sample strips is shown in a figure 2, and the standard sample strips are compact and uniform in structure and have better mechanical properties; the standard sample strip is subjected to a limiting oxygen index test, a smoke density test and a mechanical property test, and the test results are shown in table 1.
As can be seen from table 1, the core-shell structure flame-retardant composite material obtained by coating graphene and zinc stannate on the surface of the modified thermoplastic polymer resin in each embodiment of the invention can significantly improve the flame retardant property and mechanical property of the thermoplastic polymer resin, and when the addition amount of graphene is 6%, the flame retardant property is optimal, and simultaneously the mechanical property is optimal, so that both the flame retardant property and the mechanical property are considered.
TABLE 1
Note: oxygen index test standard: GB/T5454-1997; smoke density test standard with flame: astm e 662; the impact strength test standard GB/T1843-2008; tensile Strength test Standard GB/T16421-1996.
According to the invention, through the combination of specific components, proportion and a preparation method, the constructed microscopic core-shell structure enables the introduction of a flame retardant, so that the flame retardant property of the composite material is improved, and the mechanical property is not affected. The zinc stannate is used as a common inorganic tin flame retardant, has non-toxic 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 of the zinc stannate, and with the introduction of the graphene, the composite material obtains a compact protective carbon layer, so that when the polymer nano composite material is degraded, the escape of combustible gas can be prevented, and the heat transfer and mass transfer are hindered.
It should be noted that, in other embodiments of the present invention, different schemes obtained by specifically selecting steps, components, ratios, and process parameters described in the present invention can achieve the technical effects described in the present invention, and therefore, the present invention is not listed one by one.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. All equivalent changes in the components, proportions and processes according to the present invention are intended to be covered by the scope of the present invention.
Claims (7)
1. An enhanced 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 modified filling flame retardant is prepared from the following components in percentage by mass: 80% of modified thermoplastic resin, 10-19% of modified filling flame retardant and 1-10% of synergistic flame retardant graphene.
The composite material has a three-layer compact core-shell structure formed by the three components and the synergistic effect of the three components, so that the mechanical property of the modified thermoplastic polymer is improved, and the smoke suppression performance and the flame retardant performance of the composite material are 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 a composition thereof modified by PDA to form functionalized PVC/PS particles.
3. The reinforced flame retardant microcapsule composite according to claim 1, wherein the modified zinc stannate is zinc hydroxystannate.
4. A method for preparing the enhanced flame retardant microcapsule composite material according to any one of claims 1 to 3, which is characterized by comprising the following steps:
s1: dispersing a set amount of water-soluble graphene into deionized water, and carrying out ultrasonic treatment for 5 hours to obtain uniform graphene slurry;
s2: preparing and weighing modified thermoplastic resin particles with required mass in proportion, immersing the modified thermoplastic resin particles into the graphene slurry obtained 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, taking out and drying 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 the 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 enhanced flame-retardant microcapsule composite material with the three-layer compact core-shell structure.
5. The method as claimed in claim 4, wherein the step S2 of preparing PDA modified thermoplastic resin particles comprises the following steps:
s21: dissolving a proper amount of Tris powder into deionized water to obtain 5mmol/L buffer solution, and dropwise adding hydrochloric acid to adjust the pH value to 8.5 to obtain Tris-HCl buffer solution;
s22: weighing a proper amount of dopamine, and dissolving the dopamine in the Tris-HCl buffer solution with the concentration of 2.5mg/ml to obtain a PDA-Tris-HCl solution;
s23: weighing a proper amount of thermoplastic resin powder, adding the thermoplastic resin powder into the PDA-Tris-HCl solution, stirring for 24 hours at the temperature of 70 ℃, and drying for 3 hours to obtain the modified thermoplastic resin particles modified by the PDA.
6. The method as set forth in claim 5, wherein the PDA modified thermoplastic resin particles are prepared in step S2, wherein the thermoplastic resin powder in step S23 is a PVC/PS mixed powder, and the mass ratio of PVC: PS particles ═ 1: and 1, finally obtaining the modified PVC/PS particles modified by the PDA.
7. The preparation method according to claim 4, wherein the modified zinc stannate prepared in step S3 and weighed in proportion comprises the following steps:
s31: weighing appropriate amount of ZnCl2Putting the powder into deionized water to prepare ZnCl with the concentration of 2mol/L2An aqueous solution;
s32: weighing a proper amount of Na2SnO3·3H2Dissolving O in deionized water to obtain Na with concentration of 2mol/L2SnO3·3H2An aqueous solution of O;
s33: measuring a proper amount of ZnCl in the step S312The aqueous solution is introduced into step S32 with Na2SnO3·3H2Dropwise adding an O aqueous solution until a white precipitate appears in the mixed solution, and reacting at 60 ℃ for 1h to obtain a wet filter cake;
s34: and (4) transferring the wet filter cake obtained in the step (S33) into n-butanol, fully mixing, carrying out azeotropic distillation at normal pressure, and drying the obtained powder in an oven at 125 ℃ to obtain zinc hydroxystannate, namely modified zinc stannate.
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