CN113583463A - Flame-retardant high-strength wood-plastic tray material and preparation method thereof - Google Patents
Flame-retardant high-strength wood-plastic tray material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant high-strength wood-plastic tray material and a preparation method thereof, belonging to the technical field of wood-plastic materials. According to the invention, silicate mineral mica is taken as a raw material, firstly, concentrated sulfuric acid and hydrogen peroxide are used for carrying out hydroxylation modification on the surface of the silicate mineral mica, then potassium permanganate is used for oxidation for carrying out carboxylation modification, aluminum hydroxide is deposited on the surface of the modified mica, finally, diphenyl phosphonic acid is used for carrying out secondary modification on the surface of the modified mica to prepare the self-made flame-retardant reinforced filler, and the self-made flame-retardant reinforced filler and the wood-plastic material are compounded to prepare the tray material.
Description
Technical Field
The invention relates to a flame-retardant high-strength wood-plastic tray material and a preparation method thereof, belonging to the technical field of wood-plastic materials.
Background
At present, the wood-plastic composite material is a novel composite material which is recently developed at home and abroad, and is a novel wood material which is prepared by mixing thermoplastic plastics such as polyethylene, polypropylene, polyvinyl chloride and the like instead of a resin adhesive with a certain amount of waste plant fibers such as wood powder, rice husks, straws and the like, and then carrying out plastic processing processes such as extrusion, mould pressing, injection molding and the like to produce a plate or a section, which is an excellent substitute of natural wood. The wood-plastic composite material has the characteristics of wood and plastic, has good dimensional stability, can fully utilize waste plant fiber and waste plastic, and reduces environmental pollution, so the wood-plastic composite material is widely applied to indoor decoration and outdoor use.
However, the wood-plastic composite material has the characteristics of a plastic material, although the wood-plastic composite material has good corrosion resistance and water resistance, the wood-plastic composite material is flammable and has low mechanical strength, and many tray products are made of the wood-plastic composite material at present, so that in the process of stacking goods, if a fire disaster happens, huge loss is generated.
In view of the above defects, the designer actively makes research and innovation to create a flame-retardant high-strength wood-plastic tray material, so that the tray material has industrial utilization value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a flame-retardant high-strength wood-plastic tray material.
The invention discloses a flame-retardant high-strength wood-plastic tray material which comprises the following raw materials in parts by weight:
50-60 parts of 50-mesh poplar powder;
60-70 parts of waste plastic;
10-13 parts of self-made flame-retardant reinforcing filler;
0.3 to 0.8 part of zinc dialkyl dithiophosphate;
5-9 parts of zinc stearate;
0.6-1.0 part of methyl methacrylate;
the self-made flame-retardant reinforced filler is prepared by reacting mica reinforcing material with deionized water and diphenyl phosphonic acid;
the mica reinforcing material is prepared by mixing and reacting modified mica powder, an aluminum sulfate solution and ammonia water;
the modified mica powder is prepared by mixing and reacting mica, concentrated sulfuric acid, hydrogen peroxide and potassium permanganate.
A preparation method of a flame-retardant high-strength wood-plastic tray material comprises the following specific preparation steps:
(1) weighing 50-60 parts by weight of 50-mesh poplar powder, 60-70 parts by weight of waste plastic, 10-13 parts by weight of self-made flame-retardant reinforced filler, 0.3-0.8 part by weight of zinc dialkyl dithiophosphate, 5-9 parts by weight of zinc stearate and 0.6-1.0 part by weight of methyl methacrylate;
(2) and (2) putting the waste plastic into a mixing roll, stirring and mixing, stopping when mixing is sufficient, adding the self-made flame-retardant reinforced filler and the poplar powder, continuously mixing for 5-20 min, finally adding zinc dialkyl dithiophosphate, zinc stearate and methyl methacrylate, continuously stirring and heating to 150-220 ℃ to obtain a mixture, and adding the mixture into a single-screw extruder to extrude the mixture to obtain the flame-retardant high-strength wood-plastic tray material.
Further, the preparation steps of the self-made flame-retardant reinforced filler are as follows:
mixing a mica reinforcing material and deionized water according to the mass ratio of 1:15, then loading the mixture into a reaction kettle, adding diphenyl phosphonic acid with the mass of 1.5-2.0 times of that of the mica reinforcing material into the reaction kettle, stirring and reacting for 10-12 h at the rotating speed of 200-300 r/min, heating to 150-160 ℃ after stirring and reacting, discharging after heat preservation and reaction for 20-24 h, filtering and separating to obtain a reaction filter cake, and drying to obtain the self-made flame-retardant reinforcing filler. The invention adopts diphenyl phosphonic acid and aluminum hydroxide on the surface of mica reinforcing material to carry out hydrothermal reaction, linear polymer formed by oxygen bridge connecting metal atoms is self-assembled into a rod-shaped structure through pi-pi accumulation, the rod-shaped structure formed in the way improves the roughness and physical anchoring points of the surface of mica powder again, is beneficial to forming firm mechanical winding between the mica powder and wood-plastic matrix material, simultaneously, the rod-shaped structure on the surface of the mica filler leads the surface of the mica filler to be in a radial needling shape, and can increase the impact stress protection performance in the radial direction vertical to the rod-shaped structure on the surface of the filler after being added into the wood-plastic matrix material, thereby finally improving the mechanical performance of the wood-plastic material, in addition, as the self-made flame-retardant reinforcing filler contains silicate, oxygen alumina and metal phosphate, the synergistic use of the three materials also has the effect of catalytic char formation, the wood-plastic matrix is promoted to form carbon, the further combustion of the wood-plastic material is inhibited, so that a synergistic flame-retardant effect is achieved, meanwhile, the self-made flame-retardant reinforcing filler is combusted along with the wood-plastic matrix at high temperature, phosphonate is initially in a liquid phase state before the polymer is pyrolyzed, the raw materials are bonded together preferentially at a temperature lower than the decomposition temperature of at least one of other gas generation components, after the composition is heated to a certain temperature, the wood-plastic polymer is dispersed into a gas phase, a hard and porous solid structure is formed on the surface of the polymer, the structure has a certain self-supporting capacity, covers the surface of the polymer, the flame is blocked from being transmitted into the polymer, the generated combustible gas is prevented from escaping outwards, the integrity of the polymer material is maintained, the function of a fireproof barrier layer is achieved, and dispersed pores carried in the liquid phase are formed through the decomposition of the phosphonate, the temporary pores can ensure that the wood-plastic composite basically keeps the original shape and size when being converted into ceramic, the released gas ensures that the viscous liquid phase can be expanded in a controlled manner, in the stage of converting into ceramic under the heating condition, residues formed by combustion and inorganic filler particles are enhanced, the controlled expansion is consistent with the volume lost by combustion, and high-strength ceramic is formed, so that the wood-plastic tray material not only has flame retardance, but also has higher mechanical strength when being combusted.
Further, the mica reinforcing material is prepared by the following steps:
mixing the modified mica powder and an aluminum sulfate solution with the mass concentration of 130g/L according to the mass ratio of 1:8, then filling the mixture into a reaction kettle to obtain a mixture, adding ammonia water with the mass fraction of 15% and the mass ratio of 3-5 times of the mixture into the reaction kettle, stirring the mixture for reaction for 2-3 hours, filtering the mixture, separating the mixture to obtain filter residues, and naturally drying the filter residues to obtain the mica reinforcement material. Mixing modified mica powder and an aluminum sulfate solution, effectively adsorbing and fixing aluminum ions on the surface of the modified mica by utilizing the chelating adsorption effect of chelating carboxyl on the surface of the modified mica powder, then adding ammonia water, reacting the ammonia water with the aluminum ions to generate aluminum hydroxide, and adsorbing and depositing the aluminum hydroxide on the surface of the modified mica once aluminum hydroxide crystal nucleus is formed, wherein the deposition of aluminum hydroxide particles can preliminarily improve the roughness of the surface of the mica;
further, the preparation steps of the modified mica powder are as follows:
weighing mica, placing the mica into a crusher, crushing the mica, sieving the mica with a 50-mesh sieve, collecting sieved powder, mixing concentrated sulfuric acid with the mass fraction of 98% and hydrogen peroxide with the mass fraction of 30% according to the volume ratio of 7:3 to obtain impregnation liquid, mixing the sieved powder and the impregnation liquid according to the mass ratio of 1:10, carrying out ultrasonic oscillation impregnation reaction for 20-30 min, filtering the mixture after the reaction is finished to obtain filter residue, mixing the filter residue and a potassium permanganate solution with the mass fraction of 30% according to the mass ratio of 1:10, carrying out shaking table oscillation reaction for 3-5 h, and then carrying out filtering separation to obtain a filter cake, namely the modified mica powder. The preparation method comprises the steps of firstly taking silicate mineral mica as a raw material, crushing the mica into powder with a specific size, impregnating the mica powder with a mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide in a volume ratio of 7:3 to introduce hydroxyl groups onto the surface of the mica powder, then impregnating the mica powder subjected to surface hydroxylation treatment with a potassium permanganate solution with strong oxidizing property to oxidize the hydroxyl groups on the surface of the mica powder into carboxyl groups, and thus obtaining the mica powder with chelating carboxyl groups on the surface.
By the scheme, the invention at least has the following advantages:
(1) the method comprises the steps of firstly, taking silicate mineral mica as a raw material, crushing the mica into powder with a specific size, impregnating the mica powder with a mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide in a volume ratio of 7:3 to introduce hydroxyl groups to the surface of the mica powder, then impregnating the mica powder subjected to surface hydroxylation with a potassium permanganate solution with strong oxidizing property to oxidize the hydroxyl groups on the surface of the mica powder into carboxyl groups to obtain the mica powder with chelating carboxyl groups on the surface, then mixing the modified mica powder with an aluminum sulfate solution, utilizing the chelating adsorption effect of the chelating carboxyl groups on the surface of the modified mica powder to effectively adsorb and fix aluminum ions on the surface of the modified mica, then adding ammonia water to react with the aluminum ions to generate aluminum hydroxide, and once aluminum hydroxide crystal nuclei are formed, the aluminum hydroxide can be adsorbed and deposited on the surface of the modified mica, and the roughness of the surface of the mica can be primarily improved by the deposition of the aluminum hydroxide particles, the coarse structure is beneficial to winding and hanging with the wood-plastic composite material matrix in the later period, so that firm mechanical winding is formed between the mica powder and the wood-plastic composite material, the mica powder and the wood-plastic composite material are effectively combined, and the mechanical property of the wood-plastic composite material is initially improved;
(2) the invention adopts diphenyl phosphonic acid and aluminum hydroxide on the surface of mica reinforcing material to carry out hydrothermal reaction, linear polymer formed by oxygen bridge connecting metal atoms is self-assembled into a rod-shaped structure through pi-pi accumulation, the rod-shaped structure formed in the way improves the roughness and physical anchoring points of the surface of mica powder again, is beneficial to forming firm mechanical winding between the mica powder and wood-plastic matrix material, simultaneously, the rod-shaped structure on the surface of the mica filler leads the surface of the mica filler to be in a radial needling shape, and can increase the impact stress protection performance in the radial direction vertical to the rod-shaped structure on the surface of the filler after being added into the wood-plastic matrix material, thereby finally improving the mechanical performance of the wood-plastic material, in addition, as the self-made flame-retardant reinforcing filler contains silicate, oxygen alumina and metal phosphate, the synergistic use of the three materials also has the effect of catalytic char formation, the wood-plastic matrix is promoted to form carbon, the further combustion of the wood-plastic material is inhibited, so that a synergistic flame-retardant effect is achieved, meanwhile, the self-made flame-retardant reinforcing filler is combusted along with the wood-plastic matrix at high temperature, phosphonate is initially in a liquid phase state before the polymer is pyrolyzed, the raw materials are bonded together preferentially at a temperature lower than the decomposition temperature of at least one of other gas generation components, after the composition is heated to a certain temperature, the wood-plastic polymer is dispersed into a gas phase, a hard and porous solid structure is formed on the surface of the polymer, the structure has a certain self-supporting capacity, covers the surface of the polymer, the flame is blocked from being transmitted into the polymer, the generated combustible gas is prevented from escaping outwards, the integrity of the polymer material is maintained, the function of a fireproof barrier layer is achieved, and dispersed pores carried in the liquid phase are formed through the decomposition of the phosphonate, the temporary pores can ensure that the wood-plastic composite basically keeps the original shape and size when being converted into ceramic, the released gas ensures that the viscous liquid phase can be expanded in a controlled manner, in the stage of converting into ceramic under the heating condition, residues formed by combustion and inorganic filler particles are enhanced, the controlled expansion is consistent with the volume lost by combustion, and high-strength ceramic is formed, so that the wood-plastic tray material not only has flame retardance, but also has higher mechanical strength when being combusted.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
(1) Weighing mica, putting the mica into a crusher, crushing the mica, sieving the mica with a 50-mesh sieve, collecting sieved powder, mixing concentrated sulfuric acid with the mass fraction of 98% and hydrogen peroxide with the mass fraction of 30% according to the volume ratio of 7:3 to obtain impregnation liquid, mixing the sieved powder and the impregnation liquid according to the mass ratio of 1:10, carrying out ultrasonic oscillation impregnation reaction for 20-30 min, filtering the mixture after the reaction is finished to obtain filter residue, mixing the filter residue and a potassium permanganate solution with the mass fraction of 30% according to the mass ratio of 1:10, carrying out shaking table oscillation reaction for 3-5 h, and then carrying out filtering separation to obtain filter cakes, namely modified mica powder; the preparation method comprises the steps of firstly, taking silicate mineral mica as a raw material, crushing the mica into powder with a specific size, impregnating the mica powder with a mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide in a volume ratio of 7:3 to introduce hydroxyl groups onto the surface of the mica powder, then impregnating the mica powder subjected to surface hydroxylation treatment with a potassium permanganate solution with strong oxidizing property to oxidize the hydroxyl groups on the surface of the mica powder into carboxyl groups, and thus obtaining the mica powder with chelating carboxyl groups on the surface;
(2) mixing the modified mica powder and an aluminum sulfate solution with the mass concentration of 130g/L according to the mass ratio of 1:8, then putting the mixture into a reaction kettle to obtain a mixture, adding ammonia water with the mass fraction of 15% and the mass ratio of 3-5 times of the mixture into the reaction kettle, stirring the mixture for reaction for 2-3 hours, filtering the mixture, separating the mixture to obtain filter residues, and naturally drying the filter residues to obtain a mica reinforcement material; according to the invention, modified mica powder and an aluminum sulfate solution are mixed, aluminum ions are effectively adsorbed and fixed on the surface of the modified mica by utilizing the chelating adsorption effect of chelating carboxyl on the surface of the modified mica powder, then ammonia water is added to react with the aluminum ions to generate aluminum hydroxide, once aluminum hydroxide crystal nucleus is formed, the aluminum hydroxide crystal nucleus can be adsorbed and deposited on the surface of the modified mica, and the deposition of aluminum hydroxide particles can preliminarily improve the roughness of the surface of the mica;
(3) mixing the mica reinforcing material and deionized water according to the mass ratio of 1:15, then loading the mixture into a reaction kettle, adding diphenyl phosphonic acid with the mass of 1.5-2.0 times of that of the mica reinforcing material into the reaction kettle, stirring and reacting for 10-12 h at the rotating speed of 200-300 r/min, heating to 150-160 ℃ after stirring and reacting, discharging after heat preservation and reaction for 20-24 h, filtering and separating to obtain a reaction filter cake, and drying to obtain the self-made flame-retardant reinforcing filler; the invention adopts diphenyl phosphonic acid and aluminum hydroxide on the surface of mica reinforcing material to carry out hydrothermal reaction, linear polymer formed by oxygen bridge connecting metal atoms is self-assembled into a rod-shaped structure through pi-pi accumulation, the rod-shaped structure formed in the way improves the roughness and physical anchoring points of the surface of mica powder again, is beneficial to forming firm mechanical winding between the mica powder and wood-plastic matrix material, simultaneously, the rod-shaped structure on the surface of the mica filler leads the surface of the mica filler to be in a radial needling shape, and can increase the impact stress protection performance in the radial direction vertical to the rod-shaped structure on the surface of the filler after being added into the wood-plastic matrix material, thereby finally improving the mechanical performance of the wood-plastic material, in addition, as the self-made flame-retardant reinforcing filler contains silicate, oxygen alumina and metal phosphate, the synergistic use of the three materials also has the effect of catalytic char formation, the wood-plastic matrix is promoted to form carbon, the further combustion of the wood-plastic material is inhibited, so that a synergistic flame-retardant effect is achieved, meanwhile, the self-made flame-retardant reinforcing filler is combusted along with the wood-plastic matrix at high temperature, phosphonate is initially in a liquid phase state before the polymer is pyrolyzed, the raw materials are bonded together preferentially at a temperature lower than the decomposition temperature of at least one of other gas generation components, after the composition is heated to a certain temperature, the wood-plastic polymer is dispersed into a gas phase, a hard and porous solid structure is formed on the surface of the polymer, the structure has a certain self-supporting capacity, covers the surface of the polymer, the flame is blocked from being transmitted into the polymer, the generated combustible gas is prevented from escaping outwards, the integrity of the polymer material is maintained, the function of a fireproof barrier layer is achieved, and dispersed pores carried in the liquid phase are formed through the decomposition of the phosphonate, the temporary pores can enable the wood-plastic composite to basically keep the original shape and size when being converted into ceramic, the released gas enables the viscous liquid phase to be expanded in a controlled manner, in the stage of converting into ceramic under the heating condition, residues formed by combustion and inorganic filler particles are enhanced, the controlled expansion is consistent with the volume lost by combustion, and high-strength ceramic is formed, so that the wood-plastic tray material disclosed by the invention is flame-retardant, and the mechanical strength is higher when the wood-plastic tray material is combusted;
(4) weighing 50-60 parts by weight of 50-mesh poplar powder, 60-70 parts by weight of waste plastic, 10-13 parts by weight of self-made flame-retardant reinforced filler, 0.3-0.8 part by weight of zinc dialkyl dithiophosphate, 5-9 parts by weight of zinc stearate and 0.6-1.0 part by weight of methyl methacrylate;
(5) and (2) putting the waste plastic into a mixing roll, stirring and mixing, stopping when mixing is sufficient, adding the self-made flame-retardant reinforced filler and the poplar powder, continuously mixing for 5-20 min, finally adding zinc dialkyl dithiophosphate, zinc stearate and methyl methacrylate, continuously stirring and heating to 150-220 ℃ to obtain a mixture, and adding the mixture into a single-screw extruder to extrude the mixture to obtain the flame-retardant high-strength wood-plastic tray material.
Examples
Example 1
(1) Weighing mica, putting the mica into a crusher, crushing the mica, sieving the mica by a 50-mesh sieve, collecting sieved powder, mixing concentrated sulfuric acid with the mass fraction of 98% and hydrogen peroxide with the mass fraction of 30% according to the volume ratio of 7:3 to obtain impregnation liquid, mixing the sieved powder and the impregnation liquid according to the mass ratio of 1:10, carrying out ultrasonic oscillation impregnation reaction for 20min, filtering the mixture after the reaction is finished to obtain filter residue, mixing the filter residue and a potassium permanganate solution with the mass fraction of 30% according to the mass ratio of 1:10, and carrying out shaking table oscillation reaction for 3h and then filtering and separating to obtain a filter cake, namely modified mica powder;
(2) mixing the modified mica powder and an aluminum sulfate solution with the mass concentration of 130g/L according to the mass ratio of 1:8, then putting the mixture into a reaction kettle to obtain a mixture, adding ammonia water with the mass fraction of 15% and the mass ratio of 3 times that of the mixture into the reaction kettle, stirring the mixture for reaction for 2 hours, filtering the mixture, separating the mixture to obtain filter residues, and naturally airing the filter residues to obtain a mica reinforcement material;
(3) mixing the mica reinforcing material and deionized water according to the mass ratio of 1:15, then loading the mixture into a reaction kettle, adding diphenyl phosphonic acid with the mass of 1.5 times that of the mica reinforcing material into the reaction kettle, stirring and reacting for 10 hours at the rotating speed of 200r/min, heating to 150 ℃ after the stirring and reacting, keeping the temperature and reacting for 20 hours, then discharging, filtering and separating to obtain a reaction filter cake, and drying to obtain the self-made flame-retardant reinforcing filler;
(4) weighing 50 parts of 50-mesh poplar powder, 60 parts of waste plastic, 10 parts of self-made flame-retardant reinforcing filler, 0.3 part of zinc dialkyl dithiophosphate, 5 parts of zinc stearate and 0.6 part of methyl methacrylate;
(5) and (2) putting the waste plastic into a mixing roll, stirring and mixing, stopping when mixing is sufficient, adding the self-made flame-retardant reinforced filler and the poplar powder, continuously mixing for 5min, finally adding zinc dialkyl dithiophosphate, zinc stearate and methyl methacrylate, continuously stirring and heating to 150 ℃ to obtain a mixture, and adding the mixture into a single-screw extruder to extrude the mixture to obtain the flame-retardant high-strength wood-plastic tray material.
Example 2
(1) Weighing mica, putting the mica into a crusher, crushing the mica, sieving the mica by a 50-mesh sieve, collecting sieved powder, mixing concentrated sulfuric acid with the mass fraction of 98% and hydrogen peroxide with the mass fraction of 30% according to the volume ratio of 7:3 to obtain impregnation liquid, mixing the sieved powder and the impregnation liquid according to the mass ratio of 1:10, carrying out ultrasonic oscillation impregnation reaction for 25min, filtering the mixture after the reaction is finished to obtain filter residue, mixing the filter residue and a potassium permanganate solution with the mass fraction of 30% according to the mass ratio of 1:10, carrying out shaking table oscillation reaction for 4h, and filtering and separating to obtain a filter cake, namely modified mica powder;
(2) mixing the modified mica powder and an aluminum sulfate solution with the mass concentration of 130g/L according to the mass ratio of 1:8, then putting the mixture into a reaction kettle to obtain a mixture, adding ammonia water with the mass fraction of 15% and the mass ratio of 3-5 times of the mixture into the reaction kettle, stirring for reaction for 2 hours, filtering, separating to obtain filter residues, and naturally drying to obtain a mica reinforcement material;
(3) mixing the mica reinforcing material and deionized water according to the mass ratio of 1:15, then loading the mixture into a reaction kettle, adding diphenyl phosphonic acid with the mass 1.8 times that of the mica reinforcing material into the reaction kettle, stirring and reacting for 11 hours at the rotating speed of 250r/min, heating to 155 ℃ after the stirring and reacting, carrying out heat preservation reaction for 22 hours, then discharging, filtering and separating to obtain a reaction filter cake, and drying to obtain the self-made flame-retardant reinforcing filler;
(4) weighing 55 parts of 50-mesh poplar powder, 65 parts of waste plastic, 12 parts of self-made flame-retardant reinforcing filler, 0.5 part of zinc dialkyl dithiophosphate, 7 parts of zinc stearate and 0.8 part of methyl methacrylate;
(5) and (2) putting the waste plastic into a mixing roll, stirring and mixing, stopping when mixing is sufficient, adding the self-made flame-retardant reinforced filler and the poplar powder, continuously mixing for 15min, finally adding zinc dialkyl dithiophosphate, zinc stearate and methyl methacrylate, continuously stirring and heating to 170 ℃ to obtain a mixture, and adding the mixture into a single-screw extruder to extrude the mixture to obtain the flame-retardant high-strength wood-plastic tray material.
Example 3
(1) Weighing mica, putting the mica into a crusher, crushing the mica, sieving the mica by a 50-mesh sieve, collecting sieved powder, mixing concentrated sulfuric acid with the mass fraction of 98% and hydrogen peroxide with the mass fraction of 30% according to the volume ratio of 7:3 to obtain impregnation liquid, mixing the sieved powder and the impregnation liquid according to the mass ratio of 1:10, carrying out ultrasonic oscillation impregnation reaction for 30min, filtering the mixture after the reaction is finished to obtain filter residue, mixing the filter residue and a potassium permanganate solution with the mass fraction of 30% according to the mass ratio of 1:10, carrying out shaking table oscillation reaction for 5h, and filtering and separating to obtain a filter cake, namely modified mica powder;
(2) mixing the modified mica powder and an aluminum sulfate solution with the mass concentration of 130g/L according to the mass ratio of 1:8, then putting the mixture into a reaction kettle to obtain a mixture, adding ammonia water with the mass fraction of 15% and the mass ratio of 5 times of the mixture into the reaction kettle, stirring the mixture for reaction for 3 hours, filtering the mixture, separating the mixture to obtain filter residues, and naturally airing the filter residues to obtain a mica reinforcement material;
(3) mixing the mica reinforcing material and deionized water according to the mass ratio of 1:15, then loading the mixture into a reaction kettle, adding diphenyl phosphonic acid with the mass 2.0 times that of the mica reinforcing material into the reaction kettle, stirring and reacting for 12 hours at the rotating speed of 300r/min, heating to 160 ℃ after the stirring and reacting, keeping the temperature and reacting for 24 hours, then discharging, filtering and separating to obtain a reaction filter cake, and drying to obtain the self-made flame-retardant reinforcing filler;
(4) weighing 60 parts of 50-mesh poplar powder, 70 parts of waste plastic, 13 parts of self-made flame-retardant reinforcing filler, 0.8 part of zinc dialkyl dithiophosphate, 9 parts of zinc stearate and 1.0 part of methyl methacrylate;
(5) and (2) putting the waste plastic into a mixing roll, stirring and mixing, stopping when mixing is sufficient, adding the self-made flame-retardant reinforced filler and the poplar powder, continuously mixing for 20min, finally adding zinc dialkyl dithiophosphate, zinc stearate and methyl methacrylate, continuously stirring and heating to 220 ℃ to obtain a mixture, and adding the mixture into a single-screw extruder to extrude the mixture to obtain the flame-retardant high-strength wood-plastic tray material.
Example 4: the preparation method is basically the same as that of the example 1 of the invention, except that the self-made flame-retardant reinforcing filler of the invention is not added, and the components and raw materials of the rest raw materials are the same as those of the example 1;
example 5: the preparation method is basically the same as that of the example 1 of the invention, except that mica reinforcing material is used for replacing the self-made flame-retardant reinforcing filler of the invention, and the components and raw materials of the rest raw materials are the same as those of the example 1;
comparative example 1: the preparation method is basically the same as that of the example 1 of the invention, except that mica, aluminum hydroxide and diphenyl phosphonic acid are simply mixed to replace the self-made flame-retardant reinforcing filler of the invention, and the components and raw materials of the rest raw materials are the same as those of the example 1;
detection test
The performance of examples 1 to 5 of the present invention and comparative example 1 were measured, respectively, and the results are shown in table 1:
detection method
The mechanical strength detection method comprises the following steps:
1. and (3) detecting the impact strength: performing performance detection by using a GB/T1043 plastic impact strength test method;
2. drop test: testing by adopting the experimental standard of GB/T4857.4-1992, wherein the experimental temperature is 30 ℃, the humidity is 80%, the drop height is 1000mm, the experimental sample is hoisted along the diagonal direction and then dropped on an impact surface, the same angle is dropped for 3 times on the same height, and whether appearance change exists or not is observed;
the flame retardance detection method comprises the following steps:
detecting the oxygen index of the material by using an oxygen index tester, wherein the higher the oxygen index is, the better the flame retardance is;
TABLE 1 Performance test results
The test data in examples 1 to 3 of the present invention are compared, wherein the mechanical properties and flame retardancy of the material in example 3 are the best, because the raw material components are used in the highest amount in example 3, which also laterally confirms that the technical solution of the present invention can be implemented;
comparing the detection data of example 1 and example 4 of the present invention, example 5 and comparative example 1, the self-made flame retardant reinforcing filler of the present invention is not added in example 4, the components and raw materials of the rest of raw materials are the same as those of example 1, and the final mechanical properties and flame retardancy are significantly reduced compared to example 1, while example 5 replaces the self-made flame retardant reinforcing filler of the present invention with mica reinforcement, the components and raw materials of the rest of raw materials are the same as those of example 1, resulting in a reduction in mechanical properties and flame retardancy compared to example 1, but the reduction is lower than example 4, finally, comparative example 1 replaces the self-made flame retardant reinforcing filler of the present invention after simply mixing mica, aluminum hydroxide and diphenylphosphonic acid, the components and raw materials of the rest of raw materials are the same as those of example 1, resulting in a reduction in mechanical properties and flame retardancy compared to example 1, the same reduction was lower than in example 4, from which it was confirmed that: the method comprises the steps of firstly, taking silicate mineral mica as a raw material, crushing the mica into powder with a specific size, impregnating the mica powder with a mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide in a volume ratio of 7:3 to introduce hydroxyl groups to the surface of the mica powder, then impregnating the mica powder subjected to surface hydroxylation with a potassium permanganate solution with strong oxidizing property to oxidize the hydroxyl groups on the surface of the mica powder into carboxyl groups to obtain the mica powder with chelating carboxyl groups on the surface, then mixing the modified mica powder with an aluminum sulfate solution, utilizing the chelating adsorption effect of the chelating carboxyl groups on the surface of the modified mica powder to effectively adsorb and fix aluminum ions on the surface of the modified mica, then adding ammonia water to react with the aluminum ions to generate aluminum hydroxide, and once aluminum hydroxide crystal nuclei are formed, the aluminum hydroxide can be adsorbed and deposited on the surface of the modified mica, and the roughness of the surface of the mica can be primarily improved by the deposition of the aluminum hydroxide particles, the coarse structure is beneficial to winding and hanging with the wood-plastic composite material matrix in the later period, so that firm mechanical winding is formed between the mica powder and the wood-plastic composite material, the mica powder and the wood-plastic composite material are effectively combined, and the mechanical property of the wood-plastic composite material is initially improved; the invention adopts diphenyl phosphonic acid and aluminum hydroxide on the surface of mica reinforcing material to carry out hydrothermal reaction, linear polymer formed by oxygen bridge connecting metal atoms is self-assembled into a rod-shaped structure through pi-pi accumulation, the rod-shaped structure formed in the way improves the roughness and physical anchoring points of the surface of mica powder again, is beneficial to forming firm mechanical winding between the mica powder and wood-plastic matrix material, simultaneously, the rod-shaped structure on the surface of the mica filler leads the surface of the mica filler to be in a radial needling shape, and can increase the impact stress protection performance in the radial direction vertical to the rod-shaped structure on the surface of the filler after being added into the wood-plastic matrix material, thereby finally improving the mechanical performance of the wood-plastic material, in addition, as the self-made flame-retardant reinforcing filler contains silicate, oxygen alumina and metal phosphate, the synergistic use of the three materials also has the effect of catalytic char formation, the wood-plastic matrix is promoted to form carbon, the further combustion of the wood-plastic material is inhibited, so that a synergistic flame-retardant effect is achieved, meanwhile, the self-made flame-retardant reinforcing filler is combusted along with the wood-plastic matrix at high temperature, phosphonate is initially in a liquid phase state before the polymer is pyrolyzed, the raw materials are bonded together preferentially at a temperature lower than the decomposition temperature of at least one of other gas generation components, after the composition is heated to a certain temperature, the wood-plastic polymer is dispersed into a gas phase, a hard and porous solid structure is formed on the surface of the polymer, the structure has a certain self-supporting capacity, covers the surface of the polymer, the flame is blocked from being transmitted into the polymer, the generated combustible gas is prevented from escaping outwards, the integrity of the polymer material is maintained, the function of a fireproof barrier layer is achieved, and dispersed pores carried in the liquid phase are formed through the decomposition of the phosphonate, the temporary pores can ensure that the wood-plastic composite basically keeps the original shape and size when being converted into ceramic, the released gas ensures that the viscous liquid phase can be expanded in a controlled manner, in the stage of converting into ceramic under the heating condition, residues formed by combustion and inorganic filler particles are enhanced, the controlled expansion is consistent with the volume lost by combustion, and high-strength ceramic is formed, so that the wood-plastic tray material not only has flame retardance, but also has higher mechanical strength when being combusted.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The flame-retardant high-strength wood-plastic tray material is characterized in that: the composite material comprises the following raw materials in parts by weight:
50-60 parts of 50-mesh poplar powder;
60-70 parts of waste plastic;
10-13 parts of self-made flame-retardant reinforcing filler;
0.3 to 0.8 part of zinc dialkyl dithiophosphate;
5-9 parts of zinc stearate;
0.6-1.0 part of methyl methacrylate;
the self-made flame-retardant reinforced filler is prepared by reacting mica reinforcing material with deionized water and diphenyl phosphonic acid;
the mica reinforcing material is prepared by mixing and reacting modified mica powder, an aluminum sulfate solution and ammonia water;
the modified mica powder is prepared by mixing and reacting mica, concentrated sulfuric acid, hydrogen peroxide and potassium permanganate.
2. A preparation method of a flame-retardant high-strength wood-plastic tray material is characterized by comprising the following specific preparation steps:
(1) weighing 50-60 parts by weight of 50-mesh poplar powder, 60-70 parts by weight of waste plastic, 10-13 parts by weight of self-made flame-retardant reinforced filler, 0.3-0.8 part by weight of zinc dialkyl dithiophosphate, 5-9 parts by weight of zinc stearate and 0.6-1.0 part by weight of methyl methacrylate;
(2) and (2) putting the waste plastic into a mixing roll, stirring and mixing, stopping when mixing is sufficient, adding the self-made flame-retardant reinforced filler and the poplar powder, continuously mixing for 5-20 min, finally adding zinc dialkyl dithiophosphate, zinc stearate and methyl methacrylate, continuously stirring and heating to 150-220 ℃ to obtain a mixture, and adding the mixture into a single-screw extruder to extrude the mixture to obtain the flame-retardant high-strength wood-plastic tray material.
3. The preparation method of the flame-retardant high-strength wood-plastic tray material according to claim 2, characterized by comprising the following steps: the preparation steps of the self-made flame-retardant reinforced filler are as follows:
mixing a mica reinforcing material and deionized water according to the mass ratio of 1:15, then loading the mixture into a reaction kettle, adding diphenyl phosphonic acid with the mass of 1.5-2.0 times of that of the mica reinforcing material into the reaction kettle, stirring and reacting for 10-12 h at the rotating speed of 200-300 r/min, heating to 150-160 ℃ after stirring and reacting, discharging after heat preservation and reaction for 20-24 h, filtering and separating to obtain a reaction filter cake, and drying to obtain the self-made flame-retardant reinforcing filler.
4. The preparation method of the flame-retardant high-strength wood-plastic tray material according to claim 3, characterized by comprising the following steps: the preparation steps of the mica reinforcing material are as follows:
mixing the modified mica powder and an aluminum sulfate solution with the mass concentration of 130g/L according to the mass ratio of 1:8, then filling the mixture into a reaction kettle to obtain a mixture, adding ammonia water with the mass fraction of 15% and the mass ratio of 3-5 times of the mixture into the reaction kettle, stirring the mixture for reaction for 2-3 hours, filtering the mixture, separating the mixture to obtain filter residues, and naturally drying the filter residues to obtain the mica reinforcement material.
5. The preparation method of the flame-retardant high-strength wood-plastic tray material according to claim 4, characterized by comprising the following steps: the preparation steps of the modified mica powder are as follows:
weighing mica, placing the mica into a crusher, crushing the mica, sieving the mica with a 50-mesh sieve, collecting sieved powder, mixing concentrated sulfuric acid with the mass fraction of 98% and hydrogen peroxide with the mass fraction of 30% according to the volume ratio of 7:3 to obtain impregnation liquid, mixing the sieved powder and the impregnation liquid according to the mass ratio of 1:10, carrying out ultrasonic oscillation impregnation reaction for 20-30 min, filtering the mixture after the reaction is finished to obtain filter residue, mixing the filter residue and a potassium permanganate solution with the mass fraction of 30% according to the mass ratio of 1:10, carrying out shaking table oscillation reaction for 3-5 h, and then carrying out filtering separation to obtain a filter cake, namely the modified mica powder.
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| CN114231045A (en) * | 2021-12-27 | 2022-03-25 | 苏州科技大学 | Application of wood powder loaded with magnesium hydroxide in pitch carbon emission reduction |
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| CN114231045A (en) * | 2021-12-27 | 2022-03-25 | 苏州科技大学 | Application of wood powder loaded with magnesium hydroxide in pitch carbon emission reduction |
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