CN110790969A - Preparation method of layer-by-layer self-assembly flame-retardant wood-plastic composite material - Google Patents
Preparation method of layer-by-layer self-assembly flame-retardant wood-plastic composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a layer-by-layer self-assembly flame-retardant wood-plastic composite material, and relates to a preparation method of a flame-retardant wood-plastic composite material. The invention aims to solve the problems that the viscosity and modulus of a composite material are changed, the processing is difficult and the production cost is increased due to the fact that the existing method for improving the flame retardant property of the WPC or the WPC is added with a flame retardant with higher filling amount; or the problems that the size of a sample is strictly required by wood fiber impregnation treatment, the solution is easy to cross-contaminate, the concentration of the solution is reduced along with the increase of the impregnation times, the pressing process is complex, and the method is not suitable for industrial production exist. The method comprises the following steps: firstly, low-temperature plasma treatment; secondly, preparing a branched polyethyleneimine cation solution; thirdly, preparing a cation dispersion liquid; fourthly, preparing an anionic dispersion liquid; fifthly, self-assembling layer by layer.
Description
Technical Field
The invention relates to a preparation method of a flame-retardant wood-plastic composite material.
Background
Wood Plastic Composites (WPCs) are receiving more and more attention due to the advantages of wood and plastic, and their demand is increasing. The wood-plastic composite material is widely applied to the field of outdoor decoration, and the application field of the wood-plastic composite material is expected to be further expanded by the existing research, particularly the aspect of indoor decoration.
However, wood fiber and thermoplastic polymer in wood-plastic composite are inflammable and generate smoke when burning, which severely limits the use of the wood-plastic composite in large areas with dense population. ① methods of adding single-component or composite flame retardant and smoke suppressant to raw materials, ② method of penetrating flame retardant containing elements such as P/N/Si/B/Zn/Fe/Al into wood fiber, ③ method of surface flame retardant treatment of WPC are adopted in the prior art.
The patent with the publication number of CN 110003677A discloses a halogen-free flame-retardant polypropylene wood-plastic composite material and a preparation method thereof, and the flame retardant property of the wood-plastic composite material is remarkably improved by adding ammonium polyphosphate (APP). The publication No. CN 106752055A adopts the self-assembly of layers on the surface of a plant fiber and plastic premix, namely, the nanocrystalline cellulose and the ammonium polyphosphate are sequentially carried outThe nano silicon dioxide polyelectrolyte is sprayed on the surface of the plant fiber and plastic premix, and the flame-retardant wood-plastic composite material is obtained through extrusion, wherein the scheme is that the flame retardant with the content of 15-25% is added into the raw materials. Publication No. CN108192130A discloses a self-assembled flame-retardant bamboo-plastic composite material prepared by mixing H2Ti2O5·H2The O nano tube/gamma-aminopropyl triethoxysilane dispersion liquid and the sodium polystyrene sulfonate solution are soaked for a plurality of times, the size of a sample is strictly required by alternate soaking, the solution cross contamination is inevitably caused, and the solution concentration is reduced along with the increase of the soaking times. Obviously, this inefficient and disadvantageous approach is not suitable for large-scale production.
Disclosure of Invention
The invention aims to solve the problems that the viscosity and modulus of a composite material are changed, the processing is difficult and the production cost is increased due to the fact that the existing method for improving the flame retardant property of the WPC or the WPC is added with a flame retardant with higher filling amount; or the impregnation treatment of the wood fiber has strict requirements on the size of a sample, the solution is easy to cross-contaminate, the concentration of the solution is reduced along with the increase of the impregnation times, the pressing process is complex, and the method is not suitable for industrial production, thereby providing the preparation method of the layer-by-layer self-assembly flame-retardant wood-plastic composite material.
A preparation method of a layer-by-layer self-assembly flame-retardant wood-plastic composite material is completed according to the following steps:
firstly, low-temperature plasma treatment:
polishing the wood-plastic composite material to remove plastic covered on the surface, then cleaning and drying to obtain a treated sample, placing the treated sample in low-temperature plasma equipment, and under the conditions of oxygen atmosphere and treatment power of 600-1000W, the treatment time per square centimeter of the sample is 2-3 s, so as to obtain the sample treated by low-temperature plasma;
secondly, preparing a branched polyethyleneimine cation solution:
dissolving branched polyethyleneimine in deionized water, adjusting the pH to 9-10, and uniformly stirring at room temperature to obtain a branched polyethyleneimine cation solution;
the volume ratio of the mass of the branched polyethyleneimine to the deionized water is 1g (50-200) mL;
thirdly, preparing a cationic dispersion liquid:
adding the multi-walled carbon nanotube or the modified multi-walled carbon nanotube into a branched polyethyleneimine cation solution, and treating for 30-60 min by using an ultrasonic cell crusher under the condition that the power is 800-1000W to obtain a cation dispersion liquid;
the mass ratio of the multi-walled carbon nanotube or the modified multi-walled carbon nanotube to the branched polyethyleneimine obtained in the second step is (0.05-0.2): 1;
fourthly, preparing an anion dispersion liquid:
dissolving sodium-based montmorillonite in deionized water, and uniformly stirring to obtain an anion dispersion liquid;
the volume ratio of the mass of the sodium-based montmorillonite to the deionized water is 1g (50-200) mL;
fifthly, self-assembling layer by layer:
①, sequentially spraying the cationic dispersion liquid and the anionic dispersion liquid on the surface of the sample treated by the low-temperature plasma, and drying for 15-20 min at the temperature of 50-70 ℃ to obtain a sample sprayed for one time;
②, sequentially spraying the cation dispersion liquid and the anion dispersion liquid on the surface of the sample sprayed for the first time, and drying for 3-5 min at the temperature of 50-70 ℃ to obtain a sample sprayed for the second time;
③, repeating the sample sprayed for the second time 38-238 times according to the fifth ② to obtain the layer-by-layer self-assembly flame-retardant wood-plastic composite material.
The invention has the beneficial effects that:
firstly, a multilayer coating with a three-dimensional network structure is obtained by accurately matching a one-dimensional nano material (multi-walled carbon nano tube and modified multi-walled carbon nano tube) and a two-dimensional nano material (sodium-based montmorillonite) with a specific polymer (branched polyethyleneimine), and the crosslinked network structure hinders the diffusion of volatile organic matter fragments and the supply of oxygen, so that the flame retardant property and the smoke suppression property of a system are effectively improved.
The raw materials adopted by the invention are all green environment-friendly materials, the obtained product cannot cause damage to the environment and human bodies, and the formed product is a novel environment-friendly flame-retardant wood-plastic composite material.
Compared with untreated wood-plastic composite materials, the total heat release amount of the branched polyethyleneimine/multi-walled carbon nanotube or the branched polyethyleneimine/modified multi-walled carbon nanotube and the sodium-based montmorillonite formula adopted by the invention is reduced by 3.28-21.28%, the peak heat release rate is reduced by 26.77-43.17%, the total smoke release amount is reduced by 32.16-36.46%, the smoke generation rate is reduced by 52.23-64.43%, the CO generation rate is reduced by 17.99-27.58%, the CO generation amount is reduced by 4.59-18.62%, the ignition time is prolonged by 112.24-383.67%, the mass loss is reduced by 5.68-12.50%, and the carbon forming rate is improved based on the reduction of the mass loss rate.
Compared with the traditional blending mode of doping a flame retardant, the flame retardant is adsorbed on the surface of the wood-plastic composite material in the form of the ultrathin nanometer film, so that the dosage of the required flame retardant material is very low and only accounts for 0.5-1% of the mass of the layer-by-layer self-assembled flame retardant wood-plastic composite material, and the cost is greatly reduced;
compared with the existing dipping method, the method avoids the problems of cross contamination of the solution caused by alternate dipping and the need of regular replacement of the solution along with the reduction of the concentration in the using process, greatly improves the efficiency of preparing the multilayer coating, and can be used for industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of a layer-by-layer self-assembled flame-retardant wood-plastic composite material prepared in the first embodiment, wherein 1 is a multi-walled carbon nanotube, and 2 is a montmorillonite layer;
fig. 2 is a scanning electron microscope image of the layer-by-layer self-assembled flame-retardant wood-plastic composite material prepared in example two, wherein 1 is a graphitized wall carbon nanotube, and 2 is a montmorillonite layer.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of a layer-by-layer self-assembled flame-retardant wood-plastic composite material, which is completed by the following steps:
firstly, low-temperature plasma treatment:
polishing the wood-plastic composite material to remove plastic covered on the surface, then cleaning and drying to obtain a treated sample, placing the treated sample in low-temperature plasma equipment, and under the conditions of oxygen atmosphere and treatment power of 600-1000W, the treatment time per square centimeter of the sample is 2-3 s, so as to obtain the sample treated by low-temperature plasma;
secondly, preparing a branched polyethyleneimine cation solution:
dissolving branched polyethyleneimine in deionized water, adjusting the pH to 9-10, and uniformly stirring at room temperature to obtain a branched polyethyleneimine cation solution;
the volume ratio of the mass of the branched polyethyleneimine to the deionized water is 1g (50-200) mL;
thirdly, preparing a cationic dispersion liquid:
adding the multi-walled carbon nanotube or the modified multi-walled carbon nanotube into a branched polyethyleneimine cation solution, and treating for 30-60 min by using an ultrasonic cell crusher under the condition that the power is 800-1000W to obtain a cation dispersion liquid;
the mass ratio of the multi-walled carbon nanotube or the modified multi-walled carbon nanotube to the branched polyethyleneimine obtained in the second step is (0.05-0.2): 1;
fourthly, preparing an anion dispersion liquid:
dissolving sodium-based montmorillonite in deionized water, and uniformly stirring to obtain an anion dispersion liquid;
the volume ratio of the mass of the sodium-based montmorillonite to the deionized water is 1g (50-200) mL;
fifthly, self-assembling layer by layer:
①, sequentially spraying the cationic dispersion liquid and the anionic dispersion liquid on the surface of the sample treated by the low-temperature plasma, and drying for 15-20 min at the temperature of 50-70 ℃ to obtain a sample sprayed for one time;
②, sequentially spraying the cation dispersion liquid and the anion dispersion liquid on the surface of the sample sprayed for the first time, and drying for 3-5 min at the temperature of 50-70 ℃ to obtain a sample sprayed for the second time;
③, repeating the sample sprayed for the second time 38-238 times according to the fifth ② to obtain the layer-by-layer self-assembly flame-retardant wood-plastic composite material.
In the fifth step ① of the present embodiment, the first layer is dried for a long time, so that the nano material is fully and stably adsorbed on the surface of the wood-plastic composite material, and a good foundation is laid for the subsequent cyclic adsorption.
The beneficial effects of the embodiment are as follows: firstly, a multilayer coating with a three-dimensional network structure is obtained by accurately matching a one-dimensional nano material (multi-walled carbon nano tube and modified multi-walled carbon nano tube) and a two-dimensional nano material (sodium-based montmorillonite) with a specific polymer (branched polyethyleneimine), and the crosslinked network structure hinders the diffusion of volatile organic matter fragments and the supply of oxygen, so that the flame retardant property and the smoke suppression property of a system are effectively improved.
Secondly, the raw materials adopted by the embodiment are all green environment-friendly materials, the obtained product cannot cause damage to the environment and a human body, and the formed product is a novel environment-friendly flame-retardant wood-plastic composite material.
Compared with an untreated wood-plastic composite material, the total heat release amount of the branched polyethyleneimine/multi-walled carbon nanotube or the branched polyethyleneimine/modified multi-walled carbon nanotube and the sodium-based montmorillonite formula adopted by the embodiment is reduced by 3.28-21.28%, the peak heat release rate is reduced by 26.77-43.17%, the total smoke release amount is reduced by 32.16-36.46%, the smoke generation rate is reduced by 52.23-64.43%, the CO generation rate is reduced by 17.99-27.58%, the CO generation amount is reduced by 4.59-18.62%, the ignition time is prolonged by 112.24-383.67%, the mass loss is reduced by 5.68-12.50%, and the char yield is improved based on the reduction of the mass loss rate.
Compared with the traditional blending mode of doping a flame retardant, the method is absorbed on the surface of the wood-plastic composite material in the form of the ultrathin nano film, so that the dosage of the required flame retardant material is very low and only accounts for 0.5-1% of the mass of the layer-by-layer self-assembly flame retardant wood-plastic composite material, and the cost is greatly reduced;
compared with the existing dipping method, the embodiment avoids the problems of solution cross contamination caused by alternate dipping and the problem that the solution needs to be replaced at regular time along with the reduction of the concentration in the using process, greatly improves the efficiency of preparing the multilayer coating, and can be used for industrial production.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the wood-plastic composite material in the step one is a high-density polyethylene wood-plastic composite material, a polyvinyl chloride wood-plastic composite material or a polypropylene wood-plastic composite material. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the modified multi-walled carbon nanotube in the third step is a hydroxylated multi-walled carbon nanotube, a carboxylated multi-walled carbon nanotube, an aminated multi-walled carbon nanotube, a graphitized multi-walled carbon nanotube, a hydroxyl graphitized multi-walled carbon nanotube or a carboxyl graphitized multi-walled carbon nanotube. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: polishing the wood-plastic composite material in the step one to remove the plastic covered on the surface, and then cleaning and drying the wood-plastic composite material, wherein the polishing step is specifically carried out according to the following steps: the wood-plastic composite material is polished by using 100-mesh abrasive paper to remove plastic covered on the surface, then the surface is swept by using vacuum gas, washed by using ethanol and deionized water in sequence, and finally dried in an oven at the temperature of 30-60 ℃. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the first to fourth differences of this embodiment from the first to fourth embodiments are: and step two, dissolving the branched polyethyleneimine in deionized water, adjusting the pH to 9-10 by using hydrochloric acid with the concentration of 0.5-1.0 mol/L, and stirring at room temperature for 24-36 h. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the fourth step, the sodium-based montmorillonite is dissolved in the deionized water and stirred for 24 to 36 hours. The rest is the same as the first to fifth embodiments.
Seventh embodiment mode, the difference between this embodiment mode and one of the first to sixth embodiment modes is that the spray coating in the fifth ① and the fifth ② is performed by uniformly spraying the sample surface with a spray gun having a nozzle inner diameter of 0.5mm to 4mm under the conditions of a distance of 20cm to 40cm from the sample surface and a power of 400W to 800W.
Eighth embodiment this embodiment differs from one of the first to seventh embodiments in that the cationic dispersion described in step five ① is sprayed at 0.04 to 0.08mL per square centimeter, and the anionic dispersion described in step five ① is sprayed at 0.04 to 0.08mL per square centimeter, otherwise the embodiments are the same as the first to seventh embodiments.
Ninth embodiment this embodiment differs from the first to eighth embodiments in that the cationic dispersion in step five ② is sprayed at 0.02mL to 0.04mL per square centimeter, and the anionic dispersion in step five ② is sprayed at 0.02mL to 0.04mL per square centimeter, and the other embodiments are the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the volume ratio of the mass of the branched polyethyleneimine to the deionized water in the step II is 1g (100-200) mL; the mass ratio of the multi-walled carbon nanotube or the modified multi-walled carbon nanotube in the third step to the branched polyethyleneimine in the second step is (0.1-0.2): 1; the volume ratio of the mass of the sodium montmorillonite to the deionized water in the fourth step is 1g (100-200) mL. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method of a layer-by-layer self-assembly flame-retardant wood-plastic composite material is completed according to the following steps:
firstly, low-temperature plasma treatment:
polishing the wood-plastic composite material to remove plastic covered on the surface, then cleaning and drying to obtain a treated sample, placing the treated sample in low-temperature plasma equipment, and under the conditions of oxygen atmosphere and treatment power of 800W, treating the sample for 2s per square centimeter to obtain the sample treated by low-temperature plasma;
secondly, preparing a branched polyethyleneimine cation solution:
dissolving branched polyethyleneimine in deionized water, adjusting the pH to 10 by using hydrochloric acid with the concentration of 1.0mol/L, and stirring at room temperature for 24 hours to obtain a branched polyethyleneimine cation solution;
the volume ratio of the mass of the branched polyethyleneimine to the deionized water is 1g:100 mL;
thirdly, preparing a cationic dispersion liquid:
adding a multi-walled carbon nanotube into a branched polyethyleneimine cation solution, and treating for 1h by using an ultrasonic cell crushing instrument under the condition that the power is 1000W to obtain a cation dispersion liquid;
the mass ratio of the multi-walled carbon nano-tube to the branched polyethyleneimine in the second step is 0.1: 1;
fourthly, preparing an anion dispersion liquid:
dissolving sodium-based montmorillonite in deionized water, and stirring for 24h to obtain an anion dispersion liquid;
the volume ratio of the mass of the sodium-based montmorillonite to the deionized water is 1g:100 mL;
fifthly, self-assembling layer by layer:
①, sequentially spraying the cationic dispersion liquid and the anionic dispersion liquid on the surface of the sample treated by the low-temperature plasma, and drying for 20min at the temperature of 60 ℃ to obtain a sample sprayed for one time;
②, sequentially spraying the cationic dispersion liquid and the anionic dispersion liquid on the surface of the sample sprayed for the first time, and drying for 5min at the temperature of 60 ℃ to obtain a sample sprayed for the second time;
③, repeating the sample sprayed twice 78 times according to the fifth ② to obtain the layer-by-layer self-assembly flame-retardant wood-plastic composite material.
Polishing the wood-plastic composite material in the step one to remove the plastic covered on the surface, and then cleaning and drying the wood-plastic composite material, wherein the polishing step is specifically carried out according to the following steps: the wood-plastic composite material is polished by using 100-mesh abrasive paper to remove plastic covered on the surface, then the surface is swept by using vacuum gas, washed by using ethanol and deionized water in sequence, and finally dried in an oven at the temperature of 30 ℃.
And step five ①, wherein the spraying is carried out uniformly by using a spray gun with a nozzle inner diameter of 4mm under the conditions that the distance between the spray gun and the sample surface is 30cm and the power is 500W.
The spraying in the fifth step ② is to spray evenly with a spray gun with a nozzle inner diameter of 2mm under the conditions of a distance of 30cm from the surface of the sample and a power of 500W.
Spraying 0.04mL of the cationic dispersion liquid per square centimeter in step five ①, and spraying 0.04mL of the anionic dispersion liquid per square centimeter;
in step five ②, the cationic dispersion liquid is sprayed at 0.02 mL/sq cm, and the anionic dispersion liquid is sprayed at 0.02 mL/sq cm.
The wood-plastic composite material in the step one is a high-density polyethylene wood-plastic composite material, and is prepared by the following steps:
a. weighing:
weighing 20kg of wood fiber material with the water content of less than 3 percent, 1.3kg of maleic anhydride grafted polyhexene coupling agent, 11.3kg of high density polyethylene and 0.7kg of paraffin lubricant;
the grain size of the wood fiber material with the water content of less than 3 percent is 100 meshes; the wood fiber material with the water content of less than 3% is obtained by drying wood powder in an oven at the temperature of 105 ℃;
b. preparing a premix:
weighing a wood fiber material with the water content of less than 3%, a maleic anhydride grafted polyhexene coupling agent, high-density polyethylene and a paraffin lubricant, and mixing for 10min in a high-speed mixer at the temperature of 80 ℃ and the rotating speed of 500rpm to obtain a premix;
c. preparing composite material particles:
placing the premix in a double-screw extruder, melting, compounding and uniformly extruding materials at the temperature of 165 ℃, cooling and crushing by using a crusher to obtain composite material particles;
d. the high-density polyethylene wood-plastic composite material comprises the following components:
and (3) placing the composite material particles in a single-screw extruder, extruding and molding at the temperature of 170 ℃, and then cooling and shaping to obtain the high-density polyethylene wood-plastic composite material.
Example two: the difference between the present embodiment and the first embodiment is: adding the graphitized multi-walled carbon nano-tube into a branched polyethyleneimine cation solution, and treating for 1h by using an ultrasonic cell crushing instrument under the condition that the power is 1000W to obtain a cation dispersion liquid; the mass ratio of the graphitized multi-walled carbon nanotube to the branched polyethyleneimine in the second step is 0.1: 1. The rest is the same as the first embodiment.
Example three: the difference between the present embodiment and the first embodiment is: the wood-plastic composite material in the step one is a polypropylene wood-plastic composite material, and is prepared by the following steps:
a. weighing:
weighing 20kg of wood fiber material with the water content of less than 3%, 1.3kg of maleic anhydride grafted polypropylene coupling agent, 11.3kg of polypropylene and 0.7kg of paraffin lubricant;
the grain size of the wood fiber material with the water content of less than 3 percent is 100 meshes; the wood fiber material with the water content of less than 3% is obtained by drying wood powder in an oven at the temperature of 105 ℃;
b. preparing a premix:
mixing the weighed wood fiber material with the water content of less than 3%, the maleic anhydride grafted polypropylene coupling agent, the polypropylene and the paraffin lubricant for 10min in a high-speed mixer at the temperature of 80 ℃ and the rotating speed of 500rpm to obtain a premix;
c. preparing composite material particles:
placing the premix in a double-screw extruder, melting, compounding and uniformly extruding materials at the temperature of 170 ℃, cooling and crushing by using a crusher to obtain composite material particles;
d. the polypropylene wood-plastic composite material comprises the following components:
and (3) placing the composite material particles in a single-screw extruder, extruding and molding at the temperature of 180 ℃, and then cooling and shaping to obtain the polypropylene wood-plastic composite material. The rest is the same as the first embodiment.
Example four: the present embodiment is different from the third embodiment in that: adding the graphitized multi-walled carbon nano-tube into a branched polyethyleneimine cation solution, and treating for 1h by using an ultrasonic cell crushing instrument under the condition that the power is 1000W to obtain a cation dispersion liquid; the mass ratio of the graphitized multi-walled carbon nanotube to the branched polyethyleneimine in the second step is 0.1: 1. The other steps are the same as those of the embodiment.
FIG. 1 is a scanning electron microscope image of a layer-by-layer self-assembled flame-retardant wood-plastic composite material prepared in the first embodiment, wherein 1 is a multi-walled carbon nanotube, and 2 is a montmorillonite layer; as can be seen from the figure, the multi-walled carbon nanotubes are inserted between the dense and regularly arranged montmorillonite multi-layers to form a three-dimensional network structure.
Fig. 2 is a scanning electron microscope image of the layer-by-layer self-assembled flame-retardant wood-plastic composite material prepared in example two, wherein 1 is a graphitized wall carbon nanotube, and 2 is a montmorillonite layer. As can be seen from the figure, the graphitized multi-walled carbon nanotubes are inserted between the dense and regularly arranged montmorillonite multi-layers to form a three-dimensional network structure.
TABLE 1
As can be seen from the table, all the examples exhibited effective flame retardant performance after deposition of the multilayer coating, the total heat release amount was reduced by 3.28% to 21.28%, the peak heat release rate was reduced by 26.77% to 43.17%, the total smoke release amount was reduced by 32.16% to 36.46%, the smoke generation rate was reduced by 52.23% to 64.43%, the CO generation rate was reduced by 17.99% to 27.58%, the CO generation amount was reduced by 4.59% to 18.62%, the ignition time was prolonged by 112.24% to 383.67%, and the mass loss was reduced by 5.68% to 12.50%.
The second and fourth examples are branched polyethyleneimine-graphitized multi-walled carbon nanotube/sodium-based montmorillonite multilayer coatings, and the flame retardant property of the branched polyethyleneimine-multi-walled carbon nanotube/sodium-based montmorillonite multilayer coatings is better than that of the first and third examples. When the branched polyethyleneimine-graphitized multi-walled carbon nanotube/sodium-based montmorillonite multilayer coating is deposited on the surface of the high-density polyethylene-based wood-plastic composite material, the flame retardant property is most balanced, the peak heat release rate is reduced by 43.17%, the smoke generation rate is reduced by 64.43%, the CO generation rate is reduced by 25.28%, the ignition time is prolonged by 383.67%, and the mass loss is reduced by 12.50%.
Claims (10)
1. A preparation method of a layer-by-layer self-assembly flame-retardant wood-plastic composite material is characterized by comprising the following steps:
firstly, low-temperature plasma treatment:
polishing the wood-plastic composite material to remove plastic covered on the surface, then cleaning and drying to obtain a treated sample, placing the treated sample in low-temperature plasma equipment, and under the conditions of oxygen atmosphere and treatment power of 600-1000W, the treatment time per square centimeter of the sample is 2-3 s, so as to obtain the sample treated by low-temperature plasma;
secondly, preparing a branched polyethyleneimine cation solution:
dissolving branched polyethyleneimine in deionized water, adjusting the pH to 9-10, and uniformly stirring at room temperature to obtain a branched polyethyleneimine cation solution;
the volume ratio of the mass of the branched polyethyleneimine to the deionized water is 1g (50-200) mL;
thirdly, preparing a cationic dispersion liquid:
adding the multi-walled carbon nanotube or the modified multi-walled carbon nanotube into a branched polyethyleneimine cation solution, and treating for 30-60 min by using an ultrasonic cell crusher under the condition that the power is 800-1000W to obtain a cation dispersion liquid;
the mass ratio of the multi-walled carbon nanotube or the modified multi-walled carbon nanotube to the branched polyethyleneimine obtained in the second step is (0.05-0.2): 1;
fourthly, preparing an anion dispersion liquid:
dissolving sodium-based montmorillonite in deionized water, and uniformly stirring to obtain an anion dispersion liquid;
the volume ratio of the mass of the sodium-based montmorillonite to the deionized water is 1g (50-200) mL;
fifthly, self-assembling layer by layer:
①, sequentially spraying the cationic dispersion liquid and the anionic dispersion liquid on the surface of the sample treated by the low-temperature plasma, and drying for 15-20 min at the temperature of 50-70 ℃ to obtain a sample sprayed for one time;
②, sequentially spraying the cation dispersion liquid and the anion dispersion liquid on the surface of the sample sprayed for the first time, and drying for 3-5 min at the temperature of 50-70 ℃ to obtain a sample sprayed for the second time;
③, repeating the sample sprayed for the second time 38-238 times according to the fifth ② to obtain the layer-by-layer self-assembly flame-retardant wood-plastic composite material.
2. The preparation method of the layer-by-layer self-assembled flame-retardant wood-plastic composite material according to claim 1, characterized in that: the wood-plastic composite material in the step one is a high-density polyethylene wood-plastic composite material, a polyvinyl chloride wood-plastic composite material or a polypropylene wood-plastic composite material.
3. The preparation method of the layer-by-layer self-assembled flame-retardant wood-plastic composite material according to claim 1, characterized in that: the modified multi-walled carbon nanotube in the third step is a hydroxylated multi-walled carbon nanotube, a carboxylated multi-walled carbon nanotube, an aminated multi-walled carbon nanotube, a graphitized multi-walled carbon nanotube, a hydroxyl graphitized multi-walled carbon nanotube or a carboxyl graphitized multi-walled carbon nanotube.
4. The preparation method of the layer-by-layer self-assembled flame-retardant wood-plastic composite material according to claim 1, characterized in that: polishing the wood-plastic composite material in the step one to remove the plastic covered on the surface, and then cleaning and drying the wood-plastic composite material, wherein the polishing step is specifically carried out according to the following steps: the wood-plastic composite material is polished by using 100-mesh abrasive paper to remove plastic covered on the surface, then the surface is swept by using vacuum gas, washed by using ethanol and deionized water in sequence, and finally dried in an oven at the temperature of 30-60 ℃.
5. The preparation method of the layer-by-layer self-assembled flame-retardant wood-plastic composite material according to claim 1, characterized in that: and step two, dissolving the branched polyethyleneimine in deionized water, adjusting the pH to 9-10 by using hydrochloric acid with the concentration of 0.5-1.0 mol/L, and stirring at room temperature for 24-36 h.
6. The preparation method of the layer-by-layer self-assembled flame-retardant wood-plastic composite material according to claim 1, characterized in that: in the fourth step, the sodium-based montmorillonite is dissolved in the deionized water and stirred for 24 to 36 hours.
7. The preparation method of the layer-by-layer self-assembly flame-retardant wood-plastic composite material as claimed in claim 1, wherein the spraying in the step five ① and the step five ② is carried out by uniformly spraying with a spray gun having a nozzle with an inner diameter of 0.5 mm-4 mm under the conditions that the distance from the surface of a sample is 20 cm-40 cm and the power is 400W-800W.
8. The preparation method of the layer-by-layer self-assembly flame-retardant wood-plastic composite material as claimed in claim 1, wherein the cationic dispersion liquid in the step five ① is sprayed by 0.04 mL-0.08 mL per square centimeter, and the anionic dispersion liquid in the step five ① is sprayed by 0.04 mL-0.08 mL per square centimeter.
9. The preparation method of the layer-by-layer self-assembly flame-retardant wood-plastic composite material as claimed in claim 1, wherein the cationic dispersion liquid in the step five ② is sprayed by 0.02 mL-0.04 mL per square centimeter, and the anionic dispersion liquid in the step five ② is sprayed by 0.02 mL-0.04 mL per square centimeter.
10. The preparation method of the layer-by-layer self-assembled flame-retardant wood-plastic composite material according to claim 1, characterized in that: the volume ratio of the mass of the branched polyethyleneimine to the deionized water in the step II is 1g (100-200) mL; the mass ratio of the multi-walled carbon nanotube or the modified multi-walled carbon nanotube in the third step to the branched polyethyleneimine in the second step is (0.1-0.2): 1; the volume ratio of the mass of the sodium montmorillonite to the deionized water in the fourth step is 1g (100-200) mL.
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| CN114196318B (en) * | 2021-11-22 | 2022-12-23 | 广西南宁都宁通风防护设备有限公司 | Method for modifying and flame retarding high-molecular composite explosion door plate and raw material liquid used by method |
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