CN116120640B - Expansion type nano composite flame retardant, preparation method thereof and application thereof in wood-plastic composite material - Google Patents

Expansion type nano composite flame retardant, preparation method thereof and application thereof in wood-plastic composite material Download PDF

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CN116120640B
CN116120640B CN202310037031.3A CN202310037031A CN116120640B CN 116120640 B CN116120640 B CN 116120640B CN 202310037031 A CN202310037031 A CN 202310037031A CN 116120640 B CN116120640 B CN 116120640B
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wood
flame retardant
plastic composite
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montmorillonite
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CN116120640A (en
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房轶群
杨若凡
任癸林
林博昊
朱景航
王伟宏
宋永明
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Northeast Forestry University
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Abstract

The invention provides an expansion type nano composite flame retardant, a preparation method thereof and application thereof in wood-plastic composite materials. The in-situ synthesis method can enhance the binding force between the two-dimensional montmorillonite nano-sheets and the melamine metal phytate nano-sheets, so that the two-dimensional montmorillonite nano-sheets and the melamine metal phytate nano-sheets form a firmly-combined whole. The combination of the two-dimensional montmorillonite nano-plate, melamine (serving as an air source), phytic acid (serving as an acid source and a carbon source) and transition metal ions (serving as smoke suppression factors) can remarkably improve the flame retardant property and the smoke suppression property of the wood-plastic composite material. The expansion type nano composite flame retardant can greatly improve the flame retardant efficiency and smoke suppression efficiency of the wood-plastic composite material under the condition that the addition amount is not increased, and can also effectively improve the mechanical properties (such as mechanical properties) of the wood-plastic composite material, thereby solving the defect that the mechanical properties (such as mechanical properties) are greatly deteriorated due to the large addition amount of the flame retardant in the existing wood-plastic composite material.

Description

Expansion type nano composite flame retardant, preparation method thereof and application thereof in wood-plastic composite material
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to an intumescent nanocomposite flame retardant, a preparation method thereof and application thereof in wood-plastic composite materials.
Background
The wood-plastic composite material is a novel composite material which is prepared by taking wood fiber materials in the forms of fiber, powder and the like as filling or reinforcing materials, taking thermoplastic resin (such as polyethylene, polypropylene, polystyrene, polyvinyl chloride and the like) as a matrix material, adding various auxiliary agents and compounding by various processing means such as extrusion, hot pressing, mould pressing or injection molding. The wood-plastic composite material has the advantages of good processability, good sound absorption effect, energy conservation, environmental protection and the like, and the application of the wood-plastic composite material is expanded to the fields of building doors and windows, interior decoration, furniture and the like. However, the wood-plastic composite material which is not subjected to the fireproof and flame-retardant treatment is easy to burn, and generates a large amount of dense smoke and toxic gas during burning, so that the application of the wood-plastic composite material in the field with higher fireproof safety requirements is limited. Therefore, the improvement of the flame retardant property and the smoke suppression property of the wood-plastic composite material has become a necessary requirement for the further development of the material.
In recent years, in order to improve the flame retardant property and smoke suppression property of wood-plastic composite materials, flame retardants are often required to be added in the preparation of such composite materials. The intumescent flame retardant is a high-efficiency flame retardant capable of generating an acid source, an air source and a carbon source by heating, and can greatly improve the flame retardant property of the wood-plastic composite material. However, the addition amount of the intumescent flame retardant is large, and the mechanical properties of the wood-plastic composite material are deteriorated.
Disclosure of Invention
Aiming at the defects that the existing flame-retardant wood-plastic composite material has large addition amount of an intumescent flame retardant, seriously affects the mechanical properties (such as mechanical properties) of the wood-plastic composite material, has low flame retardant efficiency and smoke suppression efficiency and the like, the invention provides an intumescent nano composite flame retardant, a preparation method thereof and application thereof in the wood-plastic composite material. The expansion type nano composite flame retardant can greatly improve the flame retardant efficiency and smoke suppression efficiency of the wood-plastic composite material under the condition that the addition amount is not increased, and can also effectively improve the mechanical properties (such as mechanical properties) of the wood-plastic composite material, thereby solving the defect that the mechanical properties (such as mechanical properties) are greatly deteriorated due to the large addition amount of the flame retardant in the existing wood-plastic composite material.
The invention aims at realizing the following technical scheme:
a method for preparing an intumescent nanocomposite flame retardant, the method comprising the steps of:
(1) Mixing montmorillonite and sodium alginate to prepare a suspension 1;
(2) Dropwise adding the suspension 1 in the step (1) into an aqueous solution of transition metal salt, and performing a crosslinking reaction to prepare hydrogel spheres;
(3) Drying the hydrogel spheres in the step (2) and calcining to prepare two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides;
(4) Mixing the two-dimensional montmorillonite nano-sheets loaded with the transition metal nano-oxides in the step (3) with an aqueous solution of phytic acid, and reacting to obtain a suspension 2;
(5) And (3) dropwise adding the suspension liquid 2 obtained in the step (4) into an aqueous solution of melamine, and reacting to obtain the intumescent nanocomposite flame retardant.
According to an embodiment of the present invention, in the step (1), the montmorillonite has a lamellar structure, the average thickness of montmorillonite lamellar layers is 80nm to 120nm, and the average length of montmorillonite lamellar layers is 5 μm to 10 μm.
According to an embodiment of the present invention, in the step (1), the mass ratio of montmorillonite to sodium alginate is 1 (5-10), for example, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.
According to an embodiment of the invention, in step (1), the mixing is performed in the presence of water.
According to an embodiment of the present invention, in the step (1), the method specifically includes the following steps:
adding montmorillonite into water, stirring and ultrasonic treatment, adding sodium alginate, stirring until the sodium alginate is completely dissolved, and standing for 12-24 hours at room temperature to obtain a uniformly dispersed suspension 1.
Preferably, montmorillonite is added into deionized water, stirred and sonicated for 10-30 min, then sodium alginate is added, stirred at 60-100 ℃ until sodium alginate is completely dissolved, and left to stand at room temperature for 12-24 hours, thus obtaining uniformly dispersed suspension 1.
Preferably, the mass ratio of montmorillonite to water is (0.1-0.3): 100, for example 0.1:100, 0.2:100 or 0.3:100.
Preferably, after every 4 to 6 hours of standing in the standing process, ultrasonic treatment is performed for 1 to 2 hours, and then the standing and ultrasonic treatment are performed.
According to an embodiment of the present invention, in step (2), the transition metal salt is selected from at least one of zinc salt, tin salt, chromium salt, iron salt, cobalt salt, nickel salt and copper salt. Preferably, the transition metal salt is selected from at least one of zinc nitrate, tin chloride, chromium nitrate, iron nitrate, cobalt nitrate, nickel nitrate, and copper nitrate.
According to an embodiment of the present invention, in the step (2), the aqueous solution of the transition metal salt may include one kind of transition metal salt or may include two or more kinds of transition metal salts.
According to an embodiment of the present invention, in the step (2), the concentration of the transition metal salt in the aqueous solution of the transition metal salt is 15 to 30g/L.
According to an embodiment of the present invention, in the step (2), the mass ratio of the suspension 1 to the aqueous solution of the transition metal salt is (30 to 50): 100, for example 30:100, 35:100, 40:100, 45:100 or 50:100.
According to an embodiment of the present invention, in the step (2), the temperature of the crosslinking reaction is room temperature, and the time of the crosslinking reaction is 12 to 20 hours.
According to the embodiment of the invention, in the step (2), deionized water is adopted to wash the hydrogel sphere for 2-5 times, and the transition metal ions adsorbed on the surface of the hydrogel sphere are removed.
According to an embodiment of the present invention, in the step (2), the hydrogel sphere has a diameter of 2mm to 5mm. The diameter of the hydrogel sphere can be controlled by controlling the size of the droplets of the suspension 1.
According to an embodiment of the present invention, in step (2), the transition metal salt is used to form a transition metal nano-oxide supported on the surface of the two-dimensional montmorillonite nano-sheet.
According to an embodiment of the present invention, in step (3), the drying temperature is 50 to 100 ℃.
According to an embodiment of the present invention, in the step (3), the calcination is performed at a temperature of 400 to 800 ℃ (e.g., 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃), the calcination is performed for a time of 2 to 6 hours (e.g., 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours), and the calcination atmosphere is an air atmosphere.
According to an embodiment of the present invention, in the step (4), the mass ratio of the transition metal nano oxide loaded two-dimensional montmorillonite nano sheet to the phytic acid is 1 (4-9), for example, 1:4, 1:5, 1:6, 1:7, 1:8 or 1:9.
According to an embodiment of the present invention, in step (4), the temperature of the reaction is room temperature.
According to an embodiment of the present invention, in the step (4), the phytic acid reacts with the transition metal nano oxide to form a metal ion, and the metal ion and the phytic acid undergo a complexing reaction in situ to form a complex.
According to an embodiment of the present invention, in the step (4), the concentration of the aqueous solution of phytic acid is 0.1 to 0.2mol/L.
According to an embodiment of the invention, in step (5), the mass ratio of phytic acid to melamine in the suspension 2 is 1 (0.8-1.4), for example 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3 or 1:1.4.
According to an embodiment of the invention, in step (5), the concentration of the aqueous melamine solution is between 0.2 and 0.3mol/L.
According to an embodiment of the present invention, in the step (5), the temperature of the reaction is 80 to 95 ℃, and the time of the reaction is 3 to 6 hours.
According to an embodiment of the invention, in step (5), the hydroxyl groups of the phytic acid and the amine groups of the melamine are reacted.
According to an embodiment of the present invention, in the step (5), after the completion of the reaction, the reaction solution is cooled to normal temperature, and the reactant is precipitated in water.
According to an embodiment of the present invention, in the step (5), after the reaction is completed, collecting a precipitated product by a suction filtration method, and repeatedly washing with deionized water to be neutral; finally, drying at 60-100 ℃ to prepare the intumescent nanocomposite flame retardant.
The invention also provides the intumescent nanocomposite flame retardant prepared by the method.
According to an embodiment of the invention, the intumescent nanocomposite flame retardant comprises melamine metal phytate nano-sheets and two-dimensional montmorillonite nano-sheets, wherein the melamine metal phytate nano-sheets are loaded on the surfaces of the two-dimensional montmorillonite nano-sheets.
According to the embodiment of the invention, the mass ratio of the melamine metal phytate nano-sheet to the two-dimensional montmorillonite nano-sheet is 5 (0.7-1.2), for example, 5:0.7, 5:0.8, 5:0.9, 5:1.0, 5:1.1 or 5:1.2.
According to the embodiment of the invention, the preparation raw materials of the melamine metal phytate nanosheets comprise phytic acid, transition metal nano oxides and melamine.
According to the embodiment of the invention, the phytic acid reacts with the transition metal nano oxide to form metal ions, the metal ions and the phytic acid undergo a complex reaction in situ to form a complex, and the hydroxyl in the phytic acid reacts with the amino in the melamine to form the melamine metal phytate nano-sheet.
According to the embodiment of the invention, the melamine metal phytate nanosheets can be rapidly decomposed to generate melamine, phytic acid and metal ions under the heating condition.
The invention also provides application of the expansion type nano composite flame retardant in wood-plastic composite materials.
The invention also provides a wood-plastic composite material, which comprises the expansion type nano composite flame retardant.
According to an embodiment of the invention, the wood-plastic composite further comprises a thermoplastic resin.
According to an embodiment of the present invention, the thermoplastic resin is selected from at least one of polyethylene, polypropylene, polystyrene, and polyvinyl chloride resin.
According to an embodiment of the present invention, the wood-plastic composite further comprises at least one of plant fiber powder and a lubricant.
According to an embodiment of the present invention, the wood-plastic composite further comprises at least one of a heat stabilizer and an impact modifier.
According to the embodiment of the invention, the wood-plastic composite material comprises the following components in parts by mass:
100 parts by mass of a thermoplastic resin;
60-120 parts by mass of plant fiber powder; preferably 60, 70, 80, 90, 100, 110 or 120 parts by mass;
10-40 parts by mass of an expansion type nano composite flame retardant; preferably 10, 20, 30 or 40 parts by mass;
0.8 to 3 parts by mass of lubricant; preferably 0.8, 0.9, 1, 1.1, 1.2, 1.5, 1.7, 1.8, 2, 2.4, 2.5, 2.6, 2.8 or 3 parts by mass.
According to the embodiment of the invention, the wood-plastic composite material further comprises the following components in percentage by mass:
0-6 parts by mass of a heat stabilizer; preferably 0.5, 1, 2, 3, 4, 5 or 6 parts by mass;
0-4 parts by mass of impact modifier; preferably 0.5, 1, 1.5, 2, 2.5, 3, 3.5 or 4 parts by mass;
according to an embodiment of the present invention, when the thermoplastic resin is polyvinyl chloride, a heat stabilizer and an impact modifier are preferably added.
According to an embodiment of the present invention, the particle size of the plant fiber powder is 80 to 200 mesh.
According to an embodiment of the present invention, the plant fiber powder is selected from at least one of poplar powder, bamboo powder, crop straw powder and fruit shell powder.
According to an embodiment of the present invention, the lubricant is at least one selected from stearic acid, stearate, paraffin wax, polyethylene wax; wherein the stearate is at least one selected from sodium stearate, potassium stearate, calcium stearate and zinc stearate.
According to an embodiment of the present invention, the heat stabilizer is selected from the group consisting of organotin-based and metal soap-based heat stabilizers, for example, at least one of calcium zinc heat stabilizer, barium zinc heat stabilizer, and potassium zinc heat stabilizer.
According to an embodiment of the present invention, the impact modifier is selected from at least one of chlorinated polyethylene, polyacrylate, ethylene-vinyl acetate copolymer, and methyl methacrylate-butadiene-styrene terpolymer.
According to the embodiment of the invention, the wood-plastic composite material is a flame-retardant smoke-suppressing wood-plastic composite material.
The invention also provides a preparation method of the wood-plastic composite material, which comprises the following steps:
(a) Respectively weighing thermoplastic resin, plant fiber powder, an expansion type nano composite flame retardant, a lubricant, a heat stabilizer which is optionally added or not added and an impact modifier which is optionally added or not added according to the parts by mass, and mixing to obtain a material;
(b) And (c) extruding and molding the material obtained in the step (a) through a screw extruder to prepare the wood-plastic composite material.
According to an embodiment of the invention, in step (a), the mixing is performed in a high speed mixer.
According to an embodiment of the present invention, in step (b), the extrusion may be performed in a twin-screw extruder or in a single-screw extruder. The extrusion speed of the twin-screw extruder is 20-30 rpm, and the extrusion speed of the single-screw extruder is 5-8 rpm.
According to an embodiment of the invention, in step (b), the temperature of the processing zone is 140 to 180℃and the die temperature is 150 to 170℃during extrusion. During extrusion, the extrusion temperature is maintained below 200 ℃ to reduce thermal decomposition of the plant fiber powder and the thermoplastic resin.
The invention has the beneficial effects that:
the invention uses the negative-charged sodium alginate to weaken the interlayer acting force of the positive-charged montmorillonite, so that the montmorillonite layers gradually slip and peel off to prepare the two-dimensional montmorillonite nano-sheets, and simultaneously the carboxyl of the sodium alginate and positive ions on the two-dimensional montmorillonite nano-sheets are firmly combined together through electrostatic attraction; and then the cations of the sodium alginate are further subjected to displacement reaction with transition metal ions to crosslink the hydrogel spheres, and finally carbon in the sodium alginate is removed by calcination, so that the composite of the transition metal nano oxide loaded on the two-dimensional montmorillonite nano sheet is obtained. On the basis, phytic acid is introduced, the phytic acid can react with the transition metal nano oxide to form metal ions, the metal ions and the phytic acid are subjected to in-situ complexing reaction to form a complex, finally, the hydroxyl of the phytic acid and the amino of melamine react to form melamine metal phytate nano-sheets, and the melamine metal phytate nano-sheets are loaded on the surfaces of the two-dimensional montmorillonite nano-sheets. The two-dimensional montmorillonite nano sheet has strong rigidity, can counteract the defect that the mechanical property of the wood-plastic composite material is greatly reduced after the expansion type flame retardant is added, and can also ensure that the wood-plastic composite material has good flame retardant effect and smoke suppression effect.
Moreover, montmorillonite, sodium alginate and phytic acid belong to biomass renewable resources, and are green, nontoxic and environment-friendly, the intumescent nanocomposite flame retardant can get rid of dependence on petroleum-based raw materials, the preparation process is simple, and the reaction conditions are easy to control.
The in-situ synthesis method can enhance the binding force between the two-dimensional montmorillonite nano-sheets and the melamine metal phytate nano-sheets, so that the two-dimensional montmorillonite nano-sheets and the melamine metal phytate nano-sheets form a firmly-combined whole. The combination of the two-dimensional montmorillonite nano-sheets, the melamine (serving as an air source), the phytic acid (serving as an acid source and a carbon source) and the transition metal ions (serving as smoke suppression factors) can remarkably improve the flame retardant property and the smoke suppression property of the wood-plastic composite material, mainly because the melamine metal phytate nano-sheets can be rapidly decomposed to generate the melamine, the phytic acid and the metal ions when the wood-plastic composite material is combusted, nitrogen elements in the melamine and phosphorus elements and carbon elements in the phytic acid have flame retardant synergistic effect when the wood-plastic composite material is combusted, an intumescent flame retardant system is formed, the metal ions have the effect of catalyzing and crosslinking to form carbon, a carbon layer can be more compact and continuous, and oxygen and heat are prevented from being transmitted to the inside of the wood-plastic composite material, so that the wood-plastic composite material has better flame retardant effect and smoke suppression effect; in addition, the two-dimensional montmorillonite nano-sheets have a blocking effect, can cooperatively achieve the purpose of delaying volatilization of inflammable gas and oxygen diffusion, and further improve the flame retardant property of the wood-plastic composite material.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
(1) Adding 0.5g of montmorillonite (average thickness is 80nm, average length is 5 μm) into 180g of deionized water, stirring and ultrasonic treating for 10min, adding 2.5g of sodium alginate, stirring at 70deg.C until completely dissolved, and standing for 14 hr to obtain uniform suspension 1;
(2) Dropwise adding 30g of suspension 1 from step (1) to 100gZn (NO) 3 ) 2 . 6H 2 Stirring and crosslinking reaction for 16 hours in O aqueous solution (the concentration is 15 g/L), filtering to obtain hydrogel balls with the diameter of 3mm, and washing the hydrogel balls with deionized water for 2 times;
(3) Drying the hydrogel spheres in the step (2) at 60 ℃ for 25 hours, and calcining at 500 ℃ for 6 hours in an air atmosphere to obtain two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides;
(4) Stirring and mixing 1g of transition metal nano oxide loaded two-dimensional montmorillonite nano sheet in the step (3) with 4g of phytic acid (added in the form of phytic acid aqueous solution, wherein the concentration of the phytic acid aqueous solution is 0.1 mol/L) to obtain a suspension liquid 2;
(5) 1g of the suspension 2 obtained in the step (4) was added dropwise to 33ml of an aqueous melamine solution (concentration: 0.2 mol/L), stirred at 90℃for 6 hours, and then cooled to room temperature, and the reaction product was precipitated in water. Then filtering and collecting a precipitate, and repeatedly washing with deionized water to neutrality; and finally, drying the obtained precipitate at 80 ℃ to prepare the intumescent nanocomposite flame retardant, wherein the mass ratio of the melamine metal phytate nano-sheet to the two-dimensional montmorillonite nano-sheet in the intumescent nanocomposite flame retardant is 5:1, and the melamine metal phytate nano-sheet is loaded on the surface of the two-dimensional montmorillonite nano-sheet.
(6) Weighing 45g of polypropylene resin, 30g of poplar powder, 9g of the intumescent nanocomposite flame retardant in the step (5) and 0.8g of sodium stearate, and mixing in a high-speed mixer to obtain a material;
(7) Extruding the material obtained in the step (6) by a single screw extruder (the temperature of a processing area is controlled to be 162 ℃, the temperature of a die head is controlled to be 170 ℃, the rotating speed of a host machine is 8rpm, and the current of the host machine is 16A).
Example 2
(1) 0.5g of montmorillonite (average thickness 120nm, average length 10 μm) was added to 250g of deionized water, stirred and sonicated for 30min, then 3g of sodium alginate was added, stirred at 90 ℃ until completely dissolved, and then left to stand for 16 hours to give a uniform suspension 1.
(2) Dropwise adding 40g of suspension 1 obtained in step (1) to 100g of SnCl 4 . 5H 2 Stirring and crosslinking reaction for 24 hours in O aqueous solution (the concentration is 30 g/L), filtering to obtain hydrogel balls with the diameter of 5mm, and washing with deionized water for 4 times;
(3) Drying the hydrogel spheres in the step (2) at 70 ℃ for 20 hours, and calcining at 600 ℃ for 5 hours in an air atmosphere to obtain two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides;
(4) Stirring and mixing 1g of transition metal nano oxide loaded two-dimensional montmorillonite nano sheet in the step (3) with 5g of phytic acid (added in the form of phytic acid aqueous solution, wherein the concentration of the phytic acid aqueous solution is 0.15 mol/L) to obtain a suspension liquid 2;
(5) 1g of the suspension 2 obtained in the step (4) was added dropwise to 37ml of an aqueous melamine solution (concentration: 0.25 mol/L), stirred at 90℃for 6 hours, and then cooled to room temperature, and the reaction product was precipitated in water. Then vacuum filtering and collecting a precipitate, and repeatedly washing with deionized water until the filtrate is neutral; finally, vacuum drying the obtained precipitate at 60 ℃ to prepare the intumescent nanocomposite flame retardant, wherein the mass ratio of the melamine metal phytate nano-plate to the two-dimensional montmorillonite nano-plate in the intumescent nanocomposite flame retardant is 5:0.8, and the melamine metal phytate nano-plate is loaded on the surface of the two-dimensional montmorillonite nano-plate.
(6) Weighing 45g of polypropylene resin, 30g of poplar powder, 6.3g of the expansion type nano composite flame retardant in the step (5) and 1.2g of zinc stearate, and mixing in a high-speed mixer to obtain a material;
(7) Extruding the material obtained in the step (5) by a double-screw extruder (the temperature of a processing area is controlled at 155 ℃, the temperature of a die head is 170 ℃, the rotating speed of a host machine is 20rpm, and the current of the host machine is 22A).
Example 3
(1) Adding 0.5g of montmorillonite (with the average thickness of 100nm and the average length of 8 μm) into 300g of deionized water, stirring and carrying out ultrasonic treatment for 20min, adding 4g of sodium alginate, stirring at 80 ℃ until the sodium alginate is completely dissolved, and standing for 20 hours to obtain a uniform suspension;
(2) 120g of suspension 1 from step (1) was added dropwise to 400g of Cu (NO) 3 ) 2 . 3H 2 Stirring and crosslinking reaction for 20 hours in O aqueous solution (the concentration is 18 g/L), filtering to obtain hydrogel balls with the diameter of 4mm, and washing with deionized water for 3 times;
(3) Drying the hydrogel spheres in the step (2) at 90 ℃ for 20 hours, and calcining the hydrogel spheres at 700 ℃ for 4 hours in an air atmosphere to obtain two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides;
(4) Stirring and mixing 1g of transition metal nano oxide loaded two-dimensional montmorillonite nano sheet in the step (3) with 6g of phytic acid (added in the form of phytic acid aqueous solution, wherein the concentration of the phytic acid aqueous solution is 0.2 mol/L) to obtain a suspension liquid 2;
(5) 1g of the suspension 2 obtained in the step (4) was added dropwise to 28ml of an aqueous melamine solution (concentration: 0.3 mol/L), stirred at 90℃for 6 hours, and then cooled to room temperature, whereupon the reaction product precipitated in water. Then vacuum filtering and collecting a precipitate, and repeatedly washing with deionized water until the filtrate is neutral; finally, vacuum drying the obtained precipitate at 60 ℃ to prepare the intumescent nanocomposite flame retardant, wherein the mass ratio of the melamine metal phytate nano-plate to the two-dimensional montmorillonite nano-plate in the intumescent nanocomposite flame retardant is 5:1.1, and the melamine metal phytate nano-plate is loaded on the surface of the two-dimensional montmorillonite nano-plate.
(6) Weighing 45g of polypropylene resin, 30g of poplar powder, 11.25g of the intumescent nanocomposite flame retardant in the step (5) and 0.8g of stearic acid, and mixing in a high-speed mixer to obtain a material;
(7) Extruding the material obtained in the step (5) by a single screw extruder (the temperature of a processing area is controlled at 160 ℃, the temperature of a die head is 165 ℃, the rotating speed of a host machine is 8rpm, and the current of the host machine is 20A).
Comparative example 1
The preparation of the wood-plastic composite was the same as in example 1, except that no intumescent nanocomposite flame retardant was added.
Comparative example 2
The preparation of the wood-plastic composite is the same as in example 1, except that:
the added flame retardant is melamine metal phytate nano-sheet. The preparation method of the melamine metal phytate nanosheets is as follows:
(1) Will be 2.6gZn (NO 3 ) 2 . 6H 2 O and 4g of phytic acid (added in the form of phytic acid aqueous solution, the concentration of which is 0.1 mol/L) are stirred and mixed to obtain a uniform solution;
(2) 1g of the homogeneous solution obtained in the step (1) is added dropwise into 33ml of an aqueous solution of melamine (concentration: 0.2 mol/L), stirred at 90 ℃ for 6 hours, cooled to normal temperature after sufficient reaction, and the reactant is precipitated in water. Then filtering and collecting a precipitate, and repeatedly washing with deionized water to neutrality; and finally, drying the obtained precipitate at 80 ℃ to prepare the melamine metal phytate nanosheets.
Comparative example 3
The preparation of the wood-plastic composite is the same as in example 1, except that:
the added flame retardant is montmorillonite, the average thickness of the montmorillonite is 80nm, and the average length is 5 mu m.
Comparative example 4
The preparation of the wood-plastic composite is the same as in example 1, except that:
the added intumescent nano composite flame retardant is different, and the intumescent nano composite flame retardant of the comparative example is prepared by directly and uniformly mixing the melamine metal phytate nano sheet of the comparative example 2 and the montmorillonite of the comparative example 3 according to the mass ratio of 5:1.
Performance test:
flame retardant and smoke suppression performance: the flame retardant and smoke suppression performance of the polypropylene wood-plastic composite material is detected by adopting a cone calorimeter, and the radiation power is 50Kw/m according to the international standard ISO5660-1-2002 2 The flame retardant and smoke suppression performance test results are shown in Table 1.
Mechanical properties: the tensile properties were tested according to ASTM D638, with a tensile speed of 5mm/min. The bending performance test was conducted according to ASTM D790, three-point bending mode, span 64mm, load speed 1.9mmm/min, and mechanical properties test results are shown in Table 2.
TABLE 1 flame retardant and smoke suppressant Performance test results
TABLE 2 mechanical test results
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (20)

1. A method for preparing an intumescent nanocomposite flame retardant, the method comprising the steps of:
(1) Mixing montmorillonite and sodium alginate to prepare a suspension 1;
(2) Dropwise adding the suspension 1 in the step (1) into an aqueous solution of transition metal salt, and performing a crosslinking reaction to prepare hydrogel spheres;
(3) Drying the hydrogel spheres in the step (2) and calcining to prepare two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides;
(4) Mixing the two-dimensional montmorillonite nano-sheets loaded with the transition metal nano-oxides in the step (3) with an aqueous solution of phytic acid, and reacting to obtain a suspension 2;
(5) And (3) dropwise adding the suspension liquid 2 obtained in the step (4) into an aqueous solution of melamine, and reacting to obtain the intumescent nanocomposite flame retardant.
2. The preparation method according to claim 1, wherein in the step (1), the montmorillonite has a lamellar structure, the average thickness of the montmorillonite lamellar is 80nm to 120nm, and the average length of the montmorillonite lamellar is 5 μm to 10 μm;
and/or in the step (1), the mass ratio of the montmorillonite to the sodium alginate is 1 (5-10).
3. The production method according to claim 1, wherein in the step (2), the transition metal salt is selected from at least one of zinc salt, tin salt, chromium salt, iron salt, cobalt salt, nickel salt and copper salt;
and/or, in the step (2), the mass ratio of the suspension 1 to the aqueous solution of the transition metal salt is (30-50): 100.
4. the production method according to claim 3, wherein the transition metal salt is at least one selected from zinc nitrate, tin chloride, chromium nitrate, iron nitrate, cobalt nitrate, nickel nitrate and copper nitrate.
5. The production method according to claim 1, wherein in the step (3), the calcination temperature is 400 to 800 ℃, the calcination time is 2 to 6 hours, and the calcination atmosphere is an air atmosphere.
6. The preparation method of claim 1, wherein in the step (4), the mass ratio of the transition metal nano oxide loaded two-dimensional montmorillonite nano sheet to the phytic acid is 1 (4-9).
7. The process according to claim 1, wherein in the step (5), the mass ratio of the phytic acid to the melamine in the suspension 2 is 1 (0.8 to 1.4).
8. The production method according to claim 1, wherein in the step (5), the reaction is carried out at a temperature of 80 to 95℃for a time of 3 to 6 hours.
9. The intumescent nanocomposite flame retardant prepared by the method of any one of claims 1-8.
10. The intumescent nanocomposite flame retardant of claim 9, wherein the intumescent nanocomposite flame retardant comprises melamine metal phytate nanosheets and two-dimensional montmorillonite nanosheets, wherein the melamine metal phytate nanosheets are supported on two-dimensional montmorillonite nanosheets surfaces.
11. The intumescent nanocomposite flame retardant of claim 10, wherein the mass ratio of melamine metal phytate nano-sheets to two-dimensional montmorillonite nano-sheets is 5 (0.7-1.2).
12. Use of the intumescent nanocomposite flame retardant of any of claims 9-11 in wood plastic composites.
13. A wood-plastic composite comprising the intumescent nanocomposite flame retardant of any of claims 9-11.
14. The wood-plastic composite of claim 13, wherein the wood-plastic composite further comprises a thermoplastic resin.
15. The wood-plastic composite according to claim 14, wherein the thermoplastic resin is selected from at least one of polyethylene, polypropylene, polystyrene, and polyvinyl chloride resin.
16. The wood-plastic composite according to claim 13, wherein the wood-plastic composite further comprises at least one of plant fiber powder and a lubricant;
and/or the wood-plastic composite further comprises at least one of a heat stabilizer and an impact modifier.
17. The wood-plastic composite according to claim 13, wherein the wood-plastic composite comprises the following components in parts by mass:
100 parts by mass of a thermoplastic resin;
60-120 parts by mass of plant fiber powder;
10-40 parts by mass of an expansion type nano composite flame retardant;
0.8 to 3 parts by mass of lubricant.
18. The wood-plastic composite of claim 17, wherein the wood-plastic composite further comprises the following components in mass fraction:
0-6 parts by mass of a heat stabilizer;
0 to 4 parts by mass of impact modifier.
19. A method of preparing a wood-plastic composite according to any one of claims 13 to 18, the method comprising the steps of:
(a) Respectively weighing thermoplastic resin, plant fiber powder, an expansion type nano composite flame retardant, a lubricant, a heat stabilizer which is optionally added or not added, and an impact modifier which is optionally added or not added according to parts by mass, and mixing to obtain a material;
(b) And (c) extruding and molding the material obtained in the step (a) through a screw extruder to prepare the wood-plastic composite material.
20. The method of claim 19, wherein in step (a), the mixing is performed in a high speed mixer;
and/or, in the step (b), the temperature of the processing area is 140-180 ℃ and the temperature of the die head is 150-170 ℃ in the extrusion process.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105175786A (en) * 2015-10-21 2015-12-23 郑叶芳 Montmorillonite composite flame retardant and preparation method thereof
CN109320766A (en) * 2018-09-19 2019-02-12 九江学院 A kind of expansion type flame retardant and preparation method thereof
CN110951191A (en) * 2019-12-16 2020-04-03 无锡市华美电缆有限公司 Cable material containing supramolecular self-assembly flame retardant and preparation method thereof
CN113150382A (en) * 2021-03-03 2021-07-23 中国安全生产科学研究院 Modified melamine phytate flame retardant and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105175786A (en) * 2015-10-21 2015-12-23 郑叶芳 Montmorillonite composite flame retardant and preparation method thereof
CN109320766A (en) * 2018-09-19 2019-02-12 九江学院 A kind of expansion type flame retardant and preparation method thereof
CN110951191A (en) * 2019-12-16 2020-04-03 无锡市华美电缆有限公司 Cable material containing supramolecular self-assembly flame retardant and preparation method thereof
CN113150382A (en) * 2021-03-03 2021-07-23 中国安全生产科学研究院 Modified melamine phytate flame retardant and preparation method and application thereof

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