A flame retardant material based on antimony trioxide and a method for its production

Abstract

This invention relates to the field of flame retardant materials, specifically to an antimony trioxide-based flame retardant material and its preparation method, which is composed of antimony trioxide particles and alkoxylated black phosphorus coated thereon. The antimony trioxide particles have a porous structure. The antimony trioxide-based flame retardant material of this invention not only has excellent flame retardant properties, but also provides a new technical path for the development of efficient, low-smoke, and environmentally friendly flame retardant materials.

Description

Technical Field

[0001] This invention relates to the field of flame retardant materials, specifically to an antimony trioxide-based flame retardant material and its preparation method. Background Technology

[0002] With the rapid development of modern industry, polymer materials have been widely used in construction, transportation, electronics, aerospace and other fields due to their advantages such as light weight, ease of processing, and low cost. However, most polymer materials are flammable, releasing large amounts of heat, smoke and toxic gases when burned, seriously threatening personal safety and property security. Therefore, the development of efficient, environmentally friendly and low-toxicity flame-retardant materials has become a research hotspot and urgent need in the field of materials science.

[0003] Antimony trioxide is an important flame retardant synergist, widely used in polymer materials such as plastics, rubber, and coatings. It is also one of the most widely used inorganic flame retardants in polyvinyl chloride (PVC) materials. How to further improve the flame retardant effect of antimony trioxide has become a current research hotspot. Summary of the Invention

[0004] Purpose of the invention: To address the above-mentioned technical problems, this invention proposes an antimony trioxide-based flame retardant material and its preparation method.

[0005] The technical solution adopted is as follows: An antimony trioxide-based flame retardant material, composed of antimony trioxide particles and alkoxylated black phosphorus coated thereon.

[0006] Furthermore, the antimony trioxide particles have a porous structure.

[0007] Furthermore, the method for preparing the antimony trioxide particles is as follows: Antimony glycol and polyol phases are added to an oil phase containing a first emulsifier and white oil. After high-speed stirring, a P / O emulsion is obtained. The P / O emulsion is then added to an aqueous phase containing poloxamer and water. After high-speed stirring, the reaction is carried out by low-speed stirring. The mixture is allowed to stand, and the precipitate is collected by centrifugation, washed, and dried.

[0008] Furthermore, the polyol phase is a combination of dipropylene glycol and ethylene glycol in a mass ratio of 1-4:1-4.

[0009] Further, the first emulsifier is any one or more combinations of Span-20, Span-40, Span-60, and Span-80.

[0010] Furthermore, the pH of the aqueous phase is 3-6.

[0011] This invention also provides a method for preparing the above-mentioned antimony trioxide-based flame retardant material, comprising: Sodium alkyl alkoxide reacts with black phosphorus nanosheets to generate alkoxylated black phosphorus; Positive charge modification on the surface of antimony trioxide particles; The two are mixed and electrostatically adsorbed for self-assembly; Heat treatment under argon protection.

[0012] Furthermore, the sodium alkyl alkoxide is any one of sodium hexanoate, sodium heptanol, sodium octanol, sodium nonanol, and sodium decanoate.

[0013] Furthermore, the surface of antimony trioxide particles was positively charged using a silane coupling agent.

[0014] Furthermore, the silane coupling agent is KH-550.

[0015] Furthermore, the heat treatment temperature is 200-400℃.

[0016] Furthermore, the antimony trioxide-based flame retardant material of the present invention is applied to polyvinyl chloride.

[0017] The beneficial effects of this invention are: This invention provides an antimony trioxide-based flame retardant material. Through interfacial engineering assembly of porous antimony trioxide particles and alkoxylated black phosphorus, a core-shell composite flame retardant material with a synergistic flame retardant effect is constructed. First, utilizing the property that antimony glycolate is soluble in ethylene glycol but insoluble in white oil, the oil phase isolates the antimony glycolate from the weakly acidic aqueous phase, preventing rapid hydrolysis that could lead to abnormally large and agglomerated antimony trioxide particles. During the low-speed stirring reaction, due to shear force, trace amounts of water enter the polyol phase and hydrolyze with the antimony glycolate, thereby controlling the size of the generated antimony trioxide. The addition of phosphate to the aqueous phase adjusts the pH and causes the charged emulsion particles to repel each other, improving the system's stability. This results in the synthesis of antimony trioxide with a unique porous microstructure. This porous structure not only provides abundant surface hydroxyl groups for subsequent silane coupling agent modification, but its pores can also physically adsorb free radicals and volatile combustibles generated during combustion, exerting a condensed-phase flame retardant effect.

[0018] Black phosphorus nanosheets were prepared via liquid-phase exfoliation. Alkoxylation treatment introduced active side chains onto the surface of the black phosphorus nanosheets, improving their solubility and dispersibility in organic solvents and laying the foundation for subsequent electrostatic adsorption self-assembly. A PN heterojunction structure was formed at the interface between the black phosphorus nanosheets and antimony trioxide. This heterojunction stemmed from the band matching between the p-type semiconductor properties of the black phosphorus nanosheets and the n-type semiconductor properties of antimony trioxide. The built-in electric field formed at the interface effectively promoted the separation of photogenerated or thermally excited charge carriers. During the heating or combustion of polymers (such as polyvinyl chloride), this charge separation effect significantly enhanced the kinetics of the catalytic carbonization reaction, specifically by lowering the activation energy of the carbonization reaction, thereby catalyzing the dehydration and cross-linking graphitization of the polymer matrix to form a denser and more complete protective carbon layer.

[0019] Silane coupling agents modify porous antimony trioxide particles, with the amino end facing the solution surface and carrying a positive charge, while alkoxylated black phosphorus carries a negative charge. The two achieve directional self-assembly through electrostatic attraction, so that black phosphorus nanosheets are uniformly coated on the surface of antimony trioxide particles. This electrostatic adsorption assembly process ensures uniform dispersion and close contact of black phosphorus, avoiding the problems of agglomeration and phase separation caused by physical mixing.

[0020] Antimony trioxide, a classic flame retardant, reacts with hydrogen chloride produced from the decomposition of polyvinyl chloride (PVC) in the gas phase to generate antimony trichloride, which captures active free radicals in the combustion chain and interrupts the free radical chain reaction. Black phosphorus nanosheets, as a two-dimensional layered material, exert a physical barrier effect; the phosphorus-oxygen free radicals released during thermal decomposition synergistically enhance the gas-phase flame retardant efficiency with antimony trichloride. The core-shell structure design allows for close contact between black phosphorus and antimony trioxide at the nanoscale, enhancing the synergistic effect through interfacial interactions and further improving flame retardant efficiency. Heat treatment curing ensures the stability and reliability of the interfacial bonding, ultimately achieving excellent flame retardant performance and providing a new technical path for developing high-efficiency, low-smoke, and environmentally friendly flame retardant materials. Detailed Implementation

[0021] Unless otherwise specified in the examples, the conditions were performed under standard conditions or as recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products. Techniques not mentioned in this invention refer to existing technologies. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters. Example 1:

[0022] An antimony trioxide-based flame retardant material is composed of antimony trioxide particles with a porous structure and black phosphorus coated thereon.

[0023] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0024] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium n-octanol were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected, washed with anhydrous ethanol, and dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 300℃ for 5 hours under argon protection. Example 2:

[0025] An antimony trioxide-based flame retardant material is composed of antimony trioxide particles with a porous structure and black phosphorus coated thereon.

[0026] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0027] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium n-octanol were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with anhydrous ethanol, the precipitate was dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 200℃ for 5 hours under argon protection. Example 3:

[0028] An antimony trioxide-based flame retardant material is composed of antimony trioxide particles with a porous structure and black phosphorus coated thereon.

[0029] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0030] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium n-octanol were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected, washed with anhydrous ethanol, and dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 400℃ for 5 hours under argon protection. Example 4:

[0031] An antimony trioxide-based flame retardant material is composed of antimony trioxide particles with a porous structure and black phosphorus coated thereon.

[0032] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0033] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium hexanoate were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected, washed with anhydrous ethanol, and dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 300℃ for 5 hours under argon protection. Example 5:

[0034] An antimony trioxide-based flame retardant material is composed of antimony trioxide particles with a porous structure and black phosphorus coated thereon.

[0035] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0036] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected and centrifuged again at 20000 rpm for 20 minutes. The precipitate was collected, washed with acetone and ethanol, and then vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium n-heptanol were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, the precipitate was collected, washed with anhydrous ethanol, and dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 300℃ for 5 hours under argon protection. Example 6:

[0037] An antimony trioxide-based flame retardant material is composed of antimony trioxide particles with a porous structure and black phosphorus coated thereon.

[0038] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0039] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium nonoxide were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with anhydrous ethanol, the precipitate was dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 300℃ for 5 hours under argon protection. Example 7:

[0040] An antimony trioxide-based flame retardant material is composed of antimony trioxide particles with a porous structure and black phosphorus coated thereon.

[0041] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0042] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium n-decanoate were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with anhydrous ethanol, the precipitate was dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 300℃ for 5 hours under argon protection.

[0043] Comparative Example 1: It is basically the same as Example 1, except that sodium methoxide is used instead of sodium n-octanol.

[0044] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0045] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets were mixed with sodium methoxide at a molar ratio of 1:1.5 and dispersed in 100 ml of dimethylformamide. The mixture was stirred at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected, washed with anhydrous ethanol, and dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 300℃ for 5 hours under argon protection.

[0046] Comparative Example 2: It is basically the same as Example 1, except that grinding and mixing are used instead of electrostatic adsorption self-assembly.

[0047] A method for preparing an antimony trioxide-based flame retardant material: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The O emulsion was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, then stirred at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid. The mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and then vacuum dried to obtain KH-550 modified antimony trioxide particles.

[0048] Grind 1g of black phosphorus crystals with 10ml of N-methylpyrrolidone in an agate grinding mortar for 3 hours. Then transfer the mixture to a 100ml brown bottle, add 90ml of N-methylpyrrolidone, purge with nitrogen to isolate air and seal. Sonicate in a water bath at room temperature for 10 hours. Centrifuge at 8000r / min for 20 minutes to remove large-sized products. Collect the supernatant and centrifuge at 20000r / min for 20 minutes. Collect the precipitate, wash with acetone and ethanol, and vacuum dry to obtain black phosphorus nanosheets. Mix 100mg of black phosphorus nanosheets with sodium n-octanol at a molar ratio of 1:1.5 in 100ml of dimethylformamide. Stir and react at room temperature under argon protection for 48 hours. After the reaction, centrifuge the solution at 20000r / min for 20 minutes, collect the precipitate, wash with anhydrous ethanol, and vacuum dry to obtain alkoxy black phosphorus nanosheets. Grind and mix the above alkoxy black phosphorus nanosheets with KH-550 modified antimony trioxide particles for 2 hours.

[0049] Comparative Example 3: It is basically the same as Example 1, except that the black phosphorus nanosheets are not treated with sodium n-octanol.

[0050] The preparation method of antimony trioxide-based flame retardant materials is as follows: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0051] Grind 1g of black phosphorus crystals with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours. Then transfer the mixture to a 100ml brown bottle, add 90ml of N-methylpyrrolidone, purge with nitrogen to isolate air and seal. Sonicate in a water bath at room temperature for 10 hours, centrifuge at 8000r / min for 20 minutes to remove large-sized products, collect the supernatant and centrifuge at 20000r / min for 20 minutes, collect the precipitate, wash with acetone and ethanol, and vacuum dry to obtain black phosphorus nanosheets. Disperse 100mg of black phosphorus nanosheets in 50ml of fresh anhydrous ethanol to obtain solution B. Slowly add solution B to solution A with stirring, then adjust the pH to 5-6 and stir at room temperature for 2 hours. Centrifuge at 20000r / min for 20 minutes, collect the precipitate, and heat-treat at 300℃ for 5 hours under argon protection.

[0052] Comparative Example 4: It is basically the same as Example 1, except that it does not undergo heat treatment.

[0053] A method for preparing an antimony trioxide-based flame retardant material: 4g of dipropylene glycol and 6g of ethylene glycol were mixed to obtain a polyol phase. 0.4g of Span-80 was added to 40g of white oil and mixed thoroughly to obtain an oil phase. 2g of antimony glycol was added to the polyol phase, stirred until dissolved, and then added to the oil phase. The mixture was stirred at 10000 rpm for 5 minutes to obtain a P / O emulsion. 4g of poloxamer 407 was added to 400ml of deionized water and mixed thoroughly. Sodium dihydrogen phosphate was added to adjust the pH of the system to 5 to obtain an aqueous phase. The P / O emulsion was then... The emulsion O was added to the aqueous phase and stirred at a high speed of 10000 r / min for 30 s, followed by stirring at a low speed of 50 r / min for 60 min. After standing for 24 h, the precipitate was collected by centrifugation. The product was washed repeatedly with deionized water and ethanol and dried to obtain antimony trioxide particles with a porous structure. 1 g of the above antimony trioxide particles were placed in 50 ml of a mixed solvent composed of deionized water and anhydrous ethanol in a volume ratio of 1:4. The mixture was ultrasonically dispersed for 30 min, and then 0.5 g of KH-550 was added. The pH of the system was adjusted to 3-4 with acetic acid, and the mixture was stirred in a constant temperature water bath at 65 ℃ for 8 h. After returning to room temperature, the mixture was centrifuged, and the product was collected, washed with anhydrous ethanol, and dispersed in 100 ml of 95% ethanol to obtain solution A.

[0054] Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3 hours, then transfer to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of mortar or container]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium n-octanol were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected, washed with anhydrous ethanol, and dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and dried in a vacuum oven at 60°C for 5 hours.

[0055] Comparative Example 5: The method is basically the same as in Example 1, except that commercially available antimony trioxide particles are used instead of the self-made antimony trioxide particles with a porous structure.

[0056] The preparation method of antimony trioxide-based flame retardant materials is as follows: Take 1g of commercially available antimony trioxide particles (Yamei Nano) and place them in 50ml of a mixed solvent consisting of deionized water and anhydrous ethanol at a volume ratio of 1:4. Disperse the mixture ultrasonically for 30min, then add 0.5g of KH-550. Adjust the pH of the system to 3-4 with acetic acid. Stir the reaction mixture in a 65℃ water bath for 8h. After restoring to room temperature, centrifuge the mixture, collect the product, wash it with anhydrous ethanol, and disperse it in 100ml of 95% ethanol to obtain solution A. Grind 1g of black phosphorus crystals together with 10ml of N-methylpyrrolidone in an agate mortar for 3h, then transfer the mixture to a 100ml brown bottle and add 90ml of [unclear - possibly a specific type of ethanol]. N-methylpyrrolidone was subjected to nitrogen purging to isolate it from air and sealed. It was then sonicated in a water bath at room temperature for 10 hours, centrifuged at 8000 rpm for 20 minutes to remove large-sized products, and the supernatant was collected. The supernatant was then centrifuged again at 20000 rpm for 20 minutes, and the precipitate was collected. After washing with acetone and ethanol, the precipitate was vacuum dried to obtain black phosphorus nanosheets. 100 mg of black phosphorus nanosheets and sodium n-octanol were mixed and dispersed in 100 ml of dimethylformamide at a molar ratio of 1:1.5. The mixture was stirred and reacted at room temperature under argon protection for 48 hours. After the reaction, the solution was centrifuged at 20000 rpm for 20 minutes, and the precipitate was collected, washed with anhydrous ethanol, and dispersed in 50 ml of fresh anhydrous ethanol to obtain solution B. Solution B was slowly added to solution A with stirring, and the pH was adjusted to 5-6. The mixture was stirred at room temperature for 2 hours, then centrifuged at 20000 rpm for 20 minutes. The precipitate was collected and heat-treated at 300℃ for 5 hours under argon protection.

[0057] Performance testing The flame-retardant materials prepared in Examples 1-7 and Comparative Examples 1-5 of this invention were used as samples for corresponding performance tests.

[0058] The sample was mixed with PVC paste resin, dioctyl phthalate and calcium zinc stabilizer in a mass ratio of 0.06:1:0.45:0.03. The resulting mixture was placed in an extruder and melt-extruded at a temperature range of 140-160℃ to prepare a composite material. Then, it was placed in a micro injection molding machine and injection molded at 145℃ with a pressure of 15MPa. Finally, it was cut into test strips for performance testing.

[0059] ①Oxygen index data were collected using a JF-3 oxygen index tester. The test standard was in accordance with GB / T 2406-2009 Oxygen Index Determination Method. The sample size was 100mm×6.5mm×3mm.

[0060] ② Flame retardant performance data were collected using a cone calorimeter, with testing standards conforming to ISO 5660-1:2015. The sample size was 100mm×100mm×3mm, and the radiation intensity was selected as... .

[0061] The test results are shown in Table 1: Table 1: As shown in Table 1 above, the flame retardant material prepared by the present invention can effectively improve the flame retardant performance of PVC material.

[0062] The comparison of Examples 1-3 shows that heat treatment temperature has a significant impact on flame-retardant materials. Heat treatment at 300℃ (Example 1) yields the best flame-retardant performance, at which point the interfacial bonding strength between the black phosphorus nanosheets and antimony trioxide is highest.

[0063] A comparison of Examples 1 and 4-7 shows that the alkyl chain length in the alkoxylation reagent has an optimizing effect on the surface modification effect of black phosphorus and subsequent interfacial assembly. Sodium n-octanol (C8, Example 1) treatment exhibits the best overall performance, with its hydrophobic alkyl chain length showing the best matching degree with the chain segments of KH-550. This ensures stable dispersion of black phosphorus nanosheets in the solvent and promotes close interfacial contact with KH-550-modified antimony trioxide.

[0064] The comparison between Example 1 and Comparative Example 1 shows that sodium methoxide (C1) has a very short methyl chain segment, which leads to a poorer interface assembly effect between alkoxylated black phosphorus and KH-550 modified antimony trioxide.

[0065] The comparison between Example 1 and Comparative Example 2 shows that electrostatic adsorption self-assembly combined with heat treatment (Example 1) has an essential advantage over simple physical grinding and mixing (Comparative Example 2).

[0066] The comparison between Example 1 and Comparative Example 3 shows that the alkoxylation treatment of black phosphorus nanosheets is a necessary prerequisite for achieving effective chemical bonding with KH-550 modified antimony trioxide.

[0067] The comparison between Example 1 and Comparative Example 4 shows that heat treatment can promote interfacial chemical bonding and improve the thermal stability of materials, while the lack of heat treatment leads to the deterioration of the flame retardant properties of materials.

[0068] The comparison between Example 1 and Comparative Example 5 shows that the porous structure provides a larger specific surface area and more active sites, which enhances the interfacial interaction and synergistic flame retardant effect with black phosphorus nanosheets.

[0069] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A flame-retardant material based on antimony trioxide, characterized in that, It consists of antimony trioxide particles and alkoxylated black phosphorus coated on them.

2. The antimony trioxide-based flame retardant material as described in claim 1, characterized in that, The antimony trioxide particles have a porous structure.

3. The antimony trioxide-based flame retardant material as described in claim 2, characterized in that, The method for preparing the antimony trioxide particles is as follows: Antimony glycol and polyol phases are added to an oil phase containing a first emulsifier and white oil. After high-speed stirring, a P / O emulsion is obtained. The P / O emulsion is then added to an aqueous phase containing poloxamer and water. After high-speed stirring, the reaction is carried out by low-speed stirring. The mixture is allowed to stand, and the precipitate is collected by centrifugation, washed, and dried.

4. The antimony trioxide-based flame retardant material as described in claim 3, characterized in that, The polyol phase is a combination of dipropylene glycol and ethylene glycol in a mass ratio of 1-4:1-4.

5. The antimony trioxide-based flame retardant material as described in claim 3, characterized in that, The first emulsifier is any one or a combination of Span-20, Span-40, Span-60, and Span-80.

6. The antimony trioxide-based flame retardant material as described in claim 3, characterized in that, The pH of the aqueous phase is 3-6.

7. A method for preparing an antimony trioxide-based flame retardant material as described in any one of claims 1-6, characterized in that, include: Sodium alkyl alkoxide reacts with black phosphorus nanosheets to generate alkoxylated black phosphorus; Positive charge modification on the surface of antimony trioxide particles; The two are mixed and electrostatically adsorbed for self-assembly; Heat treatment under argon protection.

8. The method for preparing the antimony trioxide-based flame retardant material as described in claim 7, characterized in that, The sodium alkylol is any one of sodium hexanoate, sodium heptanol, sodium octanol, sodium nonyl alcohol, and sodium decanoate.

9. The method for preparing the antimony trioxide-based flame retardant material as described in claim 7, characterized in that, The surface of antimony trioxide particles was positively charged using a silane coupling agent.

10. The method for preparing the antimony trioxide-based flame retardant material as described in claim 7, characterized in that, The heat treatment temperature is 200-400℃.

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