CN113980310B - Phosphorus flame-retardant material and preparation method thereof - Google Patents

Phosphorus flame-retardant material and preparation method thereof Download PDF

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CN113980310B
CN113980310B CN202111411524.6A CN202111411524A CN113980310B CN 113980310 B CN113980310 B CN 113980310B CN 202111411524 A CN202111411524 A CN 202111411524A CN 113980310 B CN113980310 B CN 113980310B
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flame
phosphorus
black phosphorus
retardant
water
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CN113980310A (en
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焦体峰
王冉
马金铭
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Yanshan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The invention discloses a phosphorus flame-retardant material and a preparation method thereof, belonging to the technical field of flame-retardant materials. The method comprises the steps of dissolving the black phosphorus nanosheet modified by the tannic acid, the phytic acid and the cellulose nanofiber in a solvent, uniformly mixing the black phosphorus nanosheet, the phytic acid and the cellulose nanofiber by ultrasonic waves, and filtering the mixture to obtain the phosphorus flame retardant material. The invention also discloses a flame-retardant film prepared from the flame-retardant material. The flame-retardant film provided by the invention takes cellulose nanofibers as a main body, takes two-dimensional black phosphorus nanosheets and phytic acid as flame retardants, and modifies the surfaces of the black phosphorus by using tannic acid so as to improve the stability of the black phosphorus. The black phosphorus and the phytic acid as the phosphorus flame retardant can reduce the generation of combustible products, promote the formation of char and play a role in inhibiting flame. The preparation process adopted by the invention is simple and easy to operate, the film components are nontoxic, the biocompatibility and the degradability are good, and the flame retardant effect is obvious.

Description

Phosphorus flame-retardant material and preparation method thereof
Technical Field
The invention relates to the technical field of flame retardant materials, in particular to a phosphorus flame retardant material and a preparation method thereof.
Background
Cellulose is a rich natural polymer, and provides a sustainable green resource which is degradable, has high biocompatibility and low cost benefit for human beings. The cellulose-based film material regulated and controlled by the structure is widely applied to the fields of flexible electronic devices, intelligent optics, energy storage and the like. However, cellulose-based film materials are flammable under open fire and have poor stability in high temperature environments. Therefore, it is important to improve the stability and flame retardancy of cellulose-based film materials. The use of halogen-containing flame retardants is increasingly limited because they can generate harmful volatile substances during combustion that pose a threat to human health and the environment. The phosphorus flame retardant is a common flame retardant material and has the advantages of no halogen, low toxicity and environmental protection. Phytic acid is an organic phosphoric acid compound existing in seeds and rhizomes of plants, and contains abundant phosphate groups. The two-dimensional black phosphorus nanosheet has a high specific surface area and a thermally stable lamellar structure, can play a role in blocking in a composite material, and inhibits gas permeation and heat and mass exchange. The phosphorus flame retardant can promote the formation of a protective carbon layer in the combustion process, and reduces the heat conduction between flame and polymer, thereby preventing or delaying the generation of combustible gas. In addition, the phosphorus flame retardant can form PO & free radicals with oxygen, and capture a large amount of H & HO & free radicals in a gas phase, thereby interrupting the free radical chain reaction of the polymer and playing a role in inhibiting flame.
Disclosure of Invention
Aiming at the background technology, the invention provides an environment-friendly and nontoxic preparation method based on a phosphorus flame-retardant film. The invention utilizes a vacuum filtration technology, takes cellulose nanofibers as a main material of a film, and adds tannic acid modified black phosphorus nanosheets and phytic acid as flame retardants to prepare an environment-friendly and degradable flame-retardant film material.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a phosphorus flame-retardant material, which comprises the following steps:
dissolving the black phosphorus nanosheet modified by the tannic acid, the phytic acid and the cellulose nanofiber in a solvent I, uniformly mixing by ultrasonic waves, and filtering to obtain the phosphorus flame retardant material.
According to a preferable embodiment, the mass ratio of the tannin-modified black phosphorus nanosheets, the phytic acid and the cellulose nanofibers is 1-50: 700-2100: 50.
In certain specific embodiments, the mass ratio of the tannic acid-modified black phosphorus nanoplatelets, the phytic acid, and the cellulose nanofibers is 50:700:50, 50:1000:50, 25:700:50, 50:2100:50, 25:2100:50, 1:700:50, 1:1000:50, 1:2100:50, or any ratio therebetween.
In a preferred embodiment, the filtration is a suction filtration with a pore size of 0.05 to 0.22 μm.
As a preferred embodiment, the solvent I is water.
Preferably, the preparation method of the tannic acid modified black phosphorus nanosheet comprises the following steps:
(1) adding black phosphorus and tannic acid into water, uniformly mixing, deoxidizing, and carrying out ultrasonic treatment;
(2) the supernatant was collected by primary centrifugation and the precipitate was collected by secondary centrifugation.
Preferably, in the step (1), the concentration of the black phosphorus in the water is 50-100 mg per 30-100 mL of water.
In certain embodiments, the concentration of black phosphorus in water is 50mg black phosphorus per 100mL of water, 55mg black phosphorus per 80mL of water, 60mg black phosphorus per 70mL of water, 70mg black phosphorus per 60mL of water, 80mg black phosphorus per 50mL of water, 90mg black phosphorus per 40mL of water, 100mg black phosphorus per 30mL of water, or any concentration therebetween.
Preferably, in the step (1), the concentration of the tannic acid in the water is 100-200 mg of tannic acid per 30-100 mL of water.
In certain embodiments, the tannic acid is at a concentration in the water of 100mg tannic acid per 100mL of water, 120mg tannic acid per 80mL of water, 140mg tannic acid per 70mL of water, 160mg tannic acid per 60mL of water, 180mg tannic acid per 50mL of water, 190mg tannic acid per 40mL of water, 200mg tannic acid per 30mL of water, or any concentration therebetween.
In a preferred embodiment, in step (1), the ultrasonic treatment is performed by using a cell crusher, preferably by ultrasonic treatment under an ice bath.
In a preferable embodiment, in the step (2), the primary centrifugation is performed at 3000 to 3500rpm for 15 to 20 minutes.
In a preferable embodiment, in the step (2), the second centrifugation is performed at 8000 to 9000rpm for 15 to 20 minutes.
Preferably, step (2) further comprises washing and drying, said drying being selected from freeze-drying or vacuum-drying.
In the technical scheme of the invention, the length and width of the tannic acid modified black phosphorus nanosheet is 200-300 nm, such as 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm, 300nm or any value therebetween.
According to the technical scheme, the prepared tannin-modified black phosphorus nanosheet is a few-layer black phosphorus nanosheet, the number of layers is related to the centrifugal time and the centrifugal rotating speed in the reaction process, and the number of layers is usually 1-10.
The invention provides a phosphorus flame-retardant material obtained by the preparation method.
The third aspect of the present invention provides a phosphorus-based flame retardant film prepared from the above phosphorus-based flame retardant material, wherein the phosphorus-based flame retardant film is prepared by drying the above phosphorus-based flame retardant material.
Preferably, the drying is vacuum drying at 30-40 ℃.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the flame-retardant material provided by the invention is simple and easy to operate, and the reaction conditions are mild and easy to control;
2. the flame retardant material provided by the invention takes the cellulose nanofiber as a main material, has wide source, can be regenerated and degraded, and has environmental friendliness and good ecological benefit;
3. the flame-retardant material provided by the invention selects black phosphorus and phytic acid as phosphorus flame retardants, and the prepared flame-retardant film has the advantages of no toxicity, environmental protection, degradability and good flame-retardant effect, reduces the generation of combustible products, promotes char formation, and plays a role in inhibiting flame.
4. The flame retardant material provided by the invention utilizes antioxidant tannic acid to modify the surface of black phosphorus, so that the stability of the flame retardant material can be improved;
5. the flame retardant material provided by the invention can be used as a flexible material to be applied to electronic devices and fire-fighting articles.
Drawings
Fig. 1 is a transmission electron micrograph of tannic acid-modified black phosphorus nanoplates of example 1.
Fig. 2 is a picture of the black phosphorus nanoplates and tannin-modified black phosphorus nanoplates of example 1 after 3 days of standing.
FIG. 3 is a surface scanning electron micrograph of the flame retardant film of example 1.
FIG. 4 is a sectional scanning electron micrograph of the flame retardant film in example 1.
Fig. 5 is a thermogravimetric plot of the flame retardant film in example 1 and the pure cellulose nanofiber film in comparative example 1.
Fig. 6 is a graph showing the combustion effect of the pure cellulose nanofiber membrane in comparative example 1.
FIG. 7 is a graph showing the combustion effect of the flame retardant film in example 1.
Fig. 8 is a graph showing heat release rate curves of the flame-retardant film in example 1 and the pure cellulose nanofiber film in comparative example 1.
Detailed Description
The following examples are only a part of the present invention, and not all of them. Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without making creative efforts, belong to the protection scope of the invention.
In the present invention, all the equipment, materials and the like are commercially available or commonly used in the industry, if not specified. The methods in the following examples are conventional in the art unless otherwise specified.
In the following examples:
black phosphorus: according to the literature Pan, l.; zhu, x.d.; sun, k.n.; liu, y.t.; xie, x.m.; the block Black Phosphorus is prepared by the method described in Ye, X.Y.molecular Level Distribution of Black Phosphorus Quantum Dots on Nitrogen-doped Graphene Nanosheets for Superior Lithium storage. Nano Energy 2016,30,347-354.
A cell crusher: purchased from Ningbo Xinzhi Biotech, Inc., under the model SCIENTZ-IID.
Ultrasonic cleaner: ultrasonic cleaning machines are commonly used in laboratories.
Tannic acid: from Aladdin reagent, Inc.
Cellulose Nanofibers (CNF): any commercially available product may be used.
Phytic acid: a 70% aqueous phytic acid solution available from alatin reagent limited.
Example 1: flame-retardant film
(1) To 30mL of ultrapure water, 50mg of black phosphorus was added, along with 100mg of tannic acid, and nitrogen was bubbled for 30 minutes to remove oxygen from the water. Then, the mixture was sonicated for 6 hours by a cell disruptor 950W under ice bath. Subsequently, centrifugation was carried out at 3000rpm for 20 minutes and the supernatant was collected. Centrifuging the collected supernatant for 15 minutes at 8000rpm, removing the supernatant, washing the precipitate with ultrapure water, then centrifuging for 15 minutes at 8000rpm, repeating for 2-3 times, and freeze-drying the collected precipitate (-50 ℃) to obtain the tannin-modified black phosphorus nanosheet.
(2) To an aqueous dispersion of 1.35 wt% cellulose nanofibers was added water to a concentration of 0.5 wt%, and mechanically stirred at 300rpm for 12 hours to obtain a uniform dispersion.
(3) Mixing the tannic acid modified black phosphorus nanosheet obtained in the step (1), a 70% phytic acid aqueous solution and the cellulose nanofiber dispersion liquid with the concentration of 0.5 wt% obtained in the step (2) in a mass ratio of 1:1000:50, and carrying out ultrasonic treatment for 20 minutes by using an ultrasonic cleaner; the resulting dispersion was subjected to vacuum filtration for 30 seconds using an aqueous filter membrane having a pore size of 0.22 μm, followed by vacuum drying at 40 ℃ for 8 hours to obtain a flame-retardant membrane.
The relevant performance parameters of the flame retardant film prepared in this example are shown in the accompanying drawings:
as shown in FIG. 1, the dimensions of the tannic acid modified black phosphorus nanoplatelets in the present embodiment are 200-300 nm.
As shown in fig. 2, the black phosphorus nanosheet modified with tannic acid prepared in this embodiment still remains clear after being left for 3 days, while the black phosphorus nanosheet not modified still precipitates after being left for 3 days, so that the black phosphorus nanosheet modified with tannic acid prepared by the present invention has good stability.
As shown in fig. 3, the flame retardant film prepared in this example had a rough, wrinkled surface structure.
As shown in fig. 4, the cross section of the flame retardant film prepared in this example was a layered structure.
As shown in fig. 5, the flame retardant film prepared in this example still maintained a residual amount of 43.6% at 800 ℃, which is higher than 26.5% of the nanofiber fibril film.
As shown in fig. 7, after the flame retardant film prepared in this example was ignited, slow combustion resulted in almost no flame generation, indicating that the flame retardant film prepared in this example had a good flame retardant effect.
As shown in fig. 8, it can be known from the Heat Release Rate (HRR) curve of the flame retardant film prepared in this example that the Peak Heat Release Rate (PHRR) of the flame retardant film was 66.4W/g.
Comparative example 1: pure cellulose nanofiber membrane
10 g of a cellulose nanofiber dispersion having a concentration of 0.5 wt% was subjected to vacuum filtration for 30 seconds using a water-based filter membrane having a pore size of 0.22 μm, followed by vacuum drying at 40 ℃ for 8 hours to obtain a pure cellulose nanofiber membrane.
Comparative example 2: cellulose phytic acid film
Mixing 10 g of a cellulose nanofiber dispersion solution with a concentration of 0.5 wt% and a 70% phytic acid aqueous solution in a mass ratio (mass ratio of the cellulose nanofiber dispersion solution to the phytic acid aqueous solution) of 1:700 and subjecting the mixture to ultrasonic treatment for 20 minutes by using an ultrasonic cleaning apparatus; the obtained dispersion was subjected to vacuum filtration for 30 seconds using an aqueous filter membrane having a pore size of 0.22 μm, followed by vacuum drying at 40 ℃ for 8 hours to obtain a pure cellulose nanofiber membrane.
Comparative example 3: cellulose-black phosphorus film
Mixing 10 g of a cellulose nanofiber dispersion with a concentration of 0.5 wt% and tannic acid-modified black phosphorus nanoplatelets in a mass ratio (mass ratio of cellulose nanofiber dispersion to tannic acid-modified black phosphorus nanoplatelets) of 50:1 and sonicating for 20 minutes using a sonicator; the obtained dispersion was subjected to vacuum filtration for 30 seconds using a water-based filter membrane having a pore size of 0.22 μm, followed by vacuum drying at 40 ℃ for 8 hours to obtain a pure cellulose nanofiber membrane.
Effect embodiment:
the thermogravimetric analysis of the pure cellulose nanofiber membrane prepared in comparative example 1, the cellulose-phytic acid membrane prepared in comparative example 2, and the cellulose-black phosphorus membrane prepared in comparative example 3 is shown in fig. 5, from which it can be derived: the pure cellulose nanofiber membrane can maintain 26.5 percent of residual amount at 800 ℃, the cellulose-phytic acid membrane can maintain 41.4 percent of residual amount, and the cellulose-black phosphorus membrane can maintain 38.1 percent of residual amount. It can be seen from the thermogravimetric analysis graphs of the flame retardant film prepared in example 1 in fig. 5 and the different films prepared in comparative examples 1-3 that: for the pure cellulose nanofiber membrane of comparative example 1, a significant mass loss occurred around 270 ℃, and the final residual weight at 800 ℃ was about 26.5%. This is consistent with the fact that thermal degradation consists mainly of the sugar groups decomposing into a carbon layer at lower temperatures and into volatile substances at higher temperatures. In the cellulose-phytic acid film in the comparative example 2, abundant phosphate can induce the surface of the material to be mineralized to form a rigid biomineralization framework, so that the stability of the composite material is improved, and in the pyrolysis process of the cellulose-black phosphorus film in the comparative example 3, the inorganic black phosphorus nanosheet can be used as a physical barrier to hinder the transmission of oxygen and the diffusion of pyrolysis products. While the flame retardant film of example 1 showed a higher residual weight, the flame retardant film had a residual weight of 43.6% when the heating temperature reached 800 ℃, indicating that the flame retardant film of example 1 had better flame retardancy.
The picture of the pure cellulose nanofiber membrane prepared in comparative example 1 after ignition is shown in fig. 6, which is completely burned without residue. By comparing fig. 6 and 7, it is illustrated that the flame retardant film prepared in example 1 has a better flame retardant effect than the pure cellulose nanofiber film.
The heat release rate curve of the pure cellulose nanofiber membrane prepared in comparative example 1 is shown in fig. 8, and the heat release rate Peak (PHRR) of the pure cellulose nanofiber membrane is 190W/g when the temperature reaches 350 ℃. Significantly higher than the flame retardant film in example 1. From the results in fig. 8, it is illustrated that the peak value of the heat release rate of the flame-retardant film prepared in example 1 is lower than that of the pure cellulose nanofiber film in comparative example 1, and thus the flame-retardant film provided by the present invention has good flame-retardant properties.
In summary, in the flame retardant film in example 1, the sheet structure of the tannin-modified black phosphorus nanosheets can serve as a physical barrier to the pyrolysis products in the initial stage of combustionThe flame is transferred while suppressing the continuous combustion and generating heat. Subsequently, the phosphorus element in the black phosphorus and the phytic acid is oxidized into P 2 O 5 To promote dehydration and carbonization of the polymer and form a protective carbon layer. Furthermore, P 2 O 5 A series of phosphoric acids including metaphosphoric acid, pyrophosphoric acid and orthophosphoric acid are formed after water molecules are captured, and the surfaces of the materials can be covered to block external oxygen and heat.
Example 2: flame-retardant film
(1) 50mg of black phosphorus was added to 50mL of ultrapure water, 150mg of tannic acid was added thereto, and nitrogen was bubbled for 30 minutes to remove oxygen from the water. Then, the mixture was sonicated by a cell disruptor 950W for 7 hours in an ice bath. Subsequently, centrifugation was carried out at 3500rpm for 15 minutes and the supernatant was collected. Centrifuging the collected supernatant at 9000rpm for 20 minutes, removing the supernatant, washing the precipitate with ultrapure water, continuing to centrifuge at 9000rpm for 20 minutes, repeating for 2-3 times, and freeze-drying the collected precipitate (-50 ℃) to obtain the tannin-modified few-layer black phosphorus nanosheet.
(2) To 1.35 wt% of the original cellulose nanofibers was added water to a concentration of 0.5 wt%, and mechanically stirred at 400rpm for 8 hours to obtain a uniform dispersion.
(3) The method comprises the following steps of (1) preparing a black phosphorus nanosheet modified by tannic acid, a 70% phytic acid aqueous solution and a 0.5 wt% cellulose nanofiber dispersion solution by mass: mix at a ratio of 10:1000:50 and sonicate using a sonicator for 20 minutes. The resulting dispersion was subjected to vacuum filtration for 30 seconds using an aqueous filter membrane having a pore diameter of 0.22 μm, followed by vacuum drying at 30 ℃ for 8 hours to obtain a flame-retardant membrane.
Example 3: flame-retardant film
(1) To 30mL of ultrapure water, 100mg of black phosphorus was added, along with 200mg of tannic acid, and nitrogen was bubbled for 30 minutes to remove oxygen from the water. Then, the mixture was sonicated by a cell disruptor 950W for 8 hours in an ice bath. Subsequently, centrifugation was carried out at 3500rpm for 20 minutes and the supernatant was collected. Centrifuging the collected supernatant at 9000rpm for 20 minutes, removing the supernatant, washing the precipitate with ultrapure water, continuing to centrifuge at 9000rpm for 20 minutes, repeating for 2-3 times, and freeze-drying the collected precipitate (-80 ℃) to obtain the tannin-modified few-layer black phosphorus nanosheet.
(2) To 1.35 wt% of the original cellulose nanofibers was added water to a concentration of 0.5 wt%, and mechanically stirred at 400rpm for 12 hours to obtain a uniform dispersion.
(3) The method comprises the following steps of (1) preparing a black phosphorus nanosheet modified by tannic acid, a 70% phytic acid aqueous solution and a 0.5 wt% cellulose nanofiber dispersion solution by mass: mix at a ratio of 20:2000:50 and sonicate using a sonicator for 30 minutes. The resulting dispersion was subjected to vacuum filtration for 30 seconds using an aqueous filter membrane having a pore size of 0.22 μm, followed by vacuum drying at 40 ℃ for 8 hours to obtain a flame-retardant membrane.
Example 4: flame-retardant film
(1) To 50mL of ultrapure water, 100mg of black phosphorus was added, 150mg of tannic acid was added simultaneously, and nitrogen was bubbled for 30 minutes to remove oxygen from the water. Then, the mixture was sonicated for 9 hours by a cell disruptor 950W under ice bath. Subsequently, centrifugation was carried out at 3500rpm for 20 minutes and the supernatant was collected. Centrifuging the collected supernatant at 9000rpm for 20 minutes, removing the supernatant, washing the precipitate with ultrapure water, continuing to centrifuge at 9000rpm for 20 minutes, repeating for 2-3 times, and freeze-drying the collected precipitate (-80 ℃) to obtain the tannin-modified few-layer black phosphorus nanosheet.
(2) To 1.35 wt% of the original cellulose nanofibers was added water to a concentration of 1 wt%, and mechanically stirred at 400rpm for 8 hours to obtain a uniform dispersion.
(3) The method comprises the following steps of (1) preparing a black phosphorus nanosheet modified by tannic acid, a 70% phytic acid aqueous solution and a 0.5 wt% cellulose nanofiber dispersion solution by mass: mixed at a ratio of 50:3000:50 and sonicated using a sonicator for 30 minutes. The obtained dispersion was subjected to vacuum filtration for 40 seconds using an aqueous filter membrane having a pore diameter of 0.22 μm, followed by vacuum drying at 40 ℃ for 10 hours to obtain a flame-retardant membrane.
Example 5: flame-retardant film
(1) 100mg of black phosphorus was added to 50mL of ultrapure water, 200mg of tannic acid was added thereto, and nitrogen was bubbled for 30 minutes to remove oxygen from the water. Then, the mixture was sonicated by a cell disruptor 950W for 10 hours in an ice bath. Subsequently, centrifugation was carried out at 3500rpm for 20 minutes and the supernatant was collected. Centrifuging the collected supernatant at 9000rpm for 20 minutes, removing the supernatant, washing the precipitate with ultrapure water, continuing to centrifuge at 9000rpm for 20 minutes, repeating for 2-3 times, and freeze-drying the collected precipitate (-50 ℃) to obtain the tannin-modified few-layer black phosphorus nanosheet.
(2) To 1.35 wt% of the original cellulose nanofibers was added water to a concentration of 1 wt%, and mechanically stirred at 400rpm for 12 hours to obtain a uniform dispersion.
(3) The tannin modified black phosphorus nanosheet, 70% of phytic acid and 0.5 wt% of cellulose nanofiber dispersion liquid are as follows by mass: mix at a ratio of 50:1000:50 and sonicate using a sonicator for 30 minutes. The resulting dispersion was subjected to vacuum filtration for 50 seconds using an aqueous filter membrane having a pore size of 0.22 μm, followed by vacuum drying at 40 ℃ for 12 hours to obtain a flame-retardant membrane.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.

Claims (12)

1. The preparation method of the phosphorus flame-retardant material is characterized by comprising the following steps of:
dissolving the black phosphorus nanosheet modified by the tannic acid, the phytic acid and the cellulose nanofiber in a solvent I, uniformly mixing by ultrasonic waves, and filtering to obtain the phosphorus flame retardant material;
the preparation method of the tannic acid modified black phosphorus nanosheet comprises the following steps:
(1) adding black phosphorus and tannic acid into water, uniformly mixing, deoxidizing, and carrying out ultrasonic treatment;
(2) collecting supernatant by primary centrifugation, and collecting precipitate by secondary centrifugation;
the mass ratio of the tannic acid modified black phosphorus nanosheet to the phytic acid to the cellulose nanofiber is 1-50: 700-2100: 50.
2. The method according to claim 1, wherein the filtration is a suction filtration with a pore size of 0.05 to 0.22 μm.
3. The method according to claim 1, wherein the solvent I is water.
4. The preparation method according to claim 1, wherein in the step (1), the concentration of the black phosphorus in the water is 50-100 mg of the black phosphorus per 30-100 mL of the water.
5. The method according to claim 1, wherein in the step (1), the concentration of the tannic acid in the water is 100-200 mg per 30-100 mL of the water.
6. The method according to claim 1, wherein in the step (2), the primary centrifugation is carried out at 3000-3500 rpm for 15-20 minutes.
7. The method according to claim 1, wherein in the step (2), the second centrifugation is carried out at 8000 to 9000rpm for 15 to 20 minutes.
8. The method according to claim 1, wherein the step (2) further comprises drying, and the drying is selected from freeze drying or vacuum drying.
9. The preparation method of claim 1, wherein the tannin-modified black phosphorus nanosheets have a length and width of 200-300 nm.
10. The phosphorus-based flame-retardant material obtained by the preparation method according to any one of claims 1 to 9.
11. The phosphorus-based flame-retardant film prepared from the phosphorus-based flame-retardant material according to claim 10, wherein the phosphorus-based flame-retardant film is prepared by drying the phosphorus-based flame-retardant material.
12. The phosphorus-based flame-retardant film prepared from the phosphorus-based flame-retardant material according to claim 11, wherein the drying is vacuum drying at 30-40 ℃.
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