CN112321861B - Cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film and preparation method thereof - Google Patents
Cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film and preparation method thereof Download PDFInfo
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- CN112321861B CN112321861B CN202011235189.4A CN202011235189A CN112321861B CN 112321861 B CN112321861 B CN 112321861B CN 202011235189 A CN202011235189 A CN 202011235189A CN 112321861 B CN112321861 B CN 112321861B
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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
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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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
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- 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
Abstract
The invention discloses a cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film and a preparation method thereof, wherein the flame-retardant film comprises the following steps: the cellulose raw materials such as cotton and the like are fully soaked in phosphate and urea solution for swelling, and are dried and solidified. And adding a black phosphorus material, preparing a phosphorylated cellulose nanofiber/black phosphorus quantum dot suspension by utilizing ultrasonic assistance, and then obtaining the composite film with flame retardant property by vacuum suction filtration. The invention utilizes an ultrasonic auxiliary method to disintegrate and disperse cellulose for the first time, and simultaneously strips the black phosphorus material to prepare the cellulose nanofiber with the surface rich in phosphate groups and the black phosphorus quantum dot composite material, so as to further obtain the composite film with excellent mechanical property and flame retardant property, and explore the preparation and application of the high-efficiency sustainable flame retardant material.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film and a preparation method thereof.
Background
About 500 thousands of fires occur annually on a global scale, and the burning materials simultaneously release a large amount of toxic gases and corrosive smoke into the surrounding environment, resulting in hundreds of thousands of casualties. Taking the United states as an example, the automobile fires and the building fires are respectively 20 ten thousand and 48 ten thousand, and respectively account for 15.2 percent and 35.3 percent of the total national fires. In China, the fire situation is also optimistic. In 2019, china receives 23.3 thousands of fire disasters, and the casualties of 2172 people reach 36.1 hundred million yuan. In order to reduce and avoid the loss caused by fire, it is necessary to use flame retardant materials. Halogen flame retardants are widely used because of their high flame retarding efficiency and low cost, but materials added with halogen flame retardants release a great deal of toxic gases and corrosive fumes into the surrounding environment when burned, and secondary pollution damage caused by the halogen flame retardants is no less than fire hazard, and can be enriched in human and animal bodies. Therefore, it is particularly important to find efficient, low-toxicity and environment-friendly flame retardants.
The phosphorus-based compounds burn to form coke, which is less prone to volatile materials. The formed carbon can be used as a heat insulation material to cover the surface of the material, and protect the material from further decomposition, thereby having a flame retardant effect. Therefore, phosphorus-containing flame retardants are more suitable than halogen-based flame retardants. Phosphorus generally represents a new area of flame retardant material development.
The combined application of phosphorus chemistry and biomacromolecules will result in renewable resources with inherent flame retardant properties. Cellulose is a macromolecular polymer composed of glucose, is abundant in reserves in nature, is cheap and easy to obtain, and is a high-quality sustainable biomass resource. The cellulose nanofiber (Cellulose Nanofiber, CNF) can be obtained by chemical modification, mechanical disintegration and other treatments. The CNF prepared by the phosphorylation method has inherent flame retardance due to phosphate groups in the structure, so that the burning and carbonizing capacity is enhanced, the CNF can be further compounded with nano materials, and the flame retardance is improved.
Black phosphorus is a black crystal with metallic luster, and is the most stable allotrope of phosphorus under the normal temperature and pressure. The ultra-small black phosphorus nano-sheet with the size of about 3nm, which is also called as black phosphorus quantum dot, can be peeled from the solid of block-shaped black phosphorus and has the characteristics of excellent mechanical property, photo-thermal property and the like. But the stability of the material is poor under the conditions of illumination, oxygen, water, ambient temperature and the like, and the material is easy to oxidize and degrade, so that the performance is influenced. In the prior art, the black phosphorus nano material is difficult to uniformly disperse in the polymer by simple mechanical stirring and physical mixing, so that the preparation of the polymer nano composite material is limited.
The black phosphorus nano material is prepared by dispersing cellulose through ultrasonic disintegration and stripping block black phosphorus at the same time, and is hopeful to obtain a uniformly dispersed composite material, and the interface interaction force of the two materials is improved. And the synergistic strengthening effect of the two can improve the flame retardant property and the mechanical property, and fully exert the advantages of phosphorus chemistry in the field of flame retardant materials. Therefore, the preparation of the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film has important value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film and a preparation method thereof, and provides a new technical approach for preparing and developing novel degradable flame-retardant materials.
The aim of the invention is realized by the following technical scheme: soaking cellulose raw materials such as cotton and the like in phosphate and urea solution, and drying and solidifying the cellulose raw materials. And adding a black phosphorus material, preparing a phosphorylated CNF/black phosphorus quantum dot suspension by utilizing ultrasonic assistance, and then obtaining the composite film with flame retardant property through vacuum suction filtration.
Preferentially, the preparation method of the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film specifically comprises the following steps:
1) Soaking and swelling: and (3) ultrasonically dissolving phosphate and urea in deionized water, regulating the pH value of the solution to 4-8, adding cotton, heating in a water bath, and fully soaking and swelling for 3h.
2) Drying and curing: drying the fully soaked and swelled cotton cellulose at 70-100 ℃, curing after complete drying, and fully washing by vacuum filtration to remove unreacted chemical substances.
3) Preparing a composite material: adding water into the cellulose after the curing treatment, stirring and dispersing until the mass concentration is 0.2-1 wt%, adding 5-20 mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and performing ultrasonic treatment to obtain the CNF/black phosphorus quantum dot composite material suspension.
4) Preparing a composite film: and (3) carrying out suction filtration on the suspension liquid to form a film by a vacuum suction filtration device, taking out the filter film, adhering a filter film on the surface of the filter film with the flame-retardant film, clamping the filter film between two metal plates, and then placing the filter film in a blast drying box to dry the filter film at 40-80 ℃ for 12-24 hours to obtain the CNF/black phosphorus quantum dot composite film with flame-retardant property.
The phosphate in the step 1) comprises the following components: diammonium phosphate, monoammonium phosphate, disodium phosphate, and sodium dihydrogen phosphate.
In the step 1), the material molar ratio is the anhydroglucose unit: phosphate: urea=1, (0.5 to 2), 3 to 8.
The heating temperature in the step 1) is 30-60 ℃.
The curing temperature in the step 2) is 140-170 ℃.
The curing time in the step 2) is 10-90 min.
The ultrasonic time in the step 3) is 3-6 h.
The invention has the beneficial effects that:
1) The invention utilizes an ultrasonic auxiliary method to disintegrate and disperse cellulose for the first time, and simultaneously strips the black phosphorus material, thereby preparing the phosphorylated CNF/black phosphorus quantum dot composite material. In the preparation process, the black phosphorus peeled layer by layer can be uniformly mixed and dispersed into the suspension, and the hydroxyl groups on the surface of the cellulose are combined with the black phosphorus quantum dots, so that the stability of the black phosphorus quantum dots is improved.
2) The surface of the phosphorylated CNF prepared by the invention contains rich phosphate groups, the black phosphorus quantum dots are rich in phosphorus elements, the composite material prepared by the phosphorylated CNF and the black phosphorus quantum dots play a role in synergistically enhancing flame retardance, and thermally stable carbon is formed after combustion, so that the generation of volatile components is inhibited, and unburned materials are protected from direct flame contact.
3) The composite of the phosphorylated CNF and the black phosphorus quantum dots fully plays the advantages of phosphorus chemistry in the field of flame-retardant materials, endows the materials with thermal stability and flame retardance, is favorable for developing efficient and environment-friendly flame retardants, and improves the feasibility and safety of the flame retardants in industrial application.
Drawings
Fig. 1 is a transmission electron microscope image of a phosphorylated CNF/black phosphorus quantum dot composite material prepared using example 1 of the present invention.
Detailed Description
Comparative example
7g of monoammonium phosphate and 22g of urea are weighed and dissolved in deionized water, the pH value of the solution is regulated to 4, 20g of cotton is added for full immersion, and the mixture is placed in a water bath for heating to 30 ℃ and full immersion swelling for 3 hours.
And (3) placing the fully soaked and swelled cellulose in a forced air drying oven to be dried at 70-100 ℃, heating to 140 ℃ to be solidified for 90min after the fully soaked and swelled cellulose is completely dried, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing the cellulose by vacuum suction filtration until the conductivity of filtrate is less than 100 mu S/cm.
Adding water into the cellulose after the curing treatment, stirring and dispersing until the mass concentration is 0.2wt%, and carrying out ultrasonic treatment for 6 hours to obtain a phosphorylated CNF suspension.
And (3) carrying out suction filtration on the suspension liquid to form a film by a vacuum suction filtration device, taking out the filter membrane, adhering a filter membrane on the surface of the filter membrane with the flame-retardant film, clamping the filter membrane between two metal plates, and then drying the filter membrane in a blast drying oven at 60 ℃ for 24 hours to obtain the CNF film with flame-retardant property.
Example 1
7g of monoammonium phosphate and 22g of urea are weighed and dissolved in deionized water, the pH value of the solution is regulated to 4, 20g of cotton is added for full immersion, and the mixture is placed in a water bath for heating to 30 ℃ and full immersion swelling for 3 hours.
And (3) placing the fully soaked and swelled cellulose in a forced air drying oven to be dried at 70-100 ℃, heating to 140 ℃ to be solidified for 90min after the fully soaked and swelled cellulose is completely dried, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing the cellulose by vacuum suction filtration until the conductivity of filtrate is less than 100 mu S/cm.
Adding water into the cellulose after the curing treatment, stirring and dispersing until the mass concentration is 0.2wt%, adding 20mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and carrying out ultrasonic treatment for 6 hours to obtain a CNF/black phosphorus quantum dot composite material suspension.
And (3) carrying out suction filtration on the suspension liquid to form a film through a vacuum suction filtration device, taking out the filter membrane, adhering a filter membrane on the surface of the filter membrane with the flame-retardant film, clamping the filter membrane between two metal plates, and then drying the filter membrane in a blast drying oven at 60 ℃ for 24 hours to obtain the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film.
Example 2
28g of monoammonium phosphate and 60g of urea are weighed and dissolved in deionized water, the pH of the solution is adjusted to 8, 20g of cotton is added for full immersion, and the mixture is placed in a water bath for heating to 60 ℃ and full immersion swelling for 1h.
And (3) placing the fully soaked and swelled cellulose in a forced air drying oven to be dried at 70-100 ℃, heating to 170 ℃ to be solidified for 10min after the fully soaked and swelled cellulose is completely dried, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing the cellulose by vacuum suction filtration until the conductivity of filtrate is less than 100 mu S/cm.
Adding water into the cellulose after the curing treatment, stirring and dispersing until the mass concentration is 1wt%, adding 5mg of black phosphorus solid, stirring at a high speed to form uniform mixed solution, and carrying out ultrasonic treatment for 3 hours to obtain CNF/black phosphorus quantum dot composite material suspension.
And (3) carrying out suction filtration on the suspension liquid to form a film through a vacuum suction filtration device, taking out the filter membrane, adhering a filter membrane on the surface of the filter membrane with the flame-retardant film, clamping the filter membrane between two metal plates, and then drying the filter membrane in a blast drying oven at 80 ℃ for 12 hours to obtain the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film.
Example 3
30g of sodium dihydrogen phosphate and 60g of urea are weighed and dissolved in deionized water, the pH of the solution is regulated to 6, 20g of cotton is added for full immersion, and the mixture is placed in a water bath for heating to 30 ℃, and full immersion and swelling are carried out for 3 hours.
And (3) placing the fully soaked and swelled cellulose in a forced air drying oven to be dried at 70-100 ℃, heating to 140 ℃ to be solidified for 90min after the fully soaked and swelled cellulose is completely dried, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing the cellulose by vacuum suction filtration until the conductivity of filtrate is less than 100 mu S/cm.
Adding water into the cellulose after the curing treatment, stirring and dispersing until the mass concentration is 0.5wt%, adding 10mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and carrying out ultrasonic treatment for 6 hours to obtain a CNF/black phosphorus quantum dot composite material suspension.
And (3) carrying out suction filtration on the suspension liquid to form a film through a vacuum suction filtration device, taking out the filter membrane, adhering a filter membrane on the surface of the filter membrane with the flame-retardant film, clamping the filter membrane between two metal plates, and then drying the filter membrane in a blast drying oven at 80 ℃ for 12 hours to obtain the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film.
Example 4
33g of diammonium hydrogen phosphate and 60g of urea are weighed and dissolved in deionized water, the pH of the solution is adjusted to 8, 20g of cotton is added for full immersion, and the mixture is placed in a water bath for heating to 60 ℃ and full immersion swelling for 2h.
And (3) placing the fully soaked and swelled cellulose in a forced air drying oven to be dried at 70-100 ℃, heating to 140 ℃ to be solidified for 60min after the fully soaked and swelled cellulose is completely dried, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing the cellulose by vacuum suction filtration until the conductivity of filtrate is less than 100 mu S/cm.
Adding water into the cellulose after the curing treatment, stirring and dispersing until the mass concentration is 0.5wt%, adding 10mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and carrying out ultrasonic treatment for 3 hours to obtain a CNF/black phosphorus quantum dot composite material suspension.
And (3) carrying out suction filtration on the suspension liquid to form a film through a vacuum suction filtration device, taking out the filter membrane, adhering a filter membrane on the surface of the filter membrane with the flame-retardant film, clamping the filter membrane between two metal plates, and then drying the filter membrane in a blast drying oven at 60 ℃ for 24 hours to obtain the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film.
The experiment adopts a cone calorimeter to evaluate the flame retardant property of the phosphorylated CNF/black phosphorus quantum dot composite flame retardant film. Before the experiment starts, the film is placed under the environmental conditions of 23+/-1 ℃ and 50% RH for 48 hours, then the film is cut into 100 multiplied by 3mm, and is wrapped by aluminum foil paper and is placed on a sample table, and the radiation flux is set to be 35kW/m 2 The flame retardant film was tested for peak heat release rate, total heat release rate and total smoke release. The mechanical properties of the film can be measured by a mechanical property tester. Firstly, selecting a flat and defect-free film, placing the film in 23+/-1 ℃ and 50% RH for 48 hours, then cutting the film into a sample to be tested with the length of 40mm multiplied by the width of 5mm, placing the sample in a testing machine, and recording the tensile strength, young modulus and elongation at break of the obtained sample under the test condition that the loading speed is 2 mm/min. The test results are shown in the following table.
While the invention has been described with respect to the preferred embodiments, the scope of the invention is not limited thereto, and any changes or substitutions that would be apparent to those skilled in the art within the scope of the invention are intended to be included within the scope of the invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (6)
1. The preparation method of the cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film is characterized by comprising the following operation steps of:
1) Soaking and swelling: ultrasonically dissolving phosphate and urea in deionized water, adjusting the pH of the solution to 4-8, adding cotton, heating in a water bath, and fully soaking and swelling for 1-3 hours; wherein the molar ratio of the anhydroglucose units, the phosphate and the urea in the cellulose raw material is 1 (0.5-2): 3-8;
2) Drying and curing: drying the fully soaked and swelled cotton cellulose at 70-100 ℃, curing after completely drying, and fully washing by vacuum filtration to remove unreacted chemical substances;
3) Preparing a composite material: adding water into the cellulose after the curing treatment, stirring and dispersing until the mass concentration is 0.2-1wt%, adding 5-20 mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and carrying out ultrasonic treatment for 3-6 hours to obtain a cellulose nanofiber/black phosphorus quantum dot composite material suspension;
4) Preparing a composite film: and carrying out suction filtration on the suspension liquid to form a film by a vacuum suction filtration device, taking out the filter film, adhering a filter film on the surface of the filter film with the flame-retardant film, clamping the filter film between two metal plates, and then placing the filter film in a blast drying box to dry the filter film at 40-80 ℃ for 12-24 hours to obtain the cellulose nanofiber/black phosphorus quantum dot composite film with flame-retardant property.
2. The method for preparing the cellulose phosphate nanofiber/black phosphorus quantum dot composite flame retardant film according to claim 1, wherein the phosphate in the step 1) comprises the following steps: diammonium phosphate, monoammonium phosphate, disodium phosphate, and sodium dihydrogen phosphate.
3. The preparation method of the cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film according to claim 1, wherein the heating temperature in the step 1) is 30-60 ℃.
4. The preparation method of the cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film according to claim 1, wherein the curing temperature in the step 2) is 140-170 ℃.
5. The preparation method of the cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film according to claim 1, wherein the curing time in the step 2) is 10-90 min.
6. A cellulose phosphate nanofiber/black phosphorus quantum dot composite flame retardant film, characterized in that the composite flame retardant film is prepared by the preparation method of the cellulose phosphate nanofiber/black phosphorus quantum dot composite flame retardant film according to any one of claims 1 to 5.
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| CN113980310B (en) * | 2021-11-25 | 2022-08-16 | 燕山大学 | Phosphorus flame-retardant material and preparation method thereof |
| CN115044993A (en) * | 2022-06-21 | 2022-09-13 | 天津大学 | High-charge-density phosphorylated cellulose nanofiber and hot-dipping preparation method |
| CN115322443B (en) * | 2022-09-23 | 2023-09-05 | 苏州巨峰电气绝缘系统股份有限公司 | High-strength flame-retardant MXene/cellulose phosphate fibril composite film and preparation method thereof |
| CN116693702A (en) * | 2023-07-13 | 2023-09-05 | 天津永续新材料有限公司 | High-charge-quantity phosphorylated nanocellulose and preparation method thereof |
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