CN112321861A - Phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film and preparation method thereof - Google Patents
Phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
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- C08K2003/026—Phosphorus
Abstract
The invention discloses a phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film and a preparation method thereof, wherein the preparation method comprises the following steps: the cellulose raw materials such as cotton are put into phosphate and urea solution for full soaking and swelling, and then are dried and solidified. And adding a black phosphorus material, preparing a phosphorylated cellulose nanofiber/black phosphorus quantum dot suspension by ultrasonic assistance, and performing vacuum filtration to obtain the flame-retardant composite film. The invention creatively disintegrates and disperses the cellulose by an ultrasonic-assisted method for the first time, and simultaneously peels off the black phosphorus material to prepare the cellulose nanofiber and black phosphorus quantum dot composite material with the surface rich in phosphate groups, further obtains the composite film with excellent mechanical property and flame retardant property, and explores the preparation application of the efficient and sustainable flame retardant material.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film and a preparation method thereof.
Background
Around 500 million fires occur worldwide each year, and the burning material simultaneously releases large amounts of toxic gases and corrosive fumes into the surrounding environment, resulting in hundreds of thousands of casualties. For example, in the United states, 20 and 48 million car and building fires, respectively, account for 15.2 and 35.3 percent of the total number of fires in the country. In China, the fire situation is not optimistic. In 2019, 23.3 thousands of fire disasters are reported in China, 2172 casualties are killed, and the direct property loss is as high as 36.1 hundred million yuan. In order to reduce and avoid the loss caused by fire, the use of flame retardant materials is indispensable. Halogen flame retardants are widely used because of their high flame retardant efficiency and low cost, but materials added with halogen flame retardants release large amounts of toxic gases and corrosive fumes into the surrounding environment during combustion, thereby causing secondary pollution damage not inferior to fire hazards, and may also be concentrated in human and animal bodies. Therefore, it is important to find a flame retardant with high efficiency, low toxicity and environmental protection.
The phosphorus-based compound burns to form coke and is not liable to generate volatile substances. The formed carbon can be used as a heat insulating material to cover the surface of the material to protect the material from further decomposition, thereby having a flame retardant effect. Therefore, a phosphorus-containing flame retardant is more suitable than a halogen-based flame retardant. Phosphorus chemistry is generally said to represent 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 high polymer consisting of glucose, is abundant, cheap and easily available in nature, and is a high-quality sustainable biomass resource. The 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 the existence of phosphate radicals in the structure, thereby enhancing the carbon forming capability by combustion, and being further compounded with nano materials to improve the flame retardance.
Black phosphorus is a black, metallic crystal, and is the most stable allotrope of phosphorus at ambient temperature and pressure. The subminiature black phosphorus nanosheet with the size of about 3nm, also called as black phosphorus quantum dot, can be stripped from a massive black phosphorus solid, 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 be oxidized and degraded to influence the performance. In the prior art, the black phosphorus nano material is difficult to be uniformly dispersed in the polymer through simple mechanical stirring and physical mixing, so that the preparation of the polymer nano composite material is limited.
The cellulose is disintegrated and dispersed by ultrasonic waves, and the black phosphorus nano material is prepared by stripping the blocky black phosphorus, so that the uniformly dispersed composite material is expected to be obtained, and the interaction force of the material interface of the black phosphorus nano material and the material interface of the uniformly dispersed composite material 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 purpose of the invention is realized by the following technical scheme: soaking cellulose raw materials such as cotton in a phosphate and urea solution, and drying and curing. And adding a black phosphorus material, preparing a phosphorylated CNF/black phosphorus quantum dot suspension by using ultrasonic wave assistance, and then carrying out vacuum filtration to obtain the composite film with flame retardant property.
Preferentially, the preparation method of the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film comprises the following specific steps:
1) soaking and swelling: ultrasonically dissolving phosphate and urea in deionized water, adjusting the pH value of the solution to 4-8, adding cotton, heating in a water bath, and fully soaking and swelling for 3 hours.
2) Drying and curing: and drying the cotton cellulose fully soaked and swollen at 70-100 ℃, curing after completely drying, and fully washing by vacuum filtration to remove unreacted chemical substances.
3) Preparing a composite material: and adding water into the cured cellulose, stirring and dispersing until the mass concentration is 0.2-1 wt%, then 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 through a vacuum suction filtration device to form a membrane, taking out the filter membrane, sticking a filter membrane on the surface of the filter membrane attached with the flame-retardant film, clamping the filter membrane between two metal plates, and then placing the filter membrane in an air-blast drying oven to dry for 12-24 hours at 40-80 ℃ to obtain the CNF/black phosphorus quantum dot composite membrane with flame-retardant performance.
The phosphate in the step 1) comprises: diammonium phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, and sodium dihydrogen phosphate.
In the step 1), the molar ratio of materials is that the dehydrated glucose unit: phosphate salt: urea is 1, (0.5-2) and (3-8).
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.
And the ultrasonic time in the step 3) is 3-6 h.
The invention has the beneficial effects that:
1) the invention creatively disintegrates and disperses cellulose by an ultrasonic-assisted method for the first time, and peels off the black phosphorus material at the same time, thereby preparing the phosphorylated CNF/black phosphorus quantum dot composite material. In the preparation process, the black phosphorus stripped layer by layer can be uniformly mixed and dispersed into the suspension, and the hydroxyl on the surface of the cellulose is 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 phosphate groups and the black phosphorus quantum dots has a synergistic flame-retardant enhancement effect, and forms thermally stable carbon after combustion, thereby inhibiting the generation of volatile components and protecting unburned materials from direct flame contact.
3) The phosphorylation CNF and the black phosphorus quantum dot are compounded, so that the advantages of phosphorus chemistry in the field of flame retardant materials are fully exerted, the materials are endowed with thermal stability and flame retardance, the development of efficient and environment-friendly flame retardants is facilitated, and the feasibility and the safety of the flame retardants in industrial application are improved.
Drawings
Fig. 1 is a transmission electron microscope image of a phosphorylated CNF/black phosphorus quantum dot composite material prepared in example 1 of the present invention.
Detailed Description
Comparative example
Weighing 7g of ammonium dihydrogen phosphate and 22g of urea, dissolving in deionized water, adjusting the pH value of the solution to 4, adding 20g of cotton, fully immersing, heating in a water bath to 30 ℃, fully immersing and swelling for 3 h.
And (3) drying the fully soaked and swollen cellulose in an air-blast drying oven at 70-100 ℃, heating to 140 ℃ after complete drying, curing for 90min, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing by vacuum filtration until the conductivity of the filtrate is less than 100 mu S/cm.
Adding water into the solidified cellulose, stirring and dispersing until the mass concentration is 0.2 wt%, and carrying out ultrasonic treatment for 6h to obtain a phosphorylated CNF suspension.
And (3) carrying out suction filtration on the suspension liquid through a vacuum suction filtration device to form a membrane, taking out the filter membrane, sticking a filter membrane on the surface of the filter membrane attached with the flame-retardant membrane, clamping the filter membrane between two metal plates, and then placing the filter membrane in an air-blast drying oven for drying at 60 ℃ for 24 hours to obtain the CNF membrane with flame-retardant performance.
Example 1
Weighing 7g of ammonium dihydrogen phosphate and 22g of urea, dissolving in deionized water, adjusting the pH value of the solution to 4, adding 20g of cotton, fully immersing, heating in a water bath to 30 ℃, fully immersing and swelling for 3 h.
And (3) drying the fully soaked and swollen cellulose in an air-blast drying oven at 70-100 ℃, heating to 140 ℃ after complete drying, curing for 90min, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing by vacuum filtration until the conductivity of the filtrate is less than 100 mu S/cm.
And adding water into the solidified cellulose, stirring and dispersing until the mass concentration is 0.2 wt%, then adding 20mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and performing ultrasonic treatment for 6 hours to obtain the CNF/black phosphorus quantum dot composite material suspension.
And (3) carrying out suction filtration on the suspension liquid through a vacuum suction filtration device to form a membrane, taking out the filter membrane, sticking a filter membrane on the surface of the filter membrane attached with the flame-retardant membrane, clamping the filter membrane between two metal plates, and then placing the filter membrane in an air drying oven to dry for 24 hours at 60 ℃ to obtain the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant membrane.
Example 2
Weighing 28g of ammonium dihydrogen phosphate and 60g of urea, dissolving in deionized water, adjusting the pH value of the solution to 8, adding 20g of cotton, fully immersing, heating in a water bath to 60 ℃, fully immersing and swelling for 1 h.
And (3) drying the fully soaked and swollen cellulose in an air-blast drying oven at 70-100 ℃, heating to 170 ℃ after complete drying, curing for 10min, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing by vacuum filtration until the conductivity of the filtrate is less than 100 mu S/cm.
And adding water into the solidified cellulose, stirring and dispersing until the mass concentration is 1wt%, then adding 5mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and performing ultrasonic treatment for 3 hours to obtain the CNF/black phosphorus quantum dot composite material suspension.
And (3) carrying out suction filtration on the suspension liquid through a vacuum suction filtration device to form a membrane, taking out the filter membrane, sticking a filter membrane on the surface of the filter membrane attached with the flame-retardant film, clamping the filter membrane between two metal plates, and then placing the filter membrane in an air drying oven to dry for 12 hours at the temperature of 80 ℃ 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 value of the solution is adjusted to 6, 20g of cotton is added to be fully immersed, the mixture is placed in a water bath and heated to 30 ℃, and the mixture is fully immersed and swollen for 3 hours.
And (3) drying the fully soaked and swollen cellulose in an air-blast drying oven at 70-100 ℃, heating to 140 ℃ after complete drying, curing for 90min, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing by vacuum filtration until the conductivity of the filtrate is less than 100 mu S/cm.
And adding water into the solidified cellulose, stirring and dispersing until the mass concentration is 0.5 wt%, then adding 10mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and performing ultrasonic treatment for 6 hours to obtain the CNF/black phosphorus quantum dot composite material suspension.
And (3) carrying out suction filtration on the suspension liquid through a vacuum suction filtration device to form a membrane, taking out the filter membrane, sticking a filter membrane on the surface of the filter membrane attached with the flame-retardant film, clamping the filter membrane between two metal plates, and then placing the filter membrane in an air drying oven to dry for 12 hours at the temperature of 80 ℃ to obtain the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant film.
Example 4
Weighing 33g of diammonium hydrogen phosphate and 60g of urea, dissolving in deionized water, adjusting the pH value of the solution to 8, adding 20g of cotton, fully immersing, heating in a water bath to 60 ℃, and fully immersing and swelling for 2 hours.
And (3) drying the fully soaked and swollen cellulose in an air-blast drying oven at 70-100 ℃, heating to 140 ℃ after complete drying, curing for 60min, mechanically stirring and dispersing the obtained cellulose in deionized water, and fully washing by vacuum filtration until the conductivity of the filtrate is less than 100 mu S/cm.
And adding water into the solidified cellulose, stirring and dispersing until the mass concentration is 0.5 wt%, then adding 10mg of black phosphorus solid, stirring at a high speed to form a uniform mixed solution, and performing ultrasonic treatment for 3 hours to obtain the CNF/black phosphorus quantum dot composite material suspension.
And (3) carrying out suction filtration on the suspension liquid through a vacuum suction filtration device to form a membrane, taking out the filter membrane, sticking a filter membrane on the surface of the filter membrane attached with the flame-retardant membrane, clamping the filter membrane between two metal plates, and then placing the filter membrane in an air drying oven to dry for 24 hours at 60 ℃ to obtain the phosphorylated CNF/black phosphorus quantum dot composite flame-retardant membrane.
In the experiment, a cone calorimeter is adopted to evaluate the flame retardant property of the phosphorylated CNF/black phosphorus quantum dot composite flame retardant filmAnd (4) price. Before the experiment, the film was placed in an environment of 23 + -1 deg.C and 50% RH for 48h, then cut to a size of 100X 3mm, wrapped with aluminum foil paper and stopped on a sample stage, and the radiation flux was set to 35kW/m2And testing to obtain the peak heat release rate of the flame-retardant film, wherein the total heat release rate is the total smoke release amount. The mechanical properties of the film can be measured by a mechanical property tester. In the experiment, a flat and defect-free film is selected, placed in the temperature of 23 +/-1 ℃ and 50% RH for 48h, cut into a sample to be tested with the length of 40mm multiplied by the width of 5mm, placed in a testing machine, and under the testing condition that the loading speed is 2mm/min, the tensile strength, Young modulus and elongation at break of the obtained sample are recorded. The test results are shown in the following table.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of a phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film is characterized by comprising the following operation steps:
1) soaking and swelling: ultrasonically dissolving phosphate and urea in deionized water, adjusting the pH value of the solution to 4-8, adding cotton, heating in a water bath, and fully soaking and swelling for 1-3 h;
2) drying and curing: drying the cotton cellulose fully soaked and swollen 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 cured cellulose, stirring and dispersing until the mass concentration is 0.2-1 wt%, then 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 a cellulose nanofiber/black phosphorus quantum dot composite suspension;
4) preparing a composite film: and (3) carrying out suction filtration on the suspension liquid through a vacuum suction filtration device to form a membrane, taking out the filter membrane, sticking a filter membrane on the surface of the filter membrane attached with the flame-retardant membrane, clamping the filter membrane between two metal plates, and then placing the filter membrane in an air-blast drying oven to dry for 12-24 hours at 40-80 ℃ to obtain the cellulose nanofiber/black phosphorus quantum dot composite membrane with flame-retardant performance.
2. The method for preparing the phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film according to claim 1, wherein the phosphate in the step 1) comprises: diammonium phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, and sodium dihydrogen phosphate.
3. The preparation method of the phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film according to claim 1, wherein in the step 1), the molar ratio of the anhydroglucose unit, the phosphate and the urea in the cellulose raw material is 1 (0.5-2) to (3-8).
4. The preparation method of the phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film according to claim 1, wherein the heating temperature in the step 1) is 30-60 ℃.
5. The preparation method of the phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film according to claim 1, wherein the curing temperature in the step 2) is 140-170 ℃.
6. The preparation method of the phosphorylated cellulose 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.
7. The preparation method of the phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film according to claim 1, wherein the ultrasonic time in the step 3) is 3-6 hours.
8. A phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film, which is characterized in that the composite flame-retardant film is prepared by the preparation method of the phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film according to any one of claims 1 to 7.
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| CN113980310A (en) * | 2021-11-25 | 2022-01-28 | 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 |
| CN115322443A (en) * | 2022-09-23 | 2022-11-11 | 苏州巨峰电气绝缘系统股份有限公司 | High-strength flame-retardant MXene/phosphorylated cellulose fiber 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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