CN113185752A - Method for preparing flame retardant by adopting red phosphorus stripped graphite - Google Patents
Method for preparing flame retardant by adopting red phosphorus stripped graphite Download PDFInfo
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- CN113185752A CN113185752A CN202110641256.0A CN202110641256A CN113185752A CN 113185752 A CN113185752 A CN 113185752A CN 202110641256 A CN202110641256 A CN 202110641256A CN 113185752 A CN113185752 A CN 113185752A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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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
- C08K3/04—Carbon
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to a method for preparing a flame retardant by adopting red phosphorus exfoliated graphite, belonging to the technical field of flame retardant materials. According to the invention, the graphite is stripped by gaseous red phosphorus, so that a multi-layer graphene structure is constructed. The graphene-based flame retardant is synthesized by a high-vacuum calcination method for the first time, and the synthesis process is free of organic solvent, environment-friendly and free of threat to human health. The flame retardant prepared by the method is structurally formed by overlapping and stacking red phosphorus and graphene in multiple layers, and the average number of layers is 5-7. Compared with a graphene structure with more than 10 layers obtained by a traditional graphene preparation method, the graphene structure has larger specific surface area, higher thermal conductivity and thermal stability.
Description
Technical Field
The invention relates to a method for preparing a flame retardant by adopting red phosphorus exfoliated graphite, belonging to the technical field of flame retardant materials.
Background
Since the concept of polymer was proposed in 1920 years, the polymer material has been rapidly developed due to its excellent comprehensive properties and economic price, and has been widely used in national production and life. However, most of the polymer materials are flammable or combustible materials, and especially with the rise of new electronic and electrical appliances and new energy fields, the number of fire safety hazards in these industries is also increasing year by year, which not only causes huge economic loss, but also causes tens of thousands of people to lose precious life.
Aiming at the condition that a high polymer material is inflammable, a flame retardant is required to be added, and the flame retardant which is most widely applied in the market is a halogen flame retardant which has a good effect, but can generate harmful gas harmful to human health in the combustion process and seriously damage the environment. Therefore, the use of halogen flame retardants is being banned internationally, and flame retardants with environmental protection, high thermal conductivity, and high thermal stability are actively sought as substitutes, and graphene is one of them.
Currently, research on the preparation of graphene is gradually progressing. The preparation method mainly comprises a micro-mechanical stripping method, an epitaxial growth method, a graphite intercalation method, a solution stripping method, a chemical vapor deposition method and an oxidation-reduction method. Geim et al prepared few-layer or single-layer graphene by oxygen plasma etching and stripping, and had simple experimental conditions but very low production efficiency. Paton et al dispersed graphite in N-methylpyrrolidone, NMP, solvent and prepared graphene using a solution exfoliation method, the obtained graphene was very stable but low in yield and not suitable for commercial applications. The graphene prepared by oxidation-reduction has high quality, low cost, high yield and high yield, but has serious harm to the environment. Therefore, it is a very challenging and significant topic to synthesize a synergistic flame retardant that combines the flame retardancy of phosphorus flame retardants and the thermal conductivity of graphene.
Disclosure of Invention
The invention aims to provide a method for preparing a flame retardant by adopting red phosphorus exfoliated graphite, which is characterized in that a multi-layer graphene structure is constructed by inserting gaseous red phosphorus into graphite. The graphene structure has the advantages of good flame retardant effect, good thermal stability and high thermal conductivity.
The purpose of the invention is realized by the following technical scheme.
A method for preparing a flame retardant by stripping graphite with red phosphorus is characterized in that the graphite is stripped by gaseous red phosphorus to construct a multi-layer graphene structure.
The method for preparing the flame retardant by adopting the red phosphorus exfoliated graphite comprises the following steps:
step one, placing ground red phosphorus and graphite in an inert atmosphere;
step two, heating to 600-700 ℃ after preheating, sublimating red phosphorus into a gas state, and inserting graphite in a phosphorus-oxygen bond combination mode; and cooling to obtain the red phosphorus graphene multilayer overlapping structure.
The mass ratio of the red phosphorus to the graphite is 1: 1.5-1: 2.
Advantageous effects
1. According to the method for preparing the flame retardant by adopting the red phosphorus stripped graphite, the graphite is stripped by converting solid red phosphorus into gaseous red phosphorus by adopting a high-vacuum calcination method for the first time, so that the graphene-based flame retardant is synthesized, and the method is free of organic solvent in the synthesis process, environment-friendly and free of threat to human health.
2. The flame retardant prepared by the method is structurally formed by overlapping and stacking red phosphorus and graphene in multiple layers, and the average number of layers is 5-7. Compared with a graphene structure with more than 10 layers obtained by a traditional graphene preparation method, the graphene structure has larger specific surface area, higher thermal conductivity and thermal stability.
3. According to the method for preparing the flame retardant by stripping the graphite from the red phosphorus, unreacted precursors can be removed through ultrasonic cleaning, the process is simple and environment-friendly, the red phosphorus is used more safely under the special protection effect of the graphene layer on the nano red phosphorus, and the flame retardant efficiency is higher.
4. The method for preparing the flame retardant by adopting the red phosphorus exfoliated graphite has the advantages of economic and cheap raw materials and simple preparation process, and greatly reduces the difficulty of industrial industrialization.
Detailed Description
The following experimental results of the present invention are combined to give an embodiment to further explain the present invention;
example 1:
a method for preparing a flame retardant by adopting red phosphorus exfoliated graphite comprises the following steps:
step one, weighing 12 g of red phosphorus and 20 g of graphite, then placing the red phosphorus and the graphite into a clean agate mortar, grinding the red phosphorus and the graphite for 15 minutes by using a pestle, and then screening the primarily obtained powder by using a 200-mesh screen to obtain 200-mesh fine red phosphorus powder.
And step two, placing the obtained 200-mesh fine powder into a quartz tube which is subjected to necking treatment and has the diameter of 15mm, vacuumizing, and introducing nitrogen.
And step three, repeating the operation of the step two for 3 times to ensure that the quartz tube is finally in a negative pressure state, and the two kinds of fine powder are protected in a nitrogen atmosphere.
And step four, preheating the quartz tube filled with the fine powder by using a flame gun, aligning the flame of a gun head of the flame gun to the necking part of the quartz tube, heating for 2 minutes, and completely sealing the quartz tube to ensure that the quartz tube is in a vacuum state and in a nitrogen protection atmosphere.
And step five, placing the treated quartz tube in the middle of a tubular calcining furnace. Heating to 630 ℃ at a heating rate of 8 ℃ per minute, keeping the temperature constant for 5 hours, then cooling to 200 ℃ per minute at a heating rate of 3 ℃/minute, keeping the temperature constant for 5 hours, finally naturally cooling to room temperature, taking out the cooled quartz tube from the tubular calcining furnace, and putting the quartz tube into a 50ml centrifuge tube
Adding absolute ethyl alcohol into a centrifugal tube, and carrying out ultrasonic treatment in an ultrasonic cleaning machine for 30 minutes under specific power; the product was collected by centrifugation at 9000 rad/min for 5 min in a centrifuge.
And seventhly, repeating the washing step of the seventh step for 3 times to obtain the final product of the nano red phosphorus intercalated graphite.
In this embodiment, the specific surface area of the nano red phosphorus intercalated graphite flame retardant is 460.8m2·g-1Pore volume of 0.258 ml/g-1The initial decomposition temperature was 467 ℃, the maximum decomposition rate was 653 ℃, the residue amount was 42.7% at 800 ℃,
the final product in the embodiment is added into bisphenol A epoxy resin, 4, 4' -diaminodiphenylmethane is taken as a curing agent to prepare the flame-retardant epoxy resin composite material, when the addition amount is 5%, the limited oxygen index can reach 31.2%, and the vertical combustion reaches UL-94V-0 level.
Example 2:
a method for preparing a flame retardant by adopting red phosphorus exfoliated graphite comprises the following steps:
step one, weighing 24 g of red phosphorus and 38 g of graphite, putting the red phosphorus and the graphite into a clean agate mortar, grinding the red phosphorus and the graphite for 15 minutes by using a pestle, and screening the primarily obtained powder by using a 200-mesh screen to obtain 200-mesh fine red phosphorus powder.
And step two, placing the obtained 200-mesh fine powder into a quartz tube which is subjected to necking treatment and has the diameter of 15mm, vacuumizing, and introducing nitrogen.
And step three, repeating the operation of the step two for 3 times to ensure that the quartz tube is finally in a negative pressure state, and the two kinds of fine powder are protected in a nitrogen atmosphere.
And step four, preheating the quartz tube filled with the fine powder by using a flame gun, aligning the flame of a gun head of the flame gun to the necking part of the quartz tube, heating for 2 minutes, and completely sealing the quartz tube to ensure that the quartz tube is in a vacuum state and in a nitrogen protection atmosphere.
And step five, placing the treated quartz tube in the middle of a tubular calcining furnace. Heating to 700 ℃ at the heating rate of 8 ℃ per minute, keeping the constant temperature for 8 hours, then cooling to 250 ℃ per minute at the heating rate of 3 ℃/minute, keeping the constant temperature for 8 hours, finally naturally cooling to room temperature, then taking out the cooled quartz tube from the tubular calcining furnace, and putting the quartz tube into a 50ml centrifuge tube.
Adding absolute ethyl alcohol into a centrifugal tube, and carrying out ultrasonic treatment in an ultrasonic cleaning machine for 30 minutes under specific power; the product was collected by centrifugation at 9000 rad/min for 5 min in a centrifuge.
And seventhly, repeating the washing step of the seventh step for 3 times to obtain the final product of the nano red phosphorus intercalated graphite.
In this embodiment, the specific surface area of the nano red phosphorus intercalated graphite flame retardant is 457.6m2·g-1Pore volume of 0.256 ml/g-1The initial decomposition temperature is 465 ℃ and the maximum decomposition temperature isThe decomposition rate was 650 ℃ and the residue amount at 800 ℃ was 42.5%.
The final product in the embodiment is added into bisphenol A epoxy resin, 4, 4' -diaminodiphenylmethane is taken as a curing agent to prepare the flame-retardant epoxy resin composite material, when the addition amount is 5%, the limited oxygen index can reach 31.0%, and the vertical combustion reaches UL-94V-0 level.
Example 3
A method for preparing a flame retardant by adopting red phosphorus exfoliated graphite comprises the following steps:
step one, weighing 10 g of red phosphorus and 20 g of graphite, then placing the red phosphorus and the graphite into a clean agate mortar, grinding the red phosphorus and the graphite for 15 minutes by using a pestle, and then screening the primarily obtained powder by using a 200-mesh screen to obtain 200-mesh fine red phosphorus powder.
And step two, placing the obtained 200-mesh fine powder into a quartz tube which is subjected to necking treatment and has the diameter of 15mm, vacuumizing, and introducing nitrogen.
And step three, repeating the operation of the step two for 3 times to ensure that the quartz tube is finally in a negative pressure state, and the two kinds of fine powder are protected in a nitrogen atmosphere.
And step four, preheating the quartz tube filled with the fine powder by using a flame gun, aligning the flame of a gun head of the flame gun to the necking part of the quartz tube, heating for 2 minutes, and completely sealing the quartz tube to ensure that the quartz tube is in a vacuum state and in a nitrogen protection atmosphere.
And step five, placing the treated quartz tube in the middle of a tubular calcining furnace. Heating to 630 ℃ at a heating rate of 8 ℃ per minute, keeping the temperature constant for 4 hours, then cooling to 200 ℃ per minute at a heating rate of 3 ℃/minute, keeping the temperature constant for 2 hours, finally naturally cooling to room temperature, taking out the cooled quartz tube from the tubular calcining furnace, and putting the quartz tube into a 50ml centrifuge tube
Adding absolute ethyl alcohol into a centrifugal tube, and carrying out ultrasonic treatment in an ultrasonic cleaning machine for 30 minutes under specific power; the product was collected by centrifugation at 9000 rad/min for 5 min in a centrifuge.
And seventhly, repeating the washing step of the seventh step for 3 times to obtain the final product of the nano red phosphorus intercalated graphite.
In this embodiment, the specific surface area of the nano red phosphorus intercalated graphite flame retardant is 465.3m2·g-1Pore volume of 0.261 ml. g-1The initial decomposition temperature is 465 ℃, the maximum decomposition rate is 658 ℃, the residue amount is 40.7 percent at 800 ℃,
the final product in the embodiment is added into bisphenol A epoxy resin, 4, 4' -diaminodiphenylmethane is taken as a curing agent to prepare the flame-retardant epoxy resin composite material, when the addition amount is 5%, the limited oxygen index can reach 32.4%, and the vertical combustion reaches UL-94V-0 level.
The specific steps of the preparation process of the product of the invention are described above, and the purpose, technical scheme and beneficial effects of the product are explained in more detail. It should be understood that the above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. A method for preparing a flame retardant by adopting red phosphorus exfoliated graphite is characterized by comprising the following steps: and stripping graphite by gaseous red phosphorus to construct a multilayer graphene structure.
2. The method of claim 1 for preparing a flame retardant using red phosphorus exfoliated graphite, wherein:
step one, placing ground red phosphorus and graphite in an inert atmosphere;
step two, heating to 600-700 ℃ after preheating, sublimating red phosphorus into a gas state, and inserting graphite in a phosphorus-oxygen bond combination mode; and cooling to obtain the red phosphorus graphene multilayer overlapping structure.
3. The method of claim 2, wherein: the mass ratio of the red phosphorus to the graphite is 1: 1.5-1: 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620264A (en) * | 2021-08-27 | 2021-11-09 | 昆明理工大学 | Preparation method of nano black phosphorus/graphene |
| CN114276762A (en) * | 2021-12-30 | 2022-04-05 | 福建科顺新材料有限公司 | Butyl hot melt adhesive composition, butyl hot melt adhesive, and preparation method and application thereof |
| KR20230074862A (en) * | 2021-11-22 | 2023-05-31 | 재단법인 한국탄소산업진흥원 | Multifunctional exfoliated graphite filler and method for manufacturing same |
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2021
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620264A (en) * | 2021-08-27 | 2021-11-09 | 昆明理工大学 | Preparation method of nano black phosphorus/graphene |
| CN113620264B (en) * | 2021-08-27 | 2023-03-17 | 昆明理工大学 | Preparation method of nano black phosphorus/graphene |
| KR20230074862A (en) * | 2021-11-22 | 2023-05-31 | 재단법인 한국탄소산업진흥원 | Multifunctional exfoliated graphite filler and method for manufacturing same |
| KR102631853B1 (en) * | 2021-11-22 | 2024-01-30 | 재단법인 한국탄소산업진흥원 | Method of manufacturing exfoliated graphite filler for flame retardant, insulating and heat dissipating composite materials |
| CN114276762A (en) * | 2021-12-30 | 2022-04-05 | 福建科顺新材料有限公司 | Butyl hot melt adhesive composition, butyl hot melt adhesive, and preparation method and application thereof |
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