CN112852155A - Preparation method of polyimide/black phosphorus alkene flame retardant powder - Google Patents
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- CN112852155A CN112852155A CN202110222790.8A CN202110222790A CN112852155A CN 112852155 A CN112852155 A CN 112852155A CN 202110222790 A CN202110222790 A CN 202110222790A CN 112852155 A CN112852155 A CN 112852155A
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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Abstract
The invention relates to the field of flame-retardant materials, in particular to a preparation method of polyimide/black phosphorus alkene flame-retardant powder. Under the protective atmosphere, dispersing black phosphorus or black phosphorus alkene in an aprotic polar organic solvent; and adding anhydride and amine of a polyimide system, fully stripping the black phosphorus or the black phosphorus into nano-scale particles, dispersing the nano-scale particles in the system, controlling the temperature of the materials to be at or below room temperature, reacting to form a polyamic acid coated black phosphorus prepolymer, carrying out thermal imidization on the prepolymer to obtain polyimide coated black phosphorus powder, washing the polyimide coated black phosphorus powder for a plurality of times by using a solvent, and carrying out vacuum drying to obtain the polyimide/black phosphorus flame-retardant powder. The solvent and the monomer of the system are creatively utilized to protect the black phosphorus alkene from being degraded, and the size of the black phosphorus alkene is controlled in the polymerization process of the system. The method prepares the flame-retardant powder by combining an ultrasonic liquid phase stripping method and a polyimide polymerization system and coating in situ, can promote the compounding of a large amount of the black phosphorus alkene and the polyimide, and overcomes the defects of low yield and low utilization rate of the black phosphorus alkene.
Description
Technical Field
The invention relates to the field of flame-retardant materials, in particular to a preparation method of polyimide/black phosphorus alkene flame-retardant powder.
Background
Polyimide (PI) is a special engineering plastic and is widely applied to the fields of aerospace, microelectronics and photoelectricity. It has excellent chemical stability, wear resistance, high temperature resistance, electric insulating property and mechanical property. The polyimide powder resin is required to be molded or extruded, and particularly, the polyimide powder resin is required to be mixed with some inorganic fillers during molding, so that the powder has finer and more uniform particle size. The conventional polyimide powder is generally obtained by heating a solution of polyamic acid to obtain a powder, or by adding triethylamine to the solution of polyamic acid and then performing thermal imidization on the solution of polyamic acid to obtain a powder, or by performing thermal imidization on the polyamic acid with pyridine as a solvent to obtain a powder.
The application of black phosphorus alkene as a new inorganic two-dimensional nano material in polyimide is only reported. The black phosphorus alkene can be prepared from black phosphorus by a mechanical stripping method and a liquid phase stripping method. The liquid phase stripping method is advantageous in that when the surface energy of the chemical solvent is matched with that of the two-dimensional material, the interaction between the solvent and the two-dimensional material can balance the energy required for stripping the material, and the bulk material can be stripped into the laminar material by ultrasound. The atomic layer black phosphorus prepared by the liquid phase stripping method has the advantages of high yield, low equipment requirement and the like, and meanwhile, the degradation of the atomic layer black phosphorus can be slowed down by the presence of an organic reagent, but the size of the obtained product is small and the organic solvent is difficult to remove.
Through retrieval, the fresh technology relates to the report of black phosphorus alkene in-situ modification polyimide. An issued patent retrieved: a black phosphorus modified polyimide composite material and a preparation method and application thereof (CN 109880365B). The patent does not relate to black phosphorus alkene, does not relate to the polymerization of polyimide, and the patent only utilizes substances such as polymerized polyimide particles, black phosphorus and the like to be mixed in absolute ethyl alcohol, then removes the ethyl alcohol to obtain dry mixture, and finally presses and sinters to prepare the black phosphorus modified polyimide composite material. The black phosphorus is only used as a friction lubricant, and is basically a melt blending of a polymer and inorganic particles. No relevant research report or patent is found, and the polyimide/black phosphorus alkene flame retardant powder is prepared by coating black phosphorus alkene on polyamic acid in situ.
Disclosure of Invention
The invention mainly aims at the defect that the black phosphorus alkene is easy to be decomposed by water vapor, oxygen and the like in the environment. A method for preparing polyimide/black phosphorus flame-retardant powder is provided. The flame retardant powder is prepared by intercalating black phosphorus with a solvent and a monomer of a polyimide system, further stripping the black phosphorus in the system into black phosphorus by an ultrasonic stripping method, coating the black phosphorus with pre-polymerized polyamic acid, and performing thermal imidization in the solvent. Not only ensures the stability of the black phosphorus alkene in the using process, but also widens the application of the black phosphorus alkene in the flame retardant field.
The invention is realized by the following technical scheme:
the preparation method of the polyimide/black phosphorus alkene flame retardant powder comprises the following raw materials in parts by weight: 1-50 parts of black phosphorus or black phosphorus alkene, 100-400 parts of an aprotic polar solvent, 20-100 parts of anhydride of a polyimide system and 20-200 parts of amine of the polyimide system; under the protective atmosphere, dispersing black phosphorus or black phosphorus alkene in an aprotic polar organic solvent; and adding anhydride and amine of a polyimide system, fully stripping the black phosphorus or the black phosphorus into nano-scale particles, dispersing the nano-scale particles in the system, controlling the temperature of the materials to be at or below room temperature, reacting to form a polyamic acid coated black phosphorus prepolymer, carrying out thermal imidization on the prepolymer to obtain polyimide coated black phosphorus powder, washing the polyimide coated black phosphorus powder for a plurality of times by using a solvent, and carrying out vacuum drying to obtain the polyimide/black phosphorus flame-retardant powder.
Further, the black phosphorus comprises blocky black phosphorus and low-dimensional black phosphorus, the blocky black phosphorus is converted from white phosphorus or red phosphorus under high temperature and high pressure, and the black phosphorus alkene is prepared in a polyimide system by a liquid phase stripping method.
Furthermore, the particle size of the black phosphorus alkene is 10 nm-100 mu m, and the thickness of the lamella is 1-200 nm.
Furthermore, the particle size of the black phosphorus is 100 mu m-100 mm, and the thickness of the lamella is 200 nm-10 mm.
Further, the protective gas is any one or mixture of nitrogen and argon.
Further, the reaction temperature of the polyimide is-20-30 ℃, and the reaction time is 1-24 hours.
Further, the temperature of the thermal imidization of the prepolymer is 100-400 ℃, and the reaction time is 1-6 h.
Further, the black phosphorus or black phosphorus alkene is stripped by an ultrasonic liquid phase stripping method, the ultrasonic power is 100-7200W, the frequency is 20-100 KHZ, and the ultrasonic time is 1-48 h. The black phosphorus or black phosphorus alkene is further stripped into nanometer grade by the ultrasonic liquid phase stripping method.
Further, the aprotic polar solvent is at least one of anhydrous acetonitrile, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, hexamethylphosphoric triamide and N, N-dimethylpropylurea.
Further, the acid anhydride of the polyimide system is a single anhydride compound, a benzene dianhydride compound, or a biphenyl dianhydride compound. For example, at least one of pyromellitic dianhydride, trimellitic anhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, hexafluoro dianhydride, and the like.
Further, the amines are monobasic amines, phenylenediamine, naphthalenediamine, benzidines and diaminodiphenylmethanes. For example, at least one of p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminophenol, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -diaminodiphenylmethane (MDA), and the like.
Further, the washing solvent is any one of NMP, acetone, hexane, methanol and ethanol.
The polyimide/black phosphorus alkene flame retardant powder can be applied to the flame retardant field of various materials such as engineering plastics, rubber, paint and fiber, such as polyamide, polyimide, polyurethane, nitrile rubber, acrylic paint and the like.
Compared with the prior art, the invention has the following beneficial effects:
the polyimide/black phosphorus alkene flame retardant powder provided by the invention creatively utilizes the solvent and the monomer of the system to protect the black phosphorus alkene from being degraded, and the size of the black phosphorus alkene can be controlled in the polymerization process of the system. The method prepares the flame-retardant powder by combining an ultrasonic liquid phase stripping method and a polyimide polymerization system and coating in situ, can compound a large amount of black phosphorus alkene and polyimide, and overcomes the defects of low yield and low utilization rate of the black phosphorus alkene.
The invention creatively carries out ultrasonic liquid phase stripping on the black phosphorus in a polyimide system, and utilizes the pre-polymerized polyamic acid to coat the black phosphorus alkene so as to lead the black phosphorus alkene to reach nano-scale dispersion without agglomeration. And then the size of the black phosphorus alkene is controlled by combining the intensity and the duration of the ultrasonic wave, the form and the degree of the black phosphorus alkene coated by the polyamic acid are controlled by selecting the acid anhydride and the amine of the polyimide system, and finally the form and the size of the powder are controlled by thermal imidization. The method isolates black phosphorus from oxygen and water in the coating process through a solvent and a monomer of a polyimide system, so that the black phosphorus is prevented from being degraded, and finally the black phosphorus is coated in the polyimide powder.
Drawings
FIG. 1 is an SEM image of a polyimide/black phosphorus flame retardant powder prepared in example 1.
FIG. 2 is an SEM image of a polyimide/black phosphorus flame retardant powder prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples. Unless otherwise indicated, the various starting materials used in the examples of the present invention are either conventionally available commercially or prepared according to conventional methods in the art using equipment commonly used in the laboratory. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention discloses a preparation method of polyimide/black phosphorus alkene flame retardant powder, which comprises the following raw materials in parts by weight: 1-50 parts of black phosphorus or black phosphorus alkene, 100-400 parts of an aprotic polar solvent, 20-100 parts of anhydride of a polyimide system and 20-200 parts of amine of the polyimide system; under the protective atmosphere, dispersing black phosphorus or black phosphorus alkene in an aprotic polar organic solvent; and adding anhydride and amine of a polyimide system, fully stripping the black phosphorus or the black phosphorus into nano-scale particles, dispersing the nano-scale particles in the system, controlling the temperature of the materials to be at or below room temperature, reacting to form a polyamic acid coated black phosphorus prepolymer, carrying out thermal imidization on the prepolymer to obtain polyimide coated black phosphorus powder, washing the polyimide coated black phosphorus powder for a plurality of times by using a solvent, and carrying out vacuum drying to obtain the polyimide/black phosphorus flame-retardant powder.
The particle size of the black phosphorus alkene is 10 nm-100 mu m, the thickness of the lamella is 1-200 nm, the particle size of the black phosphorus alkene is 100 mu m-100 mm, and the thickness of the lamella is 200 nm-10 mm.
The black phosphorus disclosed by the invention comprises blocky black phosphorus and low-dimensional black phosphorus, wherein the blocky black phosphorus is obtained by converting white phosphorus or red phosphorus at high temperature and high pressure, and the low-dimensional black phosphorus is prepared from the blocky black phosphorus by a mechanical stripping method or a liquid phase stripping method.
The aprotic polar solvent is at least one of anhydrous acetonitrile, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, hexamethylphosphoric triamide and N, N-dimethylpropyleneurea.
The acid anhydride of the polyimide system is a single anhydride compound, a benzene dianhydride compound and a biphenyl dianhydride compound. For example, at least one of pyromellitic dianhydride, trimellitic anhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, hexafluoro dianhydride, and the like.
The amine is selected from the group consisting of monoamines, phenylenediamine, naphthalenediamine, benzidine and diaminodiphenylmethane. For example, at least one of p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminophenol, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -diaminodiphenylmethane (MDA), and the like.
Specific embodiments thereof are as follows.
Example 1
The preparation method of the polyimide/black phosphorus alkene flame retardant powder in the embodiment comprises the following steps:
s1, adding 1L of anhydrous and oxygen-free N-methyl pyrrolidone (NMP) into a prepolymerization reactor, adding 1g of black phosphorus with the particle size of 100 mu m and the thickness of 200nm, 0.25mol of pyromellitic dianhydride and 0.25mol of p-phenylenediamine into the prepolymerization reactor together, mixing with the NMP, introducing circulating nitrogen gas into the whole reaction system, and removing air and a small amount of moisture in the system;
s2, carrying out ultrasonic treatment on the prepolymerization reactor, stripping black phosphorus in the system into black phosphorus alkene by an ultrasonic liquid phase method, wherein the ultrasonic power is 3000W, the frequency is 20KHZ, the ultrasonic treatment is 12h, cooling the system by introducing cooling water into an inner coil and an outer coil, and keeping the reaction temperature at 30 ℃ to prepare polyimide acid-coated black phosphorus alkene prepolymer mixed liquid;
s3, heating to 200 ℃ in NMP solvent under the protection of circulating nitrogen or argon to react for 2h to obtain polyimide/black phosphorus alkene flame-retardant powder, filtering out the flame-retardant powder, washing with acetone for 3 times, and vacuum-drying at 150 ℃ for 24 h.
The appearance of the polyimide/black phosphorus alkene powder prepared by the method is observed by a scanning electron microscope. As is known from fig. 1. The size of the flame-retardant powder is 2-6 mu m, protrusions of polyimide microspheres are arranged on the surface of the flame-retardant powder, and the black phosphorus alkene is completely coated in the protrusions. The micron-sized flame-retardant powder can enable the flame-retardant grade of nylon 66 to reach V-0.
Example 2
The preparation method of the polyimide/black phosphorus alkene flame retardant powder in the embodiment comprises the following steps:
s1, adding 500ml of anhydrous and oxygen-free Dimethylacetamide (DMAC) into a polymerization reactor, mixing 1g of black phosphorus with the particle size of 30-50 microns and the sheet thickness of 200nm with the DMAC, introducing circulating nitrogen gas into the whole reaction system, removing air and a small amount of moisture in the system, and treating the system for 6 hours by an ultrasonic liquid phase method, wherein the ultrasonic power is 3000W, and the frequency is 40 KHZ;
s2, cooling the system to room temperature by utilizing circulating water and circulating nitrogen, adding 0.1mol of trimellitic anhydride and 0.1mol of naphthalene diamine into a prepolymerization reactor together, reacting at the temperature of 20 ℃ for 12 hours, and preparing the mixed solution of the polyamic acid coated black phosphorus alkene prepolymer.
S3, heating the mixture to 220 ℃ in a solvent DMAC under the protection of circulating nitrogen, reacting for 10 hours to obtain polyimide/black phosphorus alkene flame-retardant powder, cooling to room temperature, filtering out the flame-retardant powder, washing with ethanol for 3 times, and drying in vacuum at 200 ℃ for 24 hours.
The appearance of the polyimide/black phosphorus alkene flame retardant powder prepared by the method is observed by a scanning electron microscope. As is known from fig. 2. The size of the flame-retardant powder is 10-20 mu m, and besides the whole body is spherical, tiny hollows also appear in the sphere, so that the flame-retardant powder can be better compounded with other matrixes. The flame-retardant powder is compounded with nylon 66, so that the flame-retardant grade reaches V-0, and the mechanical property is improved.
Example 3
The preparation method of the polyimide/black phosphorus alkene flame retardant powder by coating black phosphorus alkene with polyamic acid in situ in the embodiment comprises the following steps:
s1, adding 800ml of anhydrous and oxygen-free Dimethylformamide (DMF) into a prepolymerization reactor, adding 2g of black phosphorus alkene with the particle size of 100-200 nm and the thickness of 50-100 nm, 0.2mol of diphenyl ether dianhydride and 0.2mol of 4, 4' -diaminodiphenylmethane (MDA) into the prepolymerization reactor together, mixing with the DMF, introducing circulating nitrogen gas into the whole reaction system, and removing air and a small amount of water in the system;
s2, carrying out ultrasonic treatment on the prepolymerization reactor, stripping black phosphorus in the system into black phosphorus alkene by an ultrasonic liquid phase method, treating for 24 hours at the ultrasonic power of 2400W and the frequency of 28KHz, cooling the system by introducing cooling water into an inner coil and an outer coil, keeping the reaction temperature at-10 ℃, and preparing polyimide acid coated black phosphorus alkene prepolymer mixed liquor;
s3, under the protection of circulating nitrogen, carrying out thermal imidization for 1h at 340 ℃ in a DMF solvent to obtain the polyimide/black phosphorus alkene flame retardant powder.
Example 4
The preparation method of the polyimide/black phosphorus alkene flame retardant powder by coating black phosphorus alkene with polyamic acid in situ in the embodiment comprises the following steps:
s1, adding 2L of anhydrous and oxygen-free dimethyl sulfoxide into a polymerization reactor, mixing 10g of black phosphorus with the particle size of 100 microns and the thickness of 100mm with the dimethyl sulfoxide, introducing circulating nitrogen gas into the whole reaction system, removing air and a small amount of moisture in the system, and treating the system by an ultrasonic liquid phase method, wherein the ultrasonic power is 3000W, the frequency is 80KHZ, and the treatment time is 24 hours;
s2, cooling the system to room temperature by utilizing circulating water and circulating nitrogen, adding 1mol of trimellitic anhydride and 1mol of diaminodiphenylmethane together, adding the mixture into a prepolymerization reactor, and reacting for 12 hours to prepare the polyimide acid-coated black phosphorus alkene prepolymer mixed solution.
And S3, heating to 180 ℃ in a dimethyl sulfoxide solvent under the protection of circulating nitrogen, and carrying out thermal imidization for 4 hours to obtain the polyimide/black phosphorus alkene flame retardant powder.
The invention creatively carries out ultrasonic liquid phase stripping on the black phosphorus in a polyimide system, and utilizes the pre-polymerized polyamic acid to coat the black phosphorus alkene so as to lead the black phosphorus alkene to reach nano-scale dispersion without agglomeration. And then the size of the black phosphorus alkene is controlled by combining the intensity and the duration of the ultrasonic wave, the form and the degree of the black phosphorus alkene coated by the polyamic acid are controlled by selecting the acid anhydride and the amine of the polyimide system, and finally the form and the size of the powder are controlled by thermal imidization. The method isolates black phosphorus from oxygen and water in the coating process through a solvent and a monomer of a polyimide system, so that the black phosphorus is prevented from being degraded, and finally the black phosphorus is coated in the polyimide powder.
Claims (10)
1. The preparation method of the polyimide/black phosphorus alkene flame retardant powder is characterized by using the following raw materials in parts by mass: 1-50 parts of black phosphorus or black phosphorus alkene, 100-400 parts of an aprotic polar solvent, 20-100 parts of anhydride of a polyimide system and 20-200 parts of amine of the polyimide system; under the protective atmosphere, dispersing black phosphorus or black phosphorus alkene in an aprotic polar organic solvent; and adding anhydride of a polyimide system and amine of the polyimide system, fully stripping the black phosphorus or the black phosphorus into nano-scale particles, dispersing the nano-scale particles in the system, controlling the temperature of the materials to be at or below room temperature, reacting to form a polyamic acid coated black phosphorus prepolymer, performing thermal imidization on the prepolymer to obtain polyimide coated black phosphorus powder, washing the polyimide coated black phosphorus powder for a plurality of times by using a solvent, and performing vacuum drying to obtain the polyimide/black phosphorus flame-retardant powder.
2. The method for preparing the polyimide/black phosphorus alkene flame retardant powder according to claim 1, wherein the particle size of the black phosphorus alkene is 10nm to 100 μm, and the thickness of the lamella is 1 nm to 200 nm; the particle size of the black phosphorus is 100 mu m-100 mm, and the thickness of the lamella is 200 nm-10 mm.
3. The method for preparing the polyimide/black phosphorus alkene flame retardant powder according to claim 1, wherein the vacuum drying is performed at 100-200 ℃ for more than 24 h.
4. The preparation method of the polyimide/black phosphorus alkene flame retardant powder according to claim 1, wherein the black phosphorus or black phosphorus alkene is stripped by an ultrasonic liquid phase stripping method, wherein the ultrasonic power is 100-7200W, the frequency is 20-100 KHZ, and the ultrasonic time is 1-48 h.
5. The method for preparing the polyimide/black phosphorus alkene flame retardant powder according to claim 1, wherein the reaction temperature of the polyimide is-20 to 30 ℃ and the reaction time is 1 to 24 hours.
6. The method for preparing the polyimide/black phosphorus alkene flame retardant powder according to claim 1, wherein the temperature of the thermal imidization of the prepolymer is 100-400 ℃ and the reaction time is 1-6 h.
7. The method of claim 1, wherein the aprotic polar solvent is at least one of anhydrous acetonitrile, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, dimethylsulfoxide, hexamethylphosphoric triamide, and N, N-dimethylpropylurea.
8. The method of claim 1, wherein the acid anhydride of the polyimide system is selected from the group consisting of monomeric anhydride compounds, benzene dianhydride compounds, and biphenyl dianhydride compounds.
9. The method of claim 1, wherein the amine of the polyimide system is selected from the group consisting of monoamines, phenylenediamine, naphthalenediamine, benzidines, and diaminodiphenylmethanes.
10. The method of claim 1, wherein the washing solvent is any one of NMP, acetone, hexane, methanol and ethanol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115960460A (en) * | 2023-03-13 | 2023-04-14 | 无锡顺铉新材料有限公司 | Flame-retardant conductive polyimide composite film and preparation method thereof |
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