CN110713615A - Carbon nano tube/polyimide composite film and preparation method thereof - Google Patents
Carbon nano tube/polyimide composite film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a carbon nano tube/polyimide composite material film, which comprises the following steps: obtaining a carbon nanotube film and molten polyimide; under the conditions that the running speed of the carbon nano tube film is 10-20 cm/min and the temperature is 350-420 ℃, spraying the fused polyimide on the surface of the carbon nano tube film in the spraying amount of 2-120 mL/min, pressurizing the carbon nano tube film sprayed with the fused polyimide, and cooling to obtain the carbon nano tube/polyimide composite material film. The preparation method of the carbon nano tube/polyimide composite film provided by the invention can realize continuous mass production by regulating the running speed of the carbon nano tube film and the spraying condition of the molten polyimide, has a simple preparation process, and is suitable for industrial large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a carbon nano tube/polyimide composite material film and a preparation method thereof.
Background
Polyimide (PI) has the characteristics of high temperature resistance, low temperature resistance, radiation resistance, chemical resistance, excellent mechanical property and the like, is engineering plastic with huge development potential, and has wide application in various fields such as aerospace, electronic and electrical devices and the like, particularly in the aerospace field. Because of the influence of space environment, the aerospace field has strict requirements on various properties of high polymer materials, and polyimide is used as a high heat-resistant material, has high chemical stability, high mechanical property, high radiation resistance and high processability, and has a large application space in aerospace industry. However, polyimide has a high resistivity, and charges are not easy to move in the material, and accumulated charges are difficult to diffuse, so that static electricity is formed, and the static electricity is extremely dangerous in the aerospace field, and easily damages aviation equipment and electronic components. The conductive additive is added into the polyimide substrate, so that electrostatic protection can be effectively achieved, and the mechanical property of the substrate can be improved.
At present, in order to improve the conductivity of polyimide films, common additives comprise graphite carbon materials, carbon nanotubes and the like, wherein P electrons of carbon atoms on the carbon nanotubes form a large-range delocalized pi bond, the conjugation effect is obvious, and the carbon nanotubes have some special electrical properties, and have the same structure as a graphite lamellar structure, so the carbon nanotubes have good electrical properties. However, the current composite of carbon nanotubes and polyimide has two problems: on one hand, the compounding of the carbon nanotube and the polyimide is usually to add the carbon nanotube into the polyimide by ultrasonic or functionalization and other methods, however, the functionalization of the carbon nanotube or the treatment of high-power ultrasonic and other methods can reduce the electrical, thermal or mechanical properties of the carbon nanotube itself, and the uniformity of dispersion can generally affect the properties of the final composite material; on the other hand, in the existing polyimide production methods, for polyimides having no significant glass transition temperature, although they have excellent high-temperature stability, they require a specific method such as sintering molding for processing when they are used for molding materials, and for polyimides having excellent processability and low glass transition temperature, high-temperature stability is poor, production conditions and modes are limited, thermal stability cannot be maintained at high temperatures for a long period of time, and continuous mass production is difficult.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a preparation method of a carbon nanotube polyimide composite film, and aims to solve the technical problems that the electrical, thermal and mechanical properties of a carbon nanotube are damaged by the functionalization and other treatments of the carbon nanotube, the polyimide has poor processability at high temperature for a long time, the film layer compounding efficiency is poor, the carbon nanotube loading capacity is low, the comprehensive properties of the composite film are not ideal and the like in the conventional preparation method of the carbon nanotube polyimide composite film.
Another object of the present invention is to provide a carbon nanotube polyimide composite film.
Means for solving the problems
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a carbon nano tube/polyimide composite film comprises the following steps:
obtaining a carbon nanotube film and molten polyimide;
under the conditions that the running speed of the carbon nano tube film is 10-20 cm/min and the temperature is 350-420 ℃, spraying the molten polyimide on the surface of the carbon nano tube film in a spraying amount of 2-120 mL/min, pressurizing the carbon nano tube film sprayed with the molten polyimide, and cooling to obtain the carbon nano tube/polyimide composite material film, wherein the volume percentage content of the carbon nano tube in the carbon nano tube/polyimide composite material film is 30-70%.
Preferably, the molten polyimide has a melt viscosity of 0.49 to 0.53 dl/g; and/or the presence of a gas in the gas,
the injection pressure of the molten polyimide is 80-150 kg/cm2(ii) a And/or the presence of a gas in the gas,
in the step of pressurizing the carbon nanotube film sprayed with the molten polyimide, the applied pressure is 50-70 kg/cm2。
Preferably, the tube length of the carbon nano tube in the carbon nano tube film is 100-1000 mu m, and the tube diameter is 6-15 nm; and/or the presence of a gas in the gas,
the carbon nanotube film is selected from: at least one of a film directly drawn from the carbon nanotube array, a film formed by unidirectional arrangement of carbon nanotube fibers, and a film formed by weaving of carbon nanotube fibers; the carbon nanotube fiber is obtained by twisting a carbon nanotube array film.
Preferably, the preparation of the polyimide comprises the steps of:
obtaining aromatic diamine, tetracarboxylic dianhydride and dicarboxylic anhydride, and dissolving the aromatic diamine, the tetracarboxylic dianhydride and the dicarboxylic anhydride in an organic solvent to react for 4-24 hours under a protective gas atmosphere at the temperature of 20-60 ℃ to obtain polyamic acid;
and imidizing the polyamic acid for 10-20 hours at a high temperature of 150-250 ℃ or under the action of a dehydrating agent and a catalyst to obtain the polyimide.
Preferably, the molar ratio of the aromatic diamine, the tetracarboxylic dianhydride, the dicarboxylic anhydride and the solvent is 1: (0.9-1.0): (0.01-0.5): (60-65); and/or the presence of a gas in the gas,
the molar ratio of the polyamic acid to the dehydrating agent and the catalyst is 1: (2-4): (2-4).
Preferably, the aromatic diamine is selected from: one or more of 4,4' -bis (3-aminophenoxy) biphenyl, 2' -bis [4- (3-aminophenoxy) phenyl) ] propane, 4' -bis (3-aminophenoxy) benzophenone; and/or the presence of a gas in the gas,
the tetracarboxylic dianhydride is selected from: one or more of ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, and 3,3',4,4' -biphenyl tetracarboxylic dianhydride; and/or the presence of a gas in the gas,
the dicarboxylic acid anhydride is selected from: one or more of glutaric anhydride, citraconic anhydride, phthalic anhydride and succinic anhydride; and/or the presence of a gas in the gas,
the solvent is selected from: at least one of N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylpyrrolidone, N-diethylacetamide, N-dimethylacetamide, and 1, 3-dimethyl-2-imidazolidinone; and/or the presence of a gas in the gas,
the dehydrating agent is selected from: at least one of acetic anhydride and propionic anhydride; and/or the presence of a gas in the gas,
the catalyst is selected from: at least one of triethylamine and pyridine.
Preferably, the method comprises the following steps:
obtaining molten polyimide;
the method comprises the steps of obtaining a carbon nanotube film, enabling the carbon nanotube film to pass through gaps of a plurality of hot rollers with the temperature of 350-420 ℃, and enabling the carbon nanotube film to run at the speed of 10-20 cm/min through the matching rotation of the hot rollers;
under the condition that the temperature is 350-420 ℃, the spraying amount of the molten polyimide is 2-120 mL/min, and 80-150 kg/cm2The ejection pressure of (a) is ejected on the surface of the carbon nanotube film;
applying 50-70 kg/cm of a carbon nanotube film perpendicular to a surface of the carbon nanotube film coated with a molten polyimide2After the pressure is pressurized, the carbon nano tube/polyimide composite material film is obtained after cooling to the room temperature, wherein the volume percentage of the carbon nano tube in the carbon nano tube/polyimide composite material film is 30-70%.
Preferably, after cooling to obtain the carbon nanotube/polyimide composite film, the method further comprises the following steps: laminating 10-25 carbon nanotube/polyimide composite films, and heating at 320-400 deg.C under 30-50 kg/cm2And carrying out hot pressing treatment under the condition to obtain the carbon nano tube/polyimide composite board.
Correspondingly, the carbon nanotube/polyimide composite material film is prepared by the method and comprises a carbon nanotube film and polyimide which is soaked and coated on the carbon nanotube film, wherein the volume percentage of the carbon nanotubes in the carbon nanotube/polyimide composite material film is 30-70%.
Correspondingly, the carbon nanotube/polyimide composite board is obtained by laminating and pressing 10-25 carbon nanotube/polyimide composite material films.
Effects of the invention
The preparation method of the carbon nano tube/polyimide composite material film provided by the invention comprises the steps of taking a carbon nano tube film as a base material, spraying molten polyimide on the surface of the carbon nano tube film in a spraying amount of 2-120 mL/min under the conditions that the running speed of the carbon nano tube film is 10-20 cm/min and the temperature is 350-420 ℃, pressurizing the carbon nano tube film sprayed with the molten polyimide, and cooling to obtain the carbon nano tube/polyimide composite material film, wherein the volume percentage content of the carbon nano tube in the carbon nano tube/polyimide composite material film is 30-70%. On one hand, the carbon nano tube film is used as a reinforcement of the composite material film, polyimide is melted and then is sprayed on the surface of the carbon nano tube film to form the composite material film, the dispersion problem of the carbon nano tube is not needed to be considered, and the damage to the structure and the performance of the carbon nano tube caused by the modification and other treatments of the carbon nano tube in order to disperse the carbon nano tube in the polyimide in the traditional method is avoided; on the other hand, the content of the carbon nano tube in the composite material film can be flexibly controlled by controlling the spraying amount of the polyimide and the running speed of the carbon nano tube film, the bearing capacity of the carbon nano tube in the polyimide composite material film is obviously improved, and the carbon nano tube and the polyimide composite material film have good bonding stability by fully infiltrating the polyimide to the carbon nano tube film layer, so that the mechanical properties such as the flexibility, the flexural modulus and the like of the composite material film and the performances such as electrochemistry are excellent; on the other hand, the carbon nanotubes in the carbon nanotube/polyimide composite film can realize high orientation, and the orientation of the carbon nanotubes in the carbon nanotube film can be flexibly regulated and controlled by controlling the orientation of the carbon nanotubes in the carbon nanotube film, so that the carbon nanotubes in the composite film are oriented uniformly, and the mechanical property, the electric conduction property and other properties of the composite film are further improved. In addition, the preparation method of the carbon nanotube/polyimide composite film provided by the invention not only enables the volume percentage of the carbon nanotube in the prepared carbon nanotube/polyimide composite film to be 30-70% by regulating the running speed of the carbon nanotube film and the spraying condition of the molten polyimide, but also has excellent mechanical and conductive properties; moreover, the method can realize continuous mass production, has simple preparation process and is suitable for industrial large-scale production and application.
The carbon nanotube/polyimide composite material film provided by the invention comprises a carbon nanotube film and polyimide permeating and coating the carbon nanotube film, wherein the volume percentage of the carbon nanotube in the carbon nanotube/polyimide composite material film is 30-70%, and the carbon nanotube film has excellent mechanical and electric conduction properties, and if the volume percentage of the carbon nanotube film in the composite material film is lower than 30%, the carbon nanotube film cannot play a role in enhancing the mechanical and other properties of the composite material film, and cannot play an excellent charge conduction role easily; if the volume is more than 70%, the interlayer strength of the molded article obtained by the subsequent processing may be significantly reduced.
The carbon nanotube/polyimide composite board provided by the invention is prepared from 10-25 carbon nanotube/polyimide composite material films with excellent mechanical and electric conductivity and other properties, so that the carbon nanotube/polyimide composite board also has excellent mechanical and electric conductivity and other properties.
Drawings
FIG. 1 is a schematic view of a continuous process for preparing a carbon nanotube/polyimide composite film according to an embodiment of the present invention.
FIG. 2 is another schematic diagram of a continuous manufacturing process of a carbon nanotube/polyimide composite film according to an embodiment of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a preparation method of a carbon nano tube/polyimide composite film, which comprises the following steps:
s10, obtaining a carbon nanotube film and molten polyimide;
s20, under the conditions that the running speed of the carbon nano tube film is 10-20 cm/min and the temperature is 350-420 ℃, spraying the molten polyimide on the surface of the carbon nano tube film in a spraying amount of 2-120 mL/min, pressurizing the carbon nano tube film sprayed with the molten polyimide, and cooling to obtain the carbon nano tube/polyimide composite material film, wherein the volume percentage content of the carbon nano tubes in the carbon nano tube/polyimide composite material film is 30-70%.
The preparation method of the carbon nano tube/polyimide composite film provided by the embodiment of the invention takes the carbon nano tube film as a base material, sprays the molten polyimide on the surface of the carbon nano tube film in the spraying amount of 2-120 mL/min under the conditions that the running speed of the carbon nano tube film is 10-20 cm/min and the temperature is 350-420 ℃, pressurizes the carbon nano tube film sprayed with the molten polyimide, and cools to obtain the carbon nano tube/polyimide composite film. On one hand, the carbon nano tube film is used as a reinforcement of the composite material film, polyimide is melted and then is sprayed on the surface of the carbon nano tube film to form the composite material film, the dispersion problem of the carbon nano tube is not needed to be considered, and the damage to the structure and the performance of the carbon nano tube caused by the modification and other treatments of the carbon nano tube in order to disperse the carbon nano tube in the polyimide in the traditional method is avoided; on the other hand, the content of the carbon nano tube in the composite material film can be flexibly controlled by controlling the spraying amount of the polyimide and the running speed of the carbon nano tube film, the bearing capacity of the carbon nano tube in the polyimide composite material film is obviously improved, and the carbon nano tube and the polyimide composite material film have good bonding stability by fully infiltrating the polyimide to the carbon nano tube film layer, so that the mechanical properties such as the flexibility, the flexural modulus and the like of the composite material film and the performances such as electrochemistry are excellent; on the other hand, the carbon nanotubes in the carbon nanotube/polyimide composite film disclosed by the embodiment of the invention can realize high orientation, and the orientation of the carbon nanotubes in the composite film can be flexibly regulated and controlled by controlling the orientation of the carbon nanotubes in the carbon nanotube film layer, so that the carbon nanotubes in the composite film are oriented uniformly, and the mechanical property, the electric conduction property and other properties of the composite film are further improved. In addition, according to the preparation method of the carbon nanotube/polyimide composite film provided by the embodiment of the invention, the volume percentage of the carbon nanotubes in the prepared carbon nanotube/polyimide composite film is 30-70% by regulating the running speed of the carbon nanotube film and the spraying condition of the molten polyimide, so that the carbon nanotube/polyimide composite film has excellent mechanical and electric conductivity properties; moreover, the method can realize continuous mass production, has simple preparation process and is suitable for industrial large-scale production and application.
Specifically, in the above step S10, the carbon nanotube film and the molten polyimide are obtained.
In a further embodiment, the carbon nanotubes in the carbon nanotube film have a tube length of 100 to 1000 μm and a tube diameter of 6 to 15 nm. The carbon nanotube film in the embodiment of the invention is prepared from carbon nanotubes with the tube length of 100-1000 mu m and the tube diameter of 6-15 nm, and the carbon nanotubes with high length-diameter ratio have excellent anisotropic conductivity, conductivity and heat dissipation performance, so that the prepared carbon nanotube/polyimide composite film has excellent charge conduction, heat dissipation and other performances.
In further embodiments, the carbon nanotube film is selected from: at least one of a film directly drawn from the carbon nanotube array, a film formed by unidirectional arrangement of carbon nanotube fibers, and a film formed by weaving of carbon nanotube fibers; the carbon nanotube fiber is obtained by twisting a carbon nanotube array film. The carbon nanotube film adopted by the embodiment of the invention is formed by directly drawing the prepared carbon nanotube array or weaving the carbon nanotube film after the array is made into fibers, so that the structure, the mechanics, the electrochemistry and other mechanical properties of the carbon nanotube are not damaged by modifying the carbon nanotube, other dispersing agents, active agents and other auxiliary agents are not additionally added, and other substance components cannot be additionally introduced into the carbon nanotube/polyimide composite material film to influence the performance of the composite material film. In addition, the carbon nanotube film is directly prepared by the highly ordered carbon nanotube array, so that the carbon nanotube film can also keep high order and high orientation, the order of the carbon nanotube film can be further improved by controlling the arrangement of carbon nanotube fibers and the like in the preparation process of the carbon nanotube film, the orientation of the carbon nanotube film is consistent, and the conductive capacity of the composite material film is effectively improved. The carbon nanotube film provided by the embodiment of the invention has high purity, good structural integrity and excellent physical and chemical properties, can increase mechanical properties such as mechanics and the like of the composite material film, can conduct charges in the composite material film in time, and avoids the limitation of charge accumulation on the application field.
The embodiment of the invention does not specifically limit the specification of the carbon nanotube film, and the carbon nanotube film with the corresponding size and specification can be manufactured according to the actual application requirement. In some embodiments, the carbon nanotube film may have a length and a width of 50 to 200 mm and a thickness of 12 to 140 μm.
In some embodiments, the film drawn directly from the carbon nanotube array may be: a film drawn from a carbon nanotube array having a carbon nanotube height of 100 to 1000 μm and a tube diameter of 6 to 15 nm. The carbon nanotube array with high length-diameter ratio has better mechanical property, each carbon nanotube is connected together through Van der Waals force to be drawn into a film, the drawn film carbon nanotube has good orientation, the process has continuity, and the carbon nanotube/polyimide composite film can be prepared by directly carrying out ink jet while drawing the carbon nanotube film from the carbon nanotube array.
In some embodiments, the film formed by the unidirectional alignment of carbon nanotube fibers may be: a single carbon nanotube fiber yarn or a carbon nanotube fiber bundle formed by combining a plurality of carbon nanotube fiber yarns is adopted to be arranged in parallel, so that the carbon nanotube film is provided in a form of unidirectional fiber cloth. The method has better strength and high orientation of the carbon nano tube fiber, and can realize continuous preparation of the carbon nano tube/polyimide composite material film through spinning and doubling equipment. Wherein, the carbon nanotube fiber is obtained by twisting the carbon nanotube array film.
In some embodiments, the membrane formed by weaving the carbon nanotube fibers may be: a plurality of carbon nanotube fibers are woven into plain weave fabric, twill fabric or satin fabric by the conventional cloth weaving process through the carbon nanotube fibers.
In a further embodiment, the molten polyimide has a melt viscosity of 0.49 to 0.53 dl/g. The embodiment of the invention adopts the polyimide with the melt viscosity of 0.49-0.53 dl/g, and is beneficial to preparing the composite material film of the carbon nano tube/polyimide by subsequent spraying. If the viscosity is too high, the subsequent spraying treatment is not facilitated, and the soaking and dispersion of polyimide in the carbon nanotube film are not facilitated, and the carbon nanotube film can be damaged in the processing process; if the viscosity is too low, the thermal stability and chemical resistance of the prepared carbon nano tube/polyimide composite material film can be influenced, and the high-requirement application fields of aerospace and the like can not be met. In some embodiments, the molten polyimide has a melt viscosity of 0.49dl/g, 0.5dl/g, 0.51dl/g, 0.52dl/g, or 0.53 dl/g.
In a further embodiment, the preparation of the polyimide comprises the steps of:
s11, obtaining aromatic diamine, tetracarboxylic dianhydride and dicarboxylic anhydride, and dissolving the aromatic diamine, the tetracarboxylic dianhydride and the dicarboxylic anhydride in an organic solvent to react for 4-24 hours under a protective gas atmosphere at the temperature of 20-60 ℃ to obtain polyamic acid;
s12, imidizing the polyamic acid for 10-20 hours at a high temperature of 150-250 ℃ or under the action of a dehydrating agent and a catalyst to obtain the polyimide.
The polyimide provided by the embodiment of the invention is prepared by reacting and polymerizing aromatic diamine, tetracarboxylic dianhydride and dicarboxylic anhydride to obtain polyamic acid in a protective gas atmosphere at the temperature of 20-60 ℃, and imidizing the polyamic acid in a high-temperature environment at the temperature of 150-250 ℃ or under the action of a dehydrating agent and a catalyst, and has the characteristics of excellent high temperature resistance, low temperature resistance, radiation resistance, chemical resistance, excellent mechanical property and the like. The polyimide powder prepared by the embodiment of the invention is subjected to melting treatment in an extruder or other devices to obtain molten polyimide which is used for preparing carbon nano tube/polyimide composite films.
Specifically, in step S11, under a protective gas atmosphere at a temperature of 20 to 60 ℃, the molar ratio of the components is 1: (0.9-1.0): (0.01-0.5): (60-65) dissolving the aromatic diamine, the tetracarboxylic dianhydride and the dicarboxylic anhydride in an organic solvent, and reacting for 4-24 hours to obtain the polyamic acid. Wherein, the molar mass of the polyimide can be adjusted by using the tetracarboxylic dianhydride, so that the melt viscosity of the polyimide is influenced; if the molar ratio of the polyimide to the aromatic diamine is less than 0.9, the molar mass of the polyimide is too low, the melt viscosity of the polyimide is low, and the subsequent processing into a film is not facilitated; if the molar ratio of the polyimide to the aromatic diamine is higher than 1.0, the melt viscosity of the polyimide becomes too high, and subsequent processing becomes difficult. Wherein, the dicarboxylic anhydride can adjust the stability and mechanical property of the polyimide, and when the molar ratio of the dicarboxylic anhydride to the aromatic diamine is less than 0.01, the polyimide in a molten state has poor thermal stability; when the molar ratio of the dicarboxylic anhydride to the aromatic diamine is more than 0.5, the mechanical properties of the polyimide are not good. The molar ratio of the solvent is (60-65), and a solvent environment is provided for polymerization, dehydration condensation and other reactions among raw material substances through the solvent ratio, so that the reaction is facilitated. In some embodiments, the molar ratio of the aromatic diamine, the tetracarboxylic dianhydride, the dicarboxylic anhydride, and the solvent may be 1:0.9:0.01:60, 1:1:0.5:62, 1:1:0.3:63, or 1:0.9:0.2:65, and the like.
In some embodiments, the aromatic diamine is selected from: 4,4' -bis (3-aminophenoxy) biphenyl, 2' -bis [4- (3-aminophenoxy) phenyl) ] propane, 4' -bis (3-aminophenoxy) benzophenone.
In some embodiments, the tetracarboxylic dianhydride is selected from: one or more of ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, and 3,3',4,4' -biphenyl tetracarboxylic dianhydride.
In some embodiments, the dicarboxylic acid anhydride is selected from: one or more of glutaric anhydride, citraconic anhydride, phthalic anhydride and succinic anhydride.
In some embodiments, the solvent is selected from: at least one of N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylpyrrolidone, N-diethylacetamide, N-dimethylacetamide, and 1, 3-dimethyl-2-imidazolidinone.
Specifically, in step S12, imidizing the polyamic acid at a high temperature of 150 to 250 ℃ or under the action of a dehydrating agent and a catalyst for 10 to 20 hours to obtain polyimide. According to the embodiment of the invention, the polyamic acid is imidized through high-temperature dehydration condensation to obtain the polyimide, or the polyamic acid is subjected to dehydration condensation imidization under the action of a dehydrating agent and a catalyst to obtain the polyimide.
In further embodiments, the molar ratio of the polyamic acid to the dehydrating agent and the catalyst is 1: (2-4): (2-4) the molar ratio is effective for imidizing the polyamic acid to obtain the polyimide.
In some embodiments, the dehydrating agent is selected from: at least one of acetic anhydride and propionic anhydride; the catalyst is selected from: at least one of triethylamine and pyridine. The dehydrating agent and the catalyst adopted by the embodiment of the invention have good catalytic dehydration performance, and can effectively imidize polyamic acid to obtain polyimide.
Specifically, in the step S20, under the conditions that the operation speed of the carbon nanotube film is 10-20 cm/min and the temperature is 350-420 ℃, the molten polyimide is sprayed onto the surface of the carbon nanotube film in a spraying amount of 2-120 mL/min, the carbon nanotube film sprayed with the molten polyimide is subjected to pressure treatment, and the carbon nanotube/polyimide composite film is obtained by cooling, wherein the volume percentage content of the carbon nanotubes in the carbon nanotube/polyimide composite film is 30-70%. According to the embodiment of the invention, the carbon nanotube film is operated at the speed of 10-20 cm/min, the molten polyimide is sprayed on the surface of the carbon nanotube film at the spraying amount of 2-120 mL/min under the condition of 350-420 ℃, and the loading amount of the carbon nanotube in the prepared composite material film can be flexibly controlled by controlling the operation speed of the carbon nanotube film and the spraying amount of the polyimide, so that the volume percentage content of the carbon nanotube in the carbon nanotube/polyimide composite material film is ensured to be 30-70%, the performances of conductivity, mechanics and the like of the composite film can be flexibly regulated and controlled, the continuous mass production can be realized, and the continuous preparation of the carbon nanotube/polyimide composite material film can be realized by continuously operating the carbon nanotube and spraying the polyimide. In addition, the polyimide is sprayed on the carbon nano tube film, so that the polyimide can uniformly infiltrate into the carbon nano tube film, and the prepared composite material film is tightly combined, has good uniformity, no bubbles, good performance and stability. And then the composite material film layer is further stabilized through pressurization treatment, and the carbon nano tube/polyimide composite material film is obtained through cooling.
Specifically, the running speed of the carbon nanotube film is 10 cm/min-20 cm/min, which can effectively ensure that the polyimide is uniformly infiltrated and coats the carbon nanotube film, and if the running speed of the carbon nanotube film is too high, the melted polyimide cannot uniformly infiltrate the carbon nanotube film; if the running speed of the carbon nanotube film is too slow, the efficiency is reduced, and the polyimide is kept at the processing temperature for a long time, which is not beneficial to the uniform mixing of the polyimide and the carbon nanotube. The polyimide film has good fluidity and meltability, can be quickly, fully and uniformly combined with the carbon nanotube film to form a composite material film layer by infiltration, and is favorable for forming the composite material film under the environmental condition that the temperature is 350-420 ℃. If the temperature is too low, the fluidity of the polyimide is affected, and if the temperature is too high, the material components of the polyimide and the carbon nano-particles are affected, the melt viscosity of the polyimide is reduced, and the molding is not facilitated. The spraying amount of the molten polyimide is 2 mL/min-120 mL/min, the spraying amount reasonably ensures that the polyimide can be uniformly infiltrated and dispersed in the carbon nanotube film and coated on the surface of the carbon nanotube film, and simultaneously, the content of the carbon nanotubes in the composite material film can be effectively regulated and controlled, so that the volume percentage content of the carbon nanotubes in the carbon nanotube/polyimide composite material film is 30-70%, and the performances of the composite material film such as conductivity, mechanics and the like are ensured. In some embodiments, the molten polyimide is sprayed onto the surface of the carbon nanotube film at a spray rate of 2mL/min, 10mL/min, 30mL/min, 50mL/min, 80mL/min, 100mL/min, or 120mL/min at a temperature of 350 ℃, 380 ℃, 400 ℃, or 420 ℃ at a running rate of 10cm/min, 15cm/min, or 20 cm/min.
In a further embodiment, the molten polyimide is sprayed at a pressure of 80 to 150kg/cm2Applying 80-150 kg/cm2The spraying pressure of the composite material enables the polyimide to be sprayed on the surface of the whole carbon nano tube film more uniformly, and the polyimide and the carbon nano tube film are combined and soaked uniformly to obtain a uniform composite material film. In some embodiments, the spray pressure of the molten polyimide may be 80kg/cm2、90kg/cm2、100kg/cm2、120kg/cm2、140kg/cm2Or 150kg/cm2。
In a further embodiment, the step of pressurizing the carbon nanotube film sprayed with the molten polyimide is performed under a pressure of 50 to 70kg/cm2. The passing pressure of the embodiment of the invention is 50-70 kg/cm2The pressurizing treatment is beneficial to fully soaking the polyimide in the carbon nano tube film to form the carbon nano tube/polyimide composite material film with uniform thickness, and is beneficial to continuously producing the carbon nano tube/polyimide composite material film. In a further preferred embodiment, in the step of pressurizing the carbon nanotube film sprayed with the molten polyimide, a pressure of 50 to 70kg/cm is applied perpendicularly to the carbon nanotube film2。
In some embodiments, as shown in FIGS. 1 and 2, a method for preparing a carbon nanotube/polyimide composite film includes the steps of:
s01, obtaining molten polyimide;
s01, obtaining a carbon nanotube film, enabling the carbon nanotube film to pass through gaps of a plurality of hot rollers with the temperature of 350-420 ℃, and enabling the carbon nanotube film to run at the speed of 10-20 cm/min through the matching rotation of the hot rollers;
s03, spraying the molten polyimide at the temperature of 350-420 ℃ in a spraying amount of 2-120 mL/min, wherein the spraying amount is 80-150 kg/cm2The ejection pressure of (a) is ejected on the surface of the carbon nanotube film;
s04, applying 50-70 kg/cm of molten polyimide on the carbon nanotube film vertically sprayed with the molten polyimide2After the pressure is pressurized, the carbon nano tube/polyimide composite material film is obtained after cooling to the room temperature, wherein the volume percentage of the carbon nano tube in the carbon nano tube/polyimide composite material film is 30-70%.
The preparation method of the carbon nano tube/polyimide composite material film provided by the embodiment of the invention adopts the cooperation of the hot roller and other rollers to drive the carbon nano tube film to run, and simultaneously can provide a heat source and pressure for the carbon nano tube to form the carbon nano tube film, and the polyimide is uniformly sprayed on the carbon nano tube film to form the carbon nano tube film, so that the continuous production of the carbon nano tube/polyimide composite material film is realized.
In some embodiments, the carbon nanotube/polyimide composite film can be prepared by a continuous production method as shown in fig. 1, wherein the carbon nanotube film is run between rollers by the cooperation of three hot rolling shafts and a collection shaft, the carbon nanotube film is vertically sprayed on the surface of the carbon nanotube film while passing through a first hot rolling shaft, then a pressure perpendicular to the surface of the carbon nanotube film is applied by a second hot rolling shaft when the carbon nanotube film reaches a second hot rolling shaft and a third hot rolling shaft, and the formed carbon nanotube/polyimide composite film is collected by the driving of the collection shaft.
In some embodiments, the carbon nanotube/polyimide composite film can be prepared by a continuous production method as shown in fig. 2, wherein the carbon nanotube film is run between rollers through the cooperation of 4 hot rolling shafts and a collection shaft, the carbon nanotube film is vertically sprayed on the surface of the carbon nanotube film while passing through a first hot rolling shaft, then a pressure perpendicular to the surface of the carbon nanotube film is applied through a second hot rolling shaft when the carbon nanotube film reaches a second hot rolling shaft and a third hot rolling shaft, and the formed carbon nanotube/polyimide composite film is collected through the driving of the collection shaft.
In a further embodiment, after cooling to obtain the carbon nanotube/polyimide composite film, the method further comprises the steps of: laminating 10-25 carbon nanotube/polyimide composite films, and heating at 320-400 deg.C under 30-50 kg/cm2And carrying out hot pressing treatment under the condition to obtain the carbon nano tube/polyimide composite board. In the embodiment of the invention, 10 to 25 carbon nano tubes/polyimide composite material films can be laminated at the temperature of 320 to 400 ℃ and the pressure of 30 to 50kg/cm2Under the condition of hot-pressing treatment, the polyimide on the outer layer of the carbon nano tube/polyimide composite material film is melted and the laminated composite material film is melted to form the composite molding plate, thereby further expanding the application field of the composite molding plate. Wherein, the temperature and the pressure are used for ensuring that the polyimide parts of the outer layers of the films are melted, and the outer layers of the films can be formed into plates after hot pressing. If the temperature is too low, the melting point of the polyimide may not be reached, and if the temperature is too high, the polyimide is completely melted, which is not favorable for molding. The pressure is too low to compact, which increases the density of the plate, and too high is not good for forming and also has influence on mechanical property.
Correspondingly, the embodiment of the invention also provides a carbon nanotube/polyimide composite material film, which is prepared by the method and comprises a carbon nanotube film and polyimide infiltrated and coated on the carbon nanotube film, wherein the volume percentage of the carbon nanotube in the carbon nanotube/polyimide composite material film is 30-70%.
The carbon nanotube/polyimide composite material film provided by the embodiment of the invention comprises a carbon nanotube film and polyimide permeating and coating the carbon nanotube film, wherein the volume percentage of the carbon nanotube in the carbon nanotube/polyimide composite material film is 30-70%, and the carbon nanotube/polyimide composite material film has excellent mechanical and electric conduction properties, and if the volume percentage of the carbon nanotube film in the composite material film is lower than 30%, the carbon nanotube/polyimide composite material film cannot play a role in enhancing the mechanical and other properties of the composite material film and is difficult to play an excellent role in electric charge conduction; if the volume is more than 70%, the interlayer strength of the molded article obtained by the subsequent processing may be significantly reduced.
In a further embodiment, the carbon nanotube/polyimide composite film provided by the embodiment of the present invention can be prepared by any one of the preparation methods described above, and the thickness of the carbon nanotube/polyimide composite film is 12 micrometers to 300 micrometers. The thickness adjusting range of the carbon nanotube/polyimide composite film in the embodiment of the invention is wide, and carbon nanotube/polyimide composite films with different thicknesses can be prepared by adjusting the thickness of the carbon nanotube film, the spraying amount of polyimide and the like according to the actual application requirements. In some embodiments, the carbon nanotube/polyimide composite film may have a thickness of 12 microns, 20 microns, 50 microns, 80 microns, 100 microns, 150 microns, 200 microns, 250 microns, 300 microns, or the like.
Correspondingly, the embodiment of the invention also provides a carbon nanotube/polyimide composite plate, which is obtained by laminating and pressing 10-25 carbon nanotube/polyimide composite material films.
The carbon nanotube/polyimide composite board provided by the invention is prepared from 10-25 carbon nanotube/polyimide composite material films with excellent mechanical and electric conductivity and other properties, so that the carbon nanotube/polyimide composite board also has excellent mechanical and electric conductivity and other properties.
In some embodiments, 10 to 25 carbon nanotube/polyimide composite films are laminated at a temperature of 320 to 400 ℃ and a pressure of 30 to 50kg/cm2And (3) carrying out hot-pressing treatment under the condition, so that the polyimide on the outer layer of the carbon nano tube/polyimide composite material film is melted and the laminated composite material film is melted to form a composite molding plate, thus obtaining the carbon nano tube/polyimide composite plate and further expanding the application field of the composite plate.
In order to clearly understand the details and operation of the above-mentioned embodiments of the present invention by those skilled in the art and to obviously show the advanced performance of the carbon nanotube/polyimide composite film and the method for preparing the same according to the embodiments of the present invention, the above-mentioned technical solution is exemplified by a plurality of embodiments.
Example 1
A carbon nanotube/polyimide composite material membrane and a carbon nanotube/polyimide composite plate comprise the following preparation steps:
① in nitrogen atmosphere, 1.03mol of 4,4' -bis (3-aminophenoxy) biphenyl was put in 61.65mol of N, N-dimethylacetamide solvent, 1mol of pyromellitic dianhydride was added in portions at room temperature to react for 20 hours, then 0.155mol of glutaric anhydride was added to the reaction system to react for one hour to obtain polyamic acid, 2mol of triethylamine and 3mol of acetic anhydride were added to imidize, and then, the mixture was filtered, washed and dried to obtain polyimide powder, and the polyimide powder was put in an extruder at 420 ℃ under 100kg/cm of pressure2Melting is carried out.
② the film was pulled from the carbon nanotube array and passed through a gap of multiple hot rolls, the gap was 70 μm, and the film passing speed was 20 cm/min.
③ spraying molten polyimide onto the hot roller, and applying pressure perpendicular to the film surface of 50kg/cm while passing through the gap of the hot roller2The hot roll temperature was 420 deg.c, and then after sufficiently cooling during the transfer, the prepared carbon nanotube/polyimide composite film was wound on a collecting drum.
④ sheets of the PI/CNT film thus obtained were stacked unidirectionally and hot-pressed to obtain a composite sheet, a pressure of 30kg/cm2And the temperature is 400 ℃ and the time is 20min, thus obtaining the carbon nano tube/polyimide composite board.
Example 2
A carbon nanotube/polyimide composite film, a carbon nanotube/polyimide composite plate, was prepared in the same manner as in example 1, in ①, ③ and ④, and in step ②, 100 carbon nanotube fibers were drawn from 100 winding cylinders on which the carbon nanotube fibers were wound, and were aligned in parallel by an adjuster to form a unidirectional carbon nanotube fiber film having a width of 15cm, which was passed through the gap of a hot roll.
Example 3
A carbon nanotube/polyimide composite film, a carbon nanotube/polyimide composite board, wherein the preparation steps ①, ③ and ④ are the same as example 1, step ② is that a weaving machine is used for weaving carbon nanotube fiber bundles into cloth, the weave is plain weave, the carbon nanotube fiber cloth is obtained, the warp and weft density is 5 bundles/square centimeter, and the prepared cloth directly passes through the gap of a hot roll.
Comparative example 1
A carbon nano tube/polyimide composite film comprises the following preparation steps:
① in nitrogen atmosphere, 1.03mol of 4,4' -bis (3-aminophenoxy) biphenyl was put into 61.65mol of N, N-dimethylacetamide solvent, 1mol of pyromellitic dianhydride was added in portions to react at room temperature for 20h, then 0.155mol of glutaric anhydride was added to the reaction system to react for one hour to obtain polyamic acid, and then 2mol of triethylamine and 3mol of acetic anhydride were added to perform imidization, filtration, washing and drying to obtain polyimide powder.
② mixing carbon nanotubes and polyimide powder in high-shear mixer, and pressing the mixture into film in a mold with a hot press at 30kg/cm2And the temperature is 400 ℃ and the time is 20min, so that the carbon nano tube/polyimide composite film is formed.
Comparative example 2
A nanotube/polyimide composite film, carbon nanotube/polyimide composite board, comprising the following preparation steps:
① in nitrogen atmosphere, 1.03mol of 4,4' -bis (3-aminophenoxy) biphenyl was put in 61.65mol of N, N-dimethylacetamide solvent, 1mol of pyromellitic dianhydride was added in portions at room temperature to react for 20 hours, then 2mol of triethylamine and 3mol of acetic anhydride were added to perform imidization, filtration, washing and drying to obtain polyimide powder, and the polyimide powder was put in an extruder at a temperature of 420 ℃ and a pressure of 100kg/cm2Melting is carried out.
② 100 carbon nanotube fibers were drawn from 100 winding drums wound with carbon nanotube fibers and arranged in parallel by an adjuster to form a unidirectional carbon nanotube fiber film 15cm in width, passing through the gap of a hot roll with a gap of 70 μm and a film passing rate of 20 cm/min.
③ spraying molten polyimide onto the hot roller, and applying pressure perpendicular to the film surface of 50kg/cm while passing through the gap of the hot roller2The hot roll temperature was 420 deg.c, and then after sufficiently cooling during the transfer, the prepared carbon nanotube/polyimide composite film was wound on a collecting drum.
④ sheets of the thus obtained carbon nanotube/polyimide composite film were unidirectionally stacked and hot-pressed to obtain a composite sheet, a pressure of 30kg/cm2And the temperature is 400 ℃ and the time is 20min, thus obtaining the carbon nano tube/polyimide composite board.
Further, in order to verify the progress of the nanotube/polyimide composite films prepared in the examples of the present invention, the examples of the present invention were subjected to performance tests.
Test example 1
The thickness and volume percentage content of the carbon nanotubes of the composite films of examples 1-3 and comparative examples 1-2, and the flexural strength, flexural modulus and resistance of the composite plate were measured at room temperature according to the standard ASTM D790 three-point load simple beam method using an electronic universal tester, and the test structure is shown in table 1 below:
TABLE 1
From the above test results, it can be seen that the nanotube/polyimide composite film prepared according to the embodiments of the present invention has high loading and high orientation. In practical application, a plurality of nanotube/polyimide composite films are laminated in different molds and pressed into composite plates with different shapes so as to meet the requirements of different occasions. The composite board obtained by laminating and pressing the carbon nanotube/polyimide composite material film prepared by the embodiment of the invention has more excellent mechanical property, and the mechanical properties such as bending strength, bending modulus and the like are obviously improved. Comparative example 1 the film prepared by dispersing the carbon nanotube powder in PI has a low degree of orientation and the carbon nanotubes are physically destroyed in the dispersion, resulting in a low strength of the carbon nanotube/PI film. The PI prepared by the comparative example 2 has the defects of high melt viscosity, poor fluidity and difficult processing, and the obtained nanotube/polyimide composite film has the defects of difficult air exhaust, more air holes and obviously reduced mechanical property.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a carbon nano tube/polyimide composite film is characterized by comprising the following steps:
obtaining a carbon nanotube film and molten polyimide;
under the conditions that the running speed of the carbon nano tube film is 10-20 cm/min and the temperature is 350-420 ℃, spraying the molten polyimide on the surface of the carbon nano tube film in a spraying amount of 2-120 mL/min, pressurizing the carbon nano tube film sprayed with the molten polyimide, and cooling to obtain the carbon nano tube/polyimide composite material film, wherein the volume percentage content of the carbon nano tube in the carbon nano tube/polyimide composite material film is 30-70%.
2. The method for producing a carbon nanotube/polyimide composite film according to claim 1, wherein the molten polyimide has a melt viscosity of 0.49 to 0.53 dl/g; and/or the presence of a gas in the gas,
the injection pressure of the molten polyimide is 80-150 kg/cm2(ii) a And/or the presence of a gas in the gas,
in the step of pressurizing the carbon nanotube film sprayed with the molten polyimide, the applied pressure is 50-70 kg/cm2。
3. The method for producing a carbon nanotube/polyimide composite film according to claim 1 or 2, wherein the carbon nanotubes in the carbon nanotube film have a tube length of 100 to 1000 μm and a tube diameter of 6 to 15 nm; and/or the presence of a gas in the gas,
the carbon nanotube film is selected from: at least one of a film directly drawn from the carbon nanotube array, a film formed by unidirectional arrangement of carbon nanotube fibers, and a film formed by weaving of carbon nanotube fibers; the carbon nanotube fiber is obtained by twisting a carbon nanotube array film.
4. The method for preparing a carbon nanotube/polyimide composite film according to claim 3, wherein the preparation of the polyimide comprises the steps of:
obtaining aromatic diamine, tetracarboxylic dianhydride and dicarboxylic anhydride, and dissolving the aromatic diamine, the tetracarboxylic dianhydride and the dicarboxylic anhydride in an organic solvent to react for 4-24 hours under a protective gas atmosphere at the temperature of 20-60 ℃ to obtain polyamic acid;
and imidizing the polyamic acid for 10-20 hours at a high temperature of 150-250 ℃ or under the action of a dehydrating agent and a catalyst to obtain the polyimide.
5. The method for producing a carbon nanotube/polyimide composite film according to claim 4, wherein the molar ratio of the aromatic diamine, the tetracarboxylic dianhydride, the dicarboxylic anhydride and the solvent is 1: (0.9-1.0): (0.01-0.5): (60-65); and/or the presence of a gas in the gas,
the molar ratio of the polyamic acid to the dehydrating agent and the catalyst is 1: (2-4): (2-4).
6. The method for preparing a carbon nanotube/polyimide composite film according to claim 5, wherein the aromatic diamine is selected from the group consisting of: one or more of 4,4' -bis (3-aminophenoxy) biphenyl, 2' -bis [4- (3-aminophenoxy) phenyl) ] propane, 4' -bis (3-aminophenoxy) benzophenone; and/or the presence of a gas in the gas,
the tetracarboxylic dianhydride is selected from: one or more of ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, and 3,3',4,4' -biphenyl tetracarboxylic dianhydride; and/or the presence of a gas in the gas,
the dicarboxylic acid anhydride is selected from: one or more of glutaric anhydride, citraconic anhydride, phthalic anhydride and succinic anhydride; and/or the presence of a gas in the gas,
the solvent is selected from: at least one of N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylpyrrolidone, N-diethylacetamide, N-dimethylacetamide, and 1, 3-dimethyl-2-imidazolidinone; and/or the presence of a gas in the gas,
the dehydrating agent is selected from: at least one of acetic anhydride and propionic anhydride; and/or the presence of a gas in the gas,
the catalyst is selected from: at least one of triethylamine and pyridine.
7. The method for preparing a carbon nanotube/polyimide composite film according to any one of claims 1, 2, 4, 5 or 6, comprising the steps of:
obtaining molten polyimide;
the method comprises the steps of obtaining a carbon nanotube film, enabling the carbon nanotube film to pass through gaps of a plurality of hot rollers with the temperature of 350-420 ℃, and enabling the carbon nanotube film to run at the speed of 10-20 cm/min through the matching rotation of the hot rollers;
under the condition that the temperature is 350-420 ℃, the spraying amount of the molten polyimide is 2-120 mL/min, and 80-150 kg/cm2The ejection pressure of (a) is ejected on the surface of the carbon nanotube film;
applying 50-70 kg/cm of a carbon nanotube film perpendicular to a surface of the carbon nanotube film coated with a molten polyimide2After the pressure is pressurized, the carbon nano tube/polyimide composite material film is obtained after cooling to the room temperature, wherein the volume percentage of the carbon nano tube in the carbon nano tube/polyimide composite material film is 30-70%.
8. The method for producing a carbon nanotube/polyimide composite film according to claim 7, wherein cooling gives a carbon nanotube/polyimideThe method also comprises the following steps: laminating 10-25 carbon nanotube/polyimide composite films, and heating at 320-400 deg.C under 30-50 kg/cm2And carrying out hot pressing treatment under the condition to obtain the carbon nano tube/polyimide composite board.
9. A carbon nanotube/polyimide composite film prepared by the method according to any one of claims 1 to 8, comprising a carbon nanotube film and polyimide impregnated and coated on the carbon nanotube film, wherein the carbon nanotube is present in the carbon nanotube/polyimide composite film in an amount of 30 to 70% by volume.
10. A carbon nanotube/polyimide composite plate, wherein the carbon nanotube/polyimide composite plate is obtained by laminating and pressing 10 to 25 sheets of the carbon nanotube/polyimide composite material film according to claim 9.
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