CN109957962B - Carboxylated carbon nanotube-polyurethane heat-conducting film and preparation method thereof - Google Patents
Carboxylated carbon nanotube-polyurethane heat-conducting film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of light industry and chemical materials, in particular to a carboxylated carbon nanotube-polyurethane heat-conducting film and a preparation method thereof. The preparation method of the carboxylated carbon nanotube-polyurethane heat conducting film comprises the first step of preparing a carboxylated carbon nanotube; secondly, preparing a carboxylated carbon nanotube dispersion liquid; step three, preparing a carboxylated carbon nanotube/polyurethane spinning solution; fourthly, electrostatic spinning; and fifthly, ultrasonically anchoring the decorative carbon nano tube. The carboxylated carbon nanotube/polyurethane spinning solution is prepared by dispersing the acidified carboxylated carbon nanotube in the mixed solvent of acetone and dimethyl formamide and then adding polyurethane, so that the carbon nanotube is forced to have good orientation in polyurethane fiber in the spinning process, and the carbon nanotube is completely coated by the polyurethane after electrostatic spinning to form a continuous heat conduction path in the polyurethane fiber, thereby achieving the purposes of low carbon nanotube content and high heat conduction coefficient.
Description
Technical Field
The invention relates to the technical field of light industry and chemical materials, in particular to a carboxylated carbon nanotube-polyurethane heat-conducting film and a preparation method thereof.
Background
With the rapid development of technology, electronic devices need to have higher processing speed, higher operating frequency and smaller size, and people have made higher demands on the heat dissipation of products, and the heat dissipation capability of electronic devices becomes a problem that must be considered when designing and manufacturing electronic equipment. The polymer is one of the best candidate materials for preparing the miniature electronic heat dissipation device because of excellent mechanical property, flexibility, bendability, stretchability and excellent processing performance. However, pure polymer materials generally have low thermal conductivity, making heat dissipation from electronic devices extremely difficult. Therefore, it is very necessary and urgent to prepare more excellent high thermal conductive polymer composite materials.
At present, methods for improving the thermal conductivity of polymer materials are generally divided into two methods, namely preparation of intrinsic heat-conducting polymer materials and preparation of filled polymer materials. Compared with the preparation of intrinsic heat-conducting polymers, the method has the advantages that the heat-conducting materials with better heat conductivity, such as carbon nano tubes, are added into the common polymer materials, the process for preparing the filled heat-conducting polymer materials by uniformly mixing the two materials through a certain process is simpler, the actual production requirements can be met, and the method is the main method for preparing the heat-conducting polymer composite material at present. However, the addition of a large amount of thermally conductive filler significantly changes the microstructure of the polymer, thereby reducing the mechanical properties and processability of the polymer. In addition, a series of problems such as dispersibility, compatibility, interfacial property and the like of the heat conductive filler in the polymer matrix need to be solved. In addition, the random distribution of the heat-conducting filler in the polymer matrix usually forms a discontinuous heat-conducting network, so that the interface thermal resistance between the filler and the filler is greatly increased, and the improvement of the heat conductivity coefficient is limited to a certain extent. Therefore, the preparation of polymer composite materials with low thermal conductivity filler and high thermal conductivity is still a great challenge faced by current research work.
In the process of exploring a novel thermal interface material, the excellent performance of the carbon nanotube in the aspect of heat conduction draws great attention (the heat conduction coefficient is about 2000W/m.K), and theoretically, the carbon nanotube has outstanding advantages in the aspect of preparing a heat conduction composite material compared with other heat conduction fillers. Therefore, the preparation of the polymer composite material containing carbon nanotubes is receiving attention from a great deal of researchers, because the polymer composite material has light weight, good corrosion resistance, strong processing capability and low manufacturing cost, and is considered to be one of the most ideal heat dissipation materials at present. But the application of the carbon nano tube is greatly limited due to the defects of poor compatibility of the carbon nano tube serving as the inorganic heat-conducting filler and a high polymer material and the like. If the problem of poor compatibility with the high polymer material can be solved, and a heat conduction path can be formed in the high polymer material by a small amount of additive, the heat conduction capability of the material is further improved, and the material becomes a high-performance heat conduction filler with good application prospect.
Disclosure of Invention
One of the objectives of the present invention is to provide a method for preparing a carboxylated carbon nanotube-polyurethane thermal conductive film, which has the advantages of low addition of thermal conductive filler and high thermal conductivity, in view of the deficiencies of the prior art.
The second objective of the present invention is to provide a carboxylated carbon nanotube-polyurethane thermal conductive film, which has the advantages of low addition amount of thermal conductive filler and high thermal conductivity, in view of the defects of the prior art.
In order to achieve one of the purposes, the invention adopts the following technical scheme:
the preparation method of the carboxylated carbon nanotube-polyurethane heat-conducting film comprises the following steps:
step one, preparing a carboxylated carbon nanotube: carboxylated carbon nanotubes are made by treating carbon nanotubes with a mixed acid formulated from concentrated sulfuric acid and concentrated nitric acid, the carboxylated carbon nanotubes having a structure represented by formula I:
step two, preparing a carboxylated carbon nanotube dispersion liquid: dispersing the carboxylated carbon nanotubes prepared in the first step into a mixed solvent of acetone and dimethylformamide, and uniformly stirring to prepare a carboxylated carbon nanotube dispersion liquid;
step three, preparing a carboxylated carbon nanotube/polyurethane spinning solution: adding polyurethane into the carboxylated carbon nanotube dispersion liquid prepared in the step one, and dissolving to prepare a carboxylated carbon nanotube/polyurethane spinning solution;
fourthly, electrostatic spinning: performing electrostatic spinning on the carboxylated carbon nanotube/polyurethane spinning solution prepared in the third step to obtain a carboxylated carbon nanotube/polyurethane composite film;
fifthly, ultrasonically anchoring and decorating the carbon nano tube: and anchoring the carboxylated carbon nanotube on the carboxylated carbon nanotube/polyurethane composite material film by using an ultrasonic anchoring technology and an ultrasonic reaction synthesizer to obtain the carboxylated carbon nanotube-polyurethane heat-conducting film.
In the above technical solution, the preparation of the carboxylated carbon nanotube in the first step includes the following steps:
step one, acidizing: adding carbon nanotubes into a container, preparing mixed acid of concentrated sulfuric acid and concentrated nitric acid, adding the mixed acid into the container filled with the carbon nanotubes after the mixed acid is cooled, carrying out condensation reflux, then adding water into the container, cooling after the condensation reflux is finished, and standing substances in the container;
step two, acid removal: and (3) removing supernatant from the substance after standing in the step one, taking the lower layer solution for centrifugal treatment, then taking the centrifuged precipitate for vacuum filtration, and washing with water until the precipitate is neutral, thus obtaining the carboxylated carbon nanotube.
In the technical scheme, in the acidification treatment in the step one, the temperature of condensation reflux is 60-80 ℃, the time of condensation reflux is 3-3.5 h, the volume ratio of added water to the mixed acid is 2-2.5: 1, and the standing time is 22-26 h;
in the step two, in the acid removal, the centrifugal rotating speed is 8000-15000 r/min; the centrifugation times are 6-8.
In the technical scheme, in the first step of preparing the carboxylated carbon nanotube, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid is 2-4: 1;
in the first step of preparing the carboxylated carbon nanotube, the mass-to-volume ratio of the carbon nanotube to the mixed acid is 10-30 g/L.
In the technical scheme, the carboxylated carbon nanotube is prepared in the first step, the diameter of the carbon nanotube is 10-20 nm, and the length of the carbon nanotube is 3-15 microns.
In the technical scheme, the second step is used for preparing the carboxylated carbon nanotube dispersion liquid, and the volume ratio of acetone to dimethylformamide in the mixed solvent is 1: 1;
the concentration of the carboxylated carbon nanotube dispersion liquid is 0.5-1.5 mg/mL.
In the technical scheme, the third step is to prepare a carboxylated carbon nanotube/polyurethane spinning solution, wherein the mass concentration of polyurethane in the carboxylated carbon nanotube/polyurethane spinning solution is 13-15%.
In the technical scheme, in the fourth step of electrostatic spinning, the voltage of the electrostatic spinning is 10-15 kV, the relative humidity of the electrostatic spinning is 20-40%, the receiving distance of the electrostatic spinning is 10-15 cm, the injection speed of the electrostatic spinning is 0.08-0.15 mm/min, and the caliber of a needle is 21-22G.
In the technical scheme, in the fifth step of ultrasonically anchoring the decorative carbon nano tube, the ultrasonic power is 400-960W, the ultrasonic time is 20-60 min, and the ultrasonic frequency is 18-22 kHz.
In order to achieve the second purpose, the invention adopts the following technical scheme:
provides a carboxylated carbon nanotube-polyurethane heat-conducting film, which is prepared by the preparation method of the carboxylated carbon nanotube-polyurethane heat-conducting film.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the prior art that the carbon nano tubes and the polyurethane are directly melted and blended or the polyurethane is dissolved and then the dispersed carbon nano tubes are added, the carbon nano tubes in the invention are dispersed in the polyurethane more uniformly.
(2) The invention provides a preparation method of a carboxylated carbon nanotube-polyurethane heat conducting film, which avoids the traditional hot press molding and blending extrusion molding, adopts an electrostatic spinning technology to prepare the carboxylated carbon nanotube-polyurethane heat conducting film, skillfully utilizes a high-voltage electrostatic field to force a carbon nanotube to generate polarization in the electrostatic field, forces the carbon nanotube to have good orientation in polyurethane fiber in the spinning process, and completely coats the carbon nanotube with polyurethane after electrostatic spinning to form a continuous heat conducting passage in the polyurethane fiber, thereby realizing the purposes of low carbon nanotube content and high heat conducting coefficient.
(3) The invention provides a preparation method of a carboxylated carbon nanotube-polyurethane heat conducting film, which adopts an ultrasonic method to evenly anchor carbon nanotubes on a spun carboxylated carbon nanotube/polyurethane composite material film to form an even carbon nanotube coating layer on the surface of polyurethane fibers, and utilizes hydrogen bonds formed by carboxyl on the surface of the carbon nanotubes and amino in a polyurethane material to firmly fix the carbon nanotubes coated on the surface of the polyurethane fibers, so that the carbon nanotubes do not fall off by ultrasonic for a long time. And the carbon nano tube coated on the surface of the polyurethane and the carbon nano tube coated by the polyurethane supplement each other, and the inner heat conduction channel and the outer heat conduction channel further improve the heat conductivity coefficient and the heat dissipation performance of the prepared carboxylated carbon nano tube-polyurethane heat conduction film.
(4) The preparation method of the carboxylated carbon nanotube-polyurethane heat-conducting film provided by the invention has the characteristics of simple preparation method, low production cost and capability of being used for large-scale production, and the prepared carboxylated carbon nanotube-polyurethane heat-conducting film has excellent heat-conducting property and mechanical property.
(5) The invention provides a carboxylated carbon nanotube-polyurethane heat conducting membrane which is formed by functionally modifying carbon nanotubes, wherein the surface of the modified carbon nanotubes contains carboxyl functional groups, the carboxyl functional groups and amino functional groups on a polyurethane polymer chain form hydrogen bond acting force, and the hydrogen bond acting force has obvious effects on reducing interface phonon scattering between the carbon nanotubes and polyurethane, reducing interfacial thermal resistance and improving thermal conductivity. In addition, the functionalized carbon nano tube can further reduce the difference of surface tension between the carbon nano tube and polyurethane, so that the carbon nano tube is more easily wetted by the polyurethane, the gap between the carbon nano tube and the polyurethane is reduced, and the interface thermal resistance of the prepared carboxylated carbon nano tube-polyurethane heat-conducting film is further reduced.
Drawings
Fig. 1 is a schematic structural diagram of a carboxylated carbon nanotube-polyurethane thermal conductive film prepared in example 1 of the present invention. Wherein Carbon nanotube stands for carboxylated Carbon nanotube, and TPU fiber stands for polyurethane fiber.
Fig. 2 is a schematic diagram of heat dissipation of a carboxylated carbon nanotube-polyurethane thermal conductive film prepared in example 1 of the present invention when being heated. Wherein Carbon nanotube stands for carboxylated Carbon nanotube, and TPU fiber stands for polyurethane fiber.
FIG. 3 is a comparative infrared spectrum of the carboxylated carbon nanotube prepared in example 1 of the present invention and an untreated carbon nanotube, which demonstrates that the surface of the prepared carboxylated carbon nanotube has carboxyl functional groups. Wherein, the curve a represents the infrared spectrum of the carboxylated carbon nano tube, and the curve b represents the infrared spectrum of the untreated carbon nano tube.
Fig. 4 is a comparative infrared spectrum of the carboxylated carbon nanotube-polyurethane thermal conductive film prepared in example 1 of the present invention and a pure polyurethane film, and this figure demonstrates that there is an interaction force between the carboxylated carbon nanotube and polyurethane in the carboxylated carbon nanotube-polyurethane thermal conductive film prepared in the present invention. Wherein, the curve b in the figure represents the carboxylated carbon nano tube-polyurethane heat conducting film, and the curve a represents the pure polyurethane film.
Fig. 5 is a comprehensive thermal analysis spectrum of a carboxylated carbon nanotube-polyurethane thermal conductive film prepared in example 1 of the present invention. This figure is to demonstrate the percentage of carbon nanotubes in the polyurethane. Wherein, curve b represents the prepared carboxylated carbon nanotube-polyurethane heat-conducting film, and curve a represents polyurethane.
Fig. 6 is SEM and TEM images of the carboxylated carbon nanotube-polyurethane thermal conductive film prepared in example 1 of the present invention. This figure is for the purpose of illustrating the distribution of carbon nanotubes on the polyurethane film. Wherein, a is a scanning electron microscope image of the carboxylated carbon nanotube/polyurethane composite film obtained by electrostatic spinning, b is a scanning electron microscope image of the carboxylated carbon nanotube-polyurethane heat-conducting film, c is an interface image of the carboxylated carbon nanotube/polyurethane composite film obtained by electrostatic spinning, and d is a transmission electron microscope image of the carboxylated carbon nanotube-polyurethane heat-conducting film.
Fig. 7 is a summary chart of the thermal conductivity coefficients of the carboxylated carbon nanotube-polyurethane thermal conductive film prepared in example 1 of the present invention at different temperatures. Wherein the a-curve represents the thermal conductivity in the vertical direction and the b-curve represents the thermal conductivity in the horizontal direction.
Fig. 8 is a stress strain diagram of the carboxylated carbon nanotube/polyurethane composite film and the carboxylated carbon nanotube-polyurethane thermal conductive film prepared in example 1 of the present invention. This figure is to demonstrate that the flexibility of the original polymer material is not sacrificed after the addition of the carbon nanotubes in the present invention. In the figure, the polyurethane film of the curve a represents the carboxylated carbon nanotube/polyurethane composite material film obtained by electrostatic spinning, and the curve b represents the carboxylated carbon nanotube-polyurethane heat-conducting film.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1.
A preparation method of a carboxylated carbon nanotube-polyurethane heat conducting film comprises the following steps:
step one, preparing a carboxylated carbon nanotube: carboxylated carbon nanotubes are made by treating carbon nanotubes with a mixed acid formulated from concentrated sulfuric acid and concentrated nitric acid, the carboxylated carbon nanotubes having a structure represented by formula I:
wherein, the preparation of the carboxylated carbon nanotube in the first step comprises the following steps:
step one, acidizing: adding carbon nanotubes into a container, preparing mixed acid of concentrated sulfuric acid and concentrated nitric acid, adding the mixed acid into the container filled with the carbon nanotubes after the mixed acid is cooled, carrying out condensation reflux, then adding water into the container, cooling after the condensation reflux is finished, and standing substances in the container for 24 hours; in the embodiment, the temperature of the condensation reflux is 70 ℃, the time of the condensation reflux is 3.2h, and the volume ratio of the added water to the mixed acid is 2.2: 1; in the mixed acid, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3: 1; the mass volume ratio of the carbon nano tube to the mixed acid is 20 g/L; in this embodiment, the diameter of the carbon nanotube is 15nm, and the length of the carbon nanotube is 10 μm;
step two, acid removal: and (3) removing supernatant from the substance after standing in the step one, taking the lower layer solution for centrifugal treatment, then taking the centrifuged precipitate for vacuum filtration, and washing with water until the precipitate is neutral, thus obtaining the carboxylated carbon nanotube. In the embodiment, the centrifugal rotating speed is 12000 r/min; the number of centrifugation was 7 times.
Step two, preparing a carboxylated carbon nanotube dispersion liquid: dispersing the carboxylated carbon nanotubes prepared in the first step into a mixed solvent of acetone and dimethylformamide, and uniformly stirring to prepare a carboxylated carbon nanotube dispersion liquid; in this example, in the mixed solvent, the volume ratio of acetone to dimethylformamide is 1: 1; the concentration of the carboxylated carbon nanotube dispersion was 1 mg/mL.
Step three, preparing a carboxylated carbon nanotube/polyurethane spinning solution: adding polyurethane into the carboxylated carbon nanotube dispersion liquid prepared in the step one, and dissolving to prepare a carboxylated carbon nanotube/polyurethane spinning solution; in this example, the mass concentration of polyurethane in the carboxylated carbon nanotube/polyurethane spinning solution was 14%.
Fourthly, electrostatic spinning: performing electrostatic spinning on the carboxylated carbon nanotube/polyurethane spinning solution prepared in the third step to obtain a carboxylated carbon nanotube/polyurethane composite film; in the embodiment, the voltage of the electrostatic spinning is 12kV, the relative humidity of the electrostatic spinning is 30%, the receiving distance of the electrostatic spinning is 13cm, the injection speed of the electrostatic spinning is 0.12mm/min, and the caliber of the needle is 21.5G.
Fifthly, ultrasonically anchoring and decorating the carbon nano tube: and anchoring the carboxylated carbon nanotube on the carboxylated carbon nanotube/polyurethane composite material film by using an ultrasonic anchoring technology and an ultrasonic reaction synthesizer to obtain the carboxylated carbon nanotube-polyurethane heat-conducting film. In this embodiment, the ultrasonic power is 700W, the ultrasonic time is 40min, and the ultrasonic frequency is 20 kHz.
Example 2.
A preparation method of a carboxylated carbon nanotube-polyurethane heat conducting film comprises the following steps:
step one, preparing a carboxylated carbon nanotube: carboxylated carbon nanotubes are made by treating carbon nanotubes with a mixed acid formulated from concentrated sulfuric acid and concentrated nitric acid, the carboxylated carbon nanotubes having a structure represented by formula I:
wherein, the preparation of the carboxylated carbon nanotube in the first step comprises the following steps:
step one, acidizing: adding carbon nanotubes into a container, preparing mixed acid of concentrated sulfuric acid and concentrated nitric acid, cooling the mixed acid, adding the mixed acid into the container filled with the carbon nanotubes, carrying out condensation reflux, then adding water into the container, cooling after the condensation reflux is finished, and standing the substances in the container for 22 hours; in the embodiment, the temperature of the condensation reflux is 60 ℃, the time of the condensation reflux is 3.5h, and the volume ratio of the added water to the mixed acid is 2: 1; in the mixed acid, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 2: 1; the mass volume ratio of the carbon nano tube to the mixed acid is 10 g/L; in this embodiment, the diameter of the carbon nanotube is 10nm, and the length of the carbon nanotube is 3 μm;
step two, acid removal: and (3) removing supernatant from the substance after standing in the step one, taking the lower layer solution for centrifugal treatment, then taking the centrifuged precipitate for vacuum filtration, and washing with water until the precipitate is neutral, thus obtaining the carboxylated carbon nanotube. In the embodiment, the centrifugal rotating speed is 8000 r/min; the number of centrifugation was 6 times.
Step two, preparing a carboxylated carbon nanotube dispersion liquid: dispersing the carboxylated carbon nanotubes prepared in the first step into a mixed solvent of acetone and dimethylformamide, and uniformly stirring to prepare a carboxylated carbon nanotube dispersion liquid; in this example, in the mixed solvent, the volume ratio of acetone to dimethylformamide is 1: 1; the concentration of the carboxylated carbon nanotube dispersion was 0.5 mg/mL.
Step three, preparing a carboxylated carbon nanotube/polyurethane spinning solution: adding polyurethane into the carboxylated carbon nanotube dispersion liquid prepared in the step one, and dissolving to prepare a carboxylated carbon nanotube/polyurethane spinning solution; in this example, the mass concentration of polyurethane in the carboxylated carbon nanotube/polyurethane spinning solution was 13%.
Fourthly, electrostatic spinning: performing electrostatic spinning on the carboxylated carbon nanotube/polyurethane spinning solution prepared in the third step to obtain a carboxylated carbon nanotube/polyurethane composite film; in the embodiment, the voltage of electrostatic spinning is 10kV, the relative humidity of electrostatic spinning is 20%, the receiving distance of electrostatic spinning is 10cm, the injection speed of electrostatic spinning is 0.08mm/min, and the needle caliber is 21G.
Fifthly, ultrasonically anchoring and decorating the carbon nano tube: and anchoring the carboxylated carbon nanotube on the carboxylated carbon nanotube/polyurethane composite material film by using an ultrasonic anchoring technology and an ultrasonic reaction synthesizer to obtain the carboxylated carbon nanotube-polyurethane heat-conducting film. In this embodiment, the ultrasonic power is 400W, the ultrasonic time is 60min, and the ultrasonic frequency is 18 kHz.
Example 3.
A preparation method of a carboxylated carbon nanotube-polyurethane heat conducting film comprises the following steps:
step one, preparing a carboxylated carbon nanotube: carboxylated carbon nanotubes are made by treating carbon nanotubes with a mixed acid formulated from concentrated sulfuric acid and concentrated nitric acid, the carboxylated carbon nanotubes having a structure represented by formula I:
wherein, the preparation of the carboxylated carbon nanotube in the first step comprises the following steps:
step one, acidizing: adding carbon nanotubes into a container, preparing mixed acid of concentrated sulfuric acid and concentrated nitric acid, cooling the mixed acid, adding the mixed acid into the container filled with the carbon nanotubes, carrying out condensation reflux, then adding water into the container, cooling after the condensation reflux is finished, and standing the substances in the container for 26 hours; in the embodiment, the temperature of the condensation reflux is 80 ℃, the time of the condensation reflux is 3 hours, and the volume ratio of the added water to the mixed acid is 2.5: 1; in the mixed acid, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 4: 1; the mass volume ratio of the carbon nano tube to the mixed acid is 30 g/L; in this embodiment, the diameter of the carbon nanotube is 20nm, and the length of the carbon nanotube is 15 μm;
step two, acid removal: and (3) removing supernatant from the substance after standing in the step one, taking the lower layer solution for centrifugal treatment, then taking the centrifuged precipitate for vacuum filtration, and washing with water until the precipitate is neutral, thus obtaining the carboxylated carbon nanotube. In this embodiment, the centrifugal speed is 15000 r/min; the number of centrifugation was 8.
Step two, preparing a carboxylated carbon nanotube dispersion liquid: dispersing the carboxylated carbon nanotubes prepared in the first step into a mixed solvent of acetone and dimethylformamide, and uniformly stirring to prepare a carboxylated carbon nanotube dispersion liquid; in this example, in the mixed solvent, the volume ratio of acetone to dimethylformamide is 1: 1; the concentration of the carboxylated carbon nanotube dispersion was 1.5 mg/mL.
Step three, preparing a carboxylated carbon nanotube/polyurethane spinning solution: adding polyurethane into the carboxylated carbon nanotube dispersion liquid prepared in the step one, and dissolving to prepare a carboxylated carbon nanotube/polyurethane spinning solution; in this example, the mass concentration of polyurethane in the carboxylated carbon nanotube/polyurethane spinning solution was 15%.
Fourthly, electrostatic spinning: performing electrostatic spinning on the carboxylated carbon nanotube/polyurethane spinning solution prepared in the third step to obtain a carboxylated carbon nanotube/polyurethane composite film; in the embodiment, the voltage of the electrostatic spinning is 15kV, the relative humidity of the electrostatic spinning is 40%, the receiving distance of the electrostatic spinning is 15cm, the injection speed of the electrostatic spinning is 0.15mm/min, and the caliber of the needle is 22G.
Fifthly, ultrasonically anchoring and decorating the carbon nano tube: and anchoring the carboxylated carbon nanotube on the carboxylated carbon nanotube/polyurethane composite material film by using an ultrasonic anchoring technology and an ultrasonic reaction synthesizer to obtain the carboxylated carbon nanotube-polyurethane heat-conducting film. In this embodiment, the ultrasonic power is 960W, the ultrasonic time is 60min, and the ultrasonic frequency is 22 kHz.
Example 4.
A preparation method of a carboxylated carbon nanotube-polyurethane heat conducting film comprises the following steps:
step one, preparing a carboxylated carbon nanotube: carboxylated carbon nanotubes are made by treating carbon nanotubes with a mixed acid formulated from concentrated sulfuric acid and concentrated nitric acid, the carboxylated carbon nanotubes having a structure represented by formula I:
wherein, the preparation of the carboxylated carbon nanotube in the first step comprises the following steps:
step one, acidizing: adding carbon nanotubes into a container, preparing mixed acid of concentrated sulfuric acid and concentrated nitric acid, cooling the mixed acid, adding the mixed acid into the container filled with the carbon nanotubes, carrying out condensation reflux, then adding water into the container, cooling after the condensation reflux is finished, and standing the substances in the container for 23 hours; in the embodiment, the temperature of the condensation reflux is 65 ℃, the time of the condensation reflux is 3.1h, and the volume ratio of the added water to the mixed acid is 2.1: 1; in the mixed acid, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 2.5: 1; the mass volume ratio of the carbon nano tube to the mixed acid is 15 g/L; in this example, the diameter of the carbon nanotube is 12nm, and the length of the carbon nanotube is 7 μm;
step two, acid removal: and (3) removing supernatant from the substance after standing in the step one, taking the lower layer solution for centrifugal treatment, then taking the centrifuged precipitate for vacuum filtration, and washing with water until the precipitate is neutral, thus obtaining the carboxylated carbon nanotube. In the embodiment, the centrifugal speed is 10000 r/min; the number of centrifugation was 6 times.
Step two, preparing a carboxylated carbon nanotube dispersion liquid: dispersing the carboxylated carbon nanotubes prepared in the first step into a mixed solvent of acetone and dimethylformamide, and uniformly stirring to prepare a carboxylated carbon nanotube dispersion liquid; in this example, in the mixed solvent, the volume ratio of acetone to dimethylformamide is 1: 1; the concentration of the carboxylated carbon nanotube dispersion was 0.8 mg/mL.
Step three, preparing a carboxylated carbon nanotube/polyurethane spinning solution: adding polyurethane into the carboxylated carbon nanotube dispersion liquid prepared in the step one, and dissolving to prepare a carboxylated carbon nanotube/polyurethane spinning solution; in this example, the mass concentration of polyurethane in the carboxylated carbon nanotube/polyurethane spinning solution was 13.5%.
Fourthly, electrostatic spinning: performing electrostatic spinning on the carboxylated carbon nanotube/polyurethane spinning solution prepared in the third step to obtain a carboxylated carbon nanotube/polyurethane composite film; in the embodiment, the voltage of electrostatic spinning is 11kV, the relative humidity of electrostatic spinning is 25%, the receiving distance of electrostatic spinning is 11cm, the pushing speed of electrostatic spinning is 0.1mm/min, and the needle caliber is 21.5G.
Fifthly, ultrasonically anchoring and decorating the carbon nano tube: and anchoring the carboxylated carbon nanotube on the carboxylated carbon nanotube/polyurethane composite material film by using an ultrasonic anchoring technology and an ultrasonic reaction synthesizer to obtain the carboxylated carbon nanotube-polyurethane heat-conducting film. In this embodiment, the ultrasonic power is 500W, the ultrasonic time is 30min, and the ultrasonic frequency is 19 kHz.
Example 5.
A preparation method of a carboxylated carbon nanotube-polyurethane heat conducting film comprises the following steps:
step one, preparing a carboxylated carbon nanotube: carboxylated carbon nanotubes are made by treating carbon nanotubes with a mixed acid formulated from concentrated sulfuric acid and concentrated nitric acid, the carboxylated carbon nanotubes having a structure represented by formula I:
wherein, the preparation of the carboxylated carbon nanotube in the first step comprises the following steps:
step one, acidizing: adding carbon nanotubes into a container, preparing mixed acid of concentrated sulfuric acid and concentrated nitric acid, cooling the mixed acid, adding the mixed acid into the container filled with the carbon nanotubes, carrying out condensation reflux, then adding water into the container, cooling after the condensation reflux is finished, and standing the substances in the container for 25 hours; in the embodiment, the temperature of the condensation reflux is 75 ℃, the time of the condensation reflux is 3.4h, and the volume ratio of the added water to the mixed acid is 2.4: 1; in the mixed acid, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3.5: 1; the mass volume ratio of the carbon nano tube to the mixed acid is 25 g/L; in this example, the diameter of the carbon nanotube is 18nm, and the length of the carbon nanotube is 13 μm;
step two, acid removal: and (3) removing supernatant from the substance after standing in the step one, taking the lower layer solution for centrifugal treatment, then taking the centrifuged precipitate for vacuum filtration, and washing with water until the precipitate is neutral, thus obtaining the carboxylated carbon nanotube. In this embodiment, the centrifugal rotation speed is 14000 r/min; the number of centrifugation was 7 times.
Step two, preparing a carboxylated carbon nanotube dispersion liquid: dispersing the carboxylated carbon nanotubes prepared in the first step into a mixed solvent of acetone and dimethylformamide, and uniformly stirring to prepare a carboxylated carbon nanotube dispersion liquid; in this example, in the mixed solvent, the volume ratio of acetone to dimethylformamide is 1: 1; the concentration of the carboxylated carbon nanotube dispersion was 1.3 mg/mL.
Step three, preparing a carboxylated carbon nanotube/polyurethane spinning solution: adding polyurethane into the carboxylated carbon nanotube dispersion liquid prepared in the step one, and dissolving to prepare a carboxylated carbon nanotube/polyurethane spinning solution; in this example, the mass concentration of polyurethane in the carboxylated carbon nanotube/polyurethane spinning solution was 14.5%.
Fourthly, electrostatic spinning: performing electrostatic spinning on the carboxylated carbon nanotube/polyurethane spinning solution prepared in the third step to obtain a carboxylated carbon nanotube/polyurethane composite film; in the embodiment, the voltage of electrostatic spinning is 14kV, the relative humidity of electrostatic spinning is 35%, the receiving distance of electrostatic spinning is 14cm, the pushing speed of electrostatic spinning is 0.14mm/min, and the needle caliber is 21G.
Fifthly, ultrasonically anchoring and decorating the carbon nano tube: and anchoring the carboxylated carbon nanotube on the carboxylated carbon nanotube/polyurethane composite material film by using an ultrasonic anchoring technology and an ultrasonic reaction synthesizer to obtain the carboxylated carbon nanotube-polyurethane heat-conducting film. In this embodiment, the ultrasonic power is 800W, the ultrasonic time is 50min, and the ultrasonic frequency is 21 kHz.
And (3) spectrum characterization and analysis:
(1) analysis of a structural schematic diagram of the heat-conducting film:
as shown in fig. 1, a schematic structural diagram of the carboxylated carbon nanotube-polyurethane thermal conductive film prepared by the present invention is drawn, by electrospinning a mixed solution of carboxylated carbon nanotubes/polyurethane, the carboxylated carbon nanotubes can form a thermal conductive path inside polyurethane fibers, as shown in a magnifying glass in fig. 1, in addition, a TEM image in fig. 6 further proves that the carbon nanotubes can form a thermal conductive path inside polyurethane, and then anchoring the carbon nanotubes on the electrospun carboxylated carbon nanotube/polyurethane composite film by an ultrasonic anchoring technology. the-COOH in the carboxylated carbon nano tube can form hydrogen bonds with-NH-functional groups in-NHCO-in a polyurethane structural unit, so that the carbon nano tube is firmly anchored on the polyurethane fiber cloth and does not fall off. Therefore, a heat conduction path can be formed simultaneously in the inner part and the outer surface of the polyurethane fiber by adding a small amount of carbon nano tubes, and a strong hydrogen bond acting force is formed, so that the interaction force between the carbon nano tubes and the polyurethane is increased, the scattering of phonons is promoted, and the heat dissipation and heat transfer capacity of the prepared carboxylated carbon nano tube-polyurethane heat conduction film is further improved. Meanwhile, the prepared carboxylated carbon nanotube-polyurethane heat-conducting film can better dissipate hot steam due to the porous fiber structure, so that the capability of protecting electronic components is improved.
In addition, fig. 2 is a schematic diagram of heat dissipation of a carboxylated carbon nanotube-polyurethane thermal conductive film when being heated. Because the carboxylated carbon nanotubes are transversely and longitudinally connected and the carbon nanotubes in the polyurethane fiber can accelerate the heat dissipation rate, the figure 2 more intuitively illustrates the reason for improving the heat conductivity coefficient of the heat-conducting film.
(2) Infrared spectroscopic analysis of carboxylated carbon nanotubes:
infrared spectroscopic analysis of the carboxylated carbon nanotube and the untreated carbon nanotube obtained in example 1 showed that, as shown in FIG. 3, curve a represents the infrared spectrum of the carboxylated carbon nanotube and curve b represents the infrared spectrum of the untreated carbon nanotube, and it can be seen from FIG. 3 that the carboxylated carbon nanotube of the present invention is 3440cm in length compared to the untreated carbon nanotube-1Has stronger absorption peaks corresponding to the stretching vibration peak of-OH and is 1631cm-1The peak of stretching vibration of-COOH is obvious, and the peak of stretching vibration of-COOH of the untreated carbon nano tube is almost not pure. From the above analysis, the carboxylated carbon nanotube has more abundant-OH and-COOH functional groups on the surface.
(3) Infrared spectroscopic analysis of the carboxylated carbon nanotube/polyurethane heat-conducting film:
the interaction force of the carboxylated carbon nanotube and the polyurethane film is researched by infrared spectroscopy. In the spectrum of FIG. 4, 3321cm-1The wave number is the stretching vibration peak of N-H bond in polyurethane chain, 2937cm-1The wave number is the stretching vibration peak of-CH bond, and the strong absorption peaks at 1729cm-1 and 1596cm-1 are attributed toAbsorption peaks of-H-N-COO-, in addition to the absorption peaks at wave numbers of 1529cm-1 and 1076cm-1, respectively, the absorption peaks are ascribed to the bending vibration of N-H bond and C-O. 3321cm when carboxylated carbon nanotubes are spun into and anchored at the surface of the polyurethane fiber-1，2937cm-1，1729cm-1，1529cm-1And 1076cm-1The absorption peak is shifted to 3315cm-1，2935cm-1，1728cm-1，1526cm-1And 1072cm-1. The wave number deviation means that an interaction force exists between the carboxylated carbon nanotubes and the polyurethane fiber film, and the carbon nanotubes can be promoted to be modified on the surface of the polyurethane fiber film to form a good heat conduction path.
(4) SEM and TEM images of carboxylated carbon nanotube @ polyurethane film and carboxylated carbon nanotube/polyurethane heat-conducting film:
fig. 6 a is a scanning electron microscope image of the carboxylated carbon nanotube/polyurethane composite film obtained by electrostatic spinning, and it can be seen from the image that the fiber surface has smooth but protrusions, which shows that the carboxylated carbon nanotube is in the fiber and can form a heat conduction path, and fig. d is a transmission electron microscope image of the carboxylated carbon nanotube-polyurethane heat conduction film, which further demonstrates the idea. And the drawing b is a scanning electron microscope image of the carboxylated carbon nanotube-polyurethane heat-conducting film obtained after the carboxylated carbon nanotubes are ultrasonically anchored, and it can be seen from the drawing that the carboxylated carbon nanotubes are uniformly dispersed on the surface of the fiber, so that a good heat-conducting path can be formed on the surface of the fiber, and the heat dissipation and heat conduction capability of the polyurethane fiber film are promoted. And the figure c is a cross-sectional view of the carboxylated carbon nanotube/polyurethane composite material film obtained by electrostatic spinning, which illustrates that the composite material is a layered porous material, the heat transfer is promoted by the presence of the carbon nanotube, and the hot gas generated by the components in a humid environment can be dissipated by the porous structure, so that the electronic components are further protected.
(5) Testing heat conduction data:
the thermal conductivity of the carboxylated carbon nanotube-polyurethane thermal conductive film prepared in the embodiment 1 is measured, and it can be seen from the thermal conductivity data that the prepared carboxylated carbon nanotube/polyurethane thermal conductive film has anisotropic thermal conductivity, and the maximum thermal conductivity in the horizontal direction can reach 6.01W/(m.k), as shown by a curve b in fig. 7, which is 3 to 4 times that of the commercially available thermal conductive silicone grease; the heat conductivity coefficient in the direction perpendicular to the plane is slightly lower but can also reach 1.70W/(mK) as shown by curve a in FIG. 7, which is higher than that of the commercially available heat conductive silicone oil by 1.5W/(mK). The heat conduction capability of the carboxylated carbon nanotube/polyurethane heat conduction film in the vertical direction or the horizontal direction is remarkably improved.
(6) And (3) stress strain analysis:
a stress-strain test was performed on the carboxylated carbon nanotube/polyurethane thermal conductive film prepared in example 1. It can be seen from fig. 8 that the addition of the carboxylated carbon nanotubes greatly increases the young's modulus of the fiber film, from the original 2.42MPa to 4.36MPa, by 114%, which shows that the addition of the carboxylated carbon nanotubes obviously increases the young's modulus of the fiber film, the elongation at break is reduced by only 12%, and the advantages of the method are obvious compared with the methods such as physical mixing, not only the flexibility of the fiber is not changed, but also the young's modulus is further improved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A preparation method of a carboxylated carbon nanotube-polyurethane heat conducting film is characterized by comprising the following steps: it comprises the following steps:
step one, preparing a carboxylated carbon nanotube: carboxylated carbon nanotubes are made by treating carbon nanotubes with a mixed acid formulated from concentrated sulfuric acid and concentrated nitric acid, the carboxylated carbon nanotubes having a structure represented by formula I:
step two, preparing a carboxylated carbon nanotube dispersion liquid: dispersing the carboxylated carbon nanotubes prepared in the first step into a mixed solvent of acetone and dimethylformamide, and uniformly stirring to prepare a carboxylated carbon nanotube dispersion liquid;
step three, preparing a carboxylated carbon nanotube/polyurethane spinning solution: adding polyurethane into the carboxylated carbon nanotube dispersion liquid prepared in the second step, and dissolving to prepare a carboxylated carbon nanotube/polyurethane spinning solution;
fourthly, electrostatic spinning: performing electrostatic spinning on the carboxylated carbon nanotube/polyurethane spinning solution prepared in the third step to obtain a carboxylated carbon nanotube/polyurethane composite film;
fifthly, ultrasonically anchoring and decorating the carbon nano tube: anchoring the carboxylated carbon nanotube on the carboxylated carbon nanotube/polyurethane composite material film by using an ultrasonic anchoring technology and an ultrasonic reaction synthesizer to obtain the carboxylated carbon nanotube-polyurethane heat-conducting film;
in the first step, preparing the carboxylated carbon nano tube, wherein the diameter of the carbon nano tube is 10-20 nm, and the length of the carbon nano tube is 3-15 mu m;
and in the fifth step of ultrasonic anchoring of the decorative carbon nano tube, the ultrasonic power is 400-960W, the ultrasonic time is 20-60 min, and the ultrasonic frequency is 18-22 kHz.
2. The method for preparing a carboxylated carbon nanotube-polyurethane heat conducting film according to claim 1, wherein the method comprises the following steps: the preparation of the carboxylated carbon nanotube in the first step comprises the following steps:
step one, acidizing: adding carbon nanotubes into a container, preparing mixed acid of concentrated sulfuric acid and concentrated nitric acid, adding the mixed acid into the container filled with the carbon nanotubes after the mixed acid is cooled, carrying out condensation reflux, then adding water into the container, cooling after the condensation reflux is finished, and standing substances in the container;
step two, acid removal: and (3) removing supernatant from the substance after standing in the step one, taking the lower layer solution for centrifugal treatment, then taking the centrifuged precipitate for vacuum filtration, and washing with water until the precipitate is neutral, thus obtaining the carboxylated carbon nanotube.
3. The method for preparing a carboxylated carbon nanotube-polyurethane heat conducting film according to claim 2, wherein the method comprises the following steps: in the acidification treatment of the first step, the temperature of the condensation reflux is 60-80 ℃, the time of the condensation reflux is 3-3.5 h, the volume ratio of the added water to the mixed acid is 2-2.5: 1, and the standing time is 22-26 h;
in the step two, in the acid removal, the centrifugal rotating speed is 8000-15000 r/min; the centrifugation times are 6-8.
4. The method for preparing a carboxylated carbon nanotube-polyurethane heat conducting film according to claim 1, wherein the method comprises the following steps: in the first step of preparing the carboxylated carbon nanotube, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid is 2-4: 1;
in the first step of preparing the carboxylated carbon nanotube, the mass-to-volume ratio of the carbon nanotube to the mixed acid is 10-30 g/L.
5. The method for preparing a carboxylated carbon nanotube-polyurethane heat conducting film according to claim 1, wherein the method comprises the following steps: preparing a carboxylated carbon nanotube dispersion liquid in the second step, wherein the volume ratio of acetone to dimethylformamide in the mixed solvent is 1: 1;
the concentration of the carboxylated carbon nanotube dispersion liquid is 0.5-1.5 mg/mL.
6. The method for preparing a carboxylated carbon nanotube-polyurethane heat conducting film according to claim 1, wherein the method comprises the following steps: and the third step is to prepare a carboxylated carbon nanotube/polyurethane spinning solution, wherein the mass concentration of the polyurethane in the carboxylated carbon nanotube/polyurethane spinning solution is 13-15%.
7. The method for preparing a carboxylated carbon nanotube-polyurethane heat conducting film according to claim 1, wherein the method comprises the following steps: and in the fourth step of electrostatic spinning, the voltage of the electrostatic spinning is 10-15 kV, the relative humidity of the electrostatic spinning is 20-40%, the receiving distance of the electrostatic spinning is 10-15 cm, the pushing speed of the electrostatic spinning is 0.08-0.15 mm/min, and the caliber of the needle head is 21-22G.
8. A carboxylated carbon nanotube-polyurethane heat conducting film is characterized in that: a carboxylated carbon nanotube-polyurethane heat-conductive film obtained by the method for preparing a carboxylated carbon nanotube-polyurethane heat-conductive film according to any one of claims 1 to 7.
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