CN112126217A - Fullerene/carbon nanotube/thermoplastic resin composite film, and preparation method and application thereof - Google Patents
Fullerene/carbon nanotube/thermoplastic resin composite film, and preparation method and application thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/045—Fullerenes
Abstract
The invention provides a fullerene/carbon nano tube/thermoplastic resin composite film, which comprises a thermoplastic resin and carbon material composite body; the carbon material composite is formed of an oxidation-modified fullerene and an oxidation-modified carbon nanotube. Compared with the prior art, the method utilizes Van der Waals force between the oxidation modified fullerene and the oxidation modified carbon nano tube to assemble and form the carbon material complex with the three-dimensional bridge structure, and then the carbon material complex is wound by thermoplastic resin to form a stable film which can deform under illumination stimulation and has optical stimulation response, so that the method is expected to be used in the field of light-operated sensors.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a fullerene/carbon nanotube/thermoplastic resin composite film, and a preparation method and application thereof.
Background
In recent years, researchers at home and abroad have conducted extensive research on responsive smart materials. The responsive intelligent material is a material which can sense the change of environment, such as temperature, humidity, illumination, pH and the like, and respond to the change mechanically, and has potential application prospects in various fields.
Among them, the light stimulation has the advantages of environmental protection, non-contact and controllability, and is widely concerned in the research of responsive intelligent materials. At present, the photoresponse is realized mainly by introducing a photoisomerization molecule such as azobenzene, but the process generally relates to a complex synthetic reaction, for example, Chinese patent with the application number of CN201911284420.6 discloses a light/heat three-form memory star-shaped polymer and a preparation method thereof, the polymer is a responsive azobenzene polymer, and the preparation process is complicated.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a fullerene/carbon nanotube/thermoplastic resin composite film with photostimulation response, and a preparation method and an application thereof.
The invention provides a fullerene/carbon nano tube/thermoplastic resin composite film, which comprises a thermoplastic resin and carbon material composite body;
the carbon material composite is formed of an oxidation-modified fullerene and an oxidation-modified carbon nanotube.
Preferably, the mass of the fullerene modified by oxidation is 0.1-1.5% of the mass of the fullerene/carbon nano tube/thermoplastic resin composite film; the mass of the carbon nano tube modified by oxidation is 0.1-1.5% of that of the fullerene/carbon nano tube/thermoplastic resin composite film.
Preferably, the mass ratio of the oxidation-modified carbon nanotube to the oxidation-modified fullerene is 1: (0.1-10).
Preferably, the number of carbon atoms of the fullerene is 20-100; the carbon nano tube is a single-wall carbon nano tube and/or a multi-wall carbon nano tube; the diameter of the single-walled carbon nanotube is 0.6-2 nm; the diameter of the multi-walled carbon nanotube is 2-100 nm; the thermoplastic resin is polyurethane.
Preferably, the thickness of the fullerene/carbon nanotube/thermoplastic resin composite film is 8-150 μm.
The invention also provides a preparation method of the fullerene/carbon nano tube/thermoplastic resin composite film, which comprises the following steps:
s1) assembling the oxidation-modified fullerene and the oxidation-modified carbon nanotube in a solvent to obtain a carbon material composite dispersion liquid;
s2) adding a thermoplastic resin to the carbon material composite dispersion liquid, mixing, and drying to obtain a fullerene/carbon nanotube/thermoplastic resin composite film.
Preferably, the fullerene oxidatively modified in the step S1) is formed by oxidatively modifying fullerene with a first strong acid; the oxidation-modified carbon nanotube is formed by oxidizing and modifying the carbon nanotube by a second strong acid; the first strong acid and the second strong acid are respectively and independently mixed acid of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1; the mass percent of the concentrated sulfuric acid is 95-98%; the mass percentage of the concentrated nitric acid is 65-68%; the time for oxidizing and modifying the fullerene by the first strong acid and the time for oxidizing and modifying the carbon nanotube by the second strong acid are respectively and independently 0.5-3 h;
the mixing speed in the step S2) is 90-300 r/min; the mixing time is 30-90 min; the drying is vacuum drying; the drying temperature is 40-110 ℃; the drying time is 8-24 h.
Preferably, the step S1) is specifically:
A1) dispersing the fullerene subjected to oxidation modification in a solvent to obtain fullerene dispersion liquid subjected to oxidation modification;
dispersing the carbon nano tube subjected to oxidation modification in a solvent to obtain carbon nano tube dispersion liquid subjected to oxidation modification;
A2) mixing and assembling the fullerene dispersion liquid subjected to oxidation modification and the carbon nano tube dispersion liquid subjected to oxidation modification to obtain a carbon material composite dispersion liquid;
the solvent is selected from one or more of methanol, ethanol, acetone, formamide and chloroform;
the concentrations of the oxidation-modified fullerene dispersion liquid and the oxidation-modified carbon nano tube dispersion liquid are respectively 0.5-2.5 mg/ml.
Preferably, a2) is specifically:
dropping the fullerene dispersion liquid subjected to oxidation modification into the carbon nanotube dispersion liquid subjected to oxidation modification under the condition of stirring, and stirring, mixing and assembling to obtain a carbon material composite dispersion liquid;
or dropping the carbon nano tube dispersion liquid subjected to oxidation modification into the fullerene dispersion liquid subjected to oxidation modification under the condition of stirring, mixing and assembling to obtain a carbon material composite dispersion liquid;
the dropping speed is 2-4 drops/second; the stirring speed is 90-300 r/min; the stirring and mixing time is 6-14 h.
The invention also provides application of the fullerene/carbon nano tube/thermoplastic resin composite film in the field of light-operated sensors.
The invention provides a fullerene/carbon nano tube/thermoplastic resin composite film, which comprises a thermoplastic resin and carbon material composite body; the carbon material composite is formed of an oxidation-modified fullerene and an oxidation-modified carbon nanotube. Compared with the prior art, the method utilizes Van der Waals force between the oxidation modified fullerene and the oxidation modified carbon nano tube to assemble and form the carbon material complex with the three-dimensional bridge structure, and then the carbon material complex is wound by thermoplastic resin to form a stable film which can deform under illumination stimulation and has optical stimulation response, so that the method is expected to be used in the field of light-operated sensors.
Drawings
FIG. 1 is a graph of the UV-VIS absorption spectrum of a pure polyurethane film;
FIG. 2 is a diagram of an ultraviolet-visible light absorption spectrum of the fullerene/carbon nanotube/polyurethane composite film obtained in example 1 of the present invention;
fig. 3 is a diagram showing a result of a light-driven experiment of the fullerene/carbon nanotube/polyurethane composite film obtained in example 1 of the present invention;
fig. 4 is a diagram showing a result of a light-driven repeatability test of the fullerene/carbon nanotube/polyurethane composite film obtained in example 1 of the present invention;
FIG. 5 is a Raman spectrum of the fullerene/carbon nanotube/polyurethane composite film obtained in example 2 of the present invention;
fig. 6 is a scanning electron microscope image of the fullerene/carbon nanotube/polyurethane composite film obtained in example 2 of the present invention;
fig. 7 is a graph of the results of the optical driving experiment of the fullerene/carbon nanotube/polyurethane composite film obtained in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a fullerene/carbon nano tube/thermoplastic resin composite film, which comprises a thermoplastic resin and carbon material composite body; the carbon material composite is formed of an oxidation-modified fullerene and an oxidation-modified carbon nanotube.
Wherein the thermoplastic resin is preferably polyurethane; the mass of the thermoplastic resin is preferably 97 to 99.8 percent, more preferably 98 to 99.5 percent, and even more preferably 98 to 99 percent of the mass of the fullerene/carbon nanotube/thermoplastic resin composite film.
The mass of the fullerene modified by oxidation is preferably 0.1 to 1.5 percent of the mass of the fullerene/carbon nano tube/thermoplastic resin composite film, more preferably 0.5 to 1.5 percent, and even more preferably 0.5 to 1 percent; the carbon atom number of fullerene in the oxidation modified fullerene is preferably 20-100, more preferably 40-80, and further preferably 50-70; the oxidation-modified fullerene is preferably a strong acid oxidation-modified fullerene; the strong acid used for oxidation modification of the strong acid is preferably a mixed acid of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1; the mass percent of the concentrated sulfuric acid is 95-98%; the mass percentage of the concentrated nitric acid is 65-68%.
The mass of the carbon nano tube modified by oxidation is preferably 0.1-1.5%, more preferably 0.5-1.5%, and even more preferably 0.5-1% of the mass of the fullerene/carbon nano tube/thermoplastic resin composite film; the carbon nanotubes are preferably single-walled carbon nanotubes and/or multi-walled carbon nanotubes; the diameter of the single-walled carbon nanotube is preferably 0.6-2 nm; the diameter of the multi-walled carbon nanotube is preferably 2-100 nm; the carbon nano tube modified by oxidation is preferably a strong acid oxidation modified carbon nano tube; the strong acid used for oxidation modification of the strong acid is preferably a mixed acid of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1; the mass percent of the concentrated sulfuric acid is 95-98%; the mass percentage of the concentrated nitric acid is 65-68%.
In the present invention, the mass ratio of the oxidation-modified carbon nanotube to the oxidation-modified fullerene is preferably 1: (0.1 to 10), more preferably 1: (0.2-5), and more preferably 1: (0.2 to 3), and most preferably 1: (0.3 to 1).
Oxygen-containing groups are introduced to the surfaces of the fullerene and the carbon nano tube which are subjected to oxidation modification, so that the van der Waals force between the fullerene and the carbon nano tube is enhanced, and the fullerene and the carbon nano tube can be assembled to form a stable carbon material complex with a three-dimensional bridge network structure; the thermoplastic resin wraps the carbon material complex, so as to form a stable fullerene/carbon nano tube/thermoplastic resin composite film; the thickness of the fullerene/carbon nanotube/thermoplastic resin composite film is preferably 8-150 μm, more preferably 10-120 μm, still more preferably 20-100 μm, and most preferably 30-80 μm.
The invention utilizes Van der Waals force between the fullerene modified by oxidation and the carbon nano tube modified by oxidation to assemble a carbon material complex with a three-dimensional bridge structure, and then the carbon material complex is wound by thermoplastic resin to form a stable film which can deform under illumination stimulation and has optical stimulation response, thus being hopeful to be used in the field of light-operated sensors.
The invention also provides a preparation method of the fullerene/carbon nanotube/thermoplastic resin composite film, which comprises the following steps: s1) assembling the oxidation-modified fullerene and the oxidation-modified carbon nanotube in a solvent to obtain a carbon material composite dispersion liquid; s2) adding a thermoplastic resin to the carbon material composite dispersion liquid, mixing and drying to obtain a fullerene/carbon nanotube/thermoplastic resin composite film.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
According to the present invention, the oxidatively modified fullerene is preferably formed by oxidatively modifying a fullerene with a first strong acid; the number of carbon atoms of the fullerene is preferably 20-100, more preferably 40-80, and further preferably 50-70; the first strong acid is preferably a mixed acid of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1; the mass percent of the concentrated sulfuric acid is 95-98%; the mass percentage of the concentrated nitric acid is 65-68%; the temperature of the first strong acid oxidation modification is preferably 40-90 ℃, and more preferably 70-90 ℃; the time of the first strong acid oxidation treatment is preferably 0.5-3 h, and more preferably 1-2 h; and (3) preferably cooling to room temperature after the first strong acid oxidation modification treatment, adding deionized water for multiple dilution, and performing suction filtration when the solution is neutral to obtain the oxidation-modified fullerene.
The oxidation-modified carbon nanotubes are preferably formed by oxidation-modifying carbon nanotubes with a second strong acid; the carbon nanotubes are preferably single-walled carbon nanotubes and/or multi-walled carbon nanotubes; the diameter of the single-walled carbon nanotube is preferably 0.6-2 nm; the diameter of the multi-walled carbon nanotube is preferably 2-100 nm; the second strong acid is preferably a mixed acid of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1; the mass percent of the concentrated sulfuric acid is 95-98%; the mass percentage of the concentrated nitric acid is 65-68%; the temperature of the second strong acid oxidation modification is preferably 40-90 ℃, and more preferably 70-90 ℃; the time of the second strong acid oxidation treatment is preferably 0.5-3 h, and more preferably 1-2 h; and (3) preferably cooling to room temperature after the second strong acid oxidation modification treatment, adding deionized water for multiple dilution, and performing suction filtration when the solution is neutral to obtain the oxidation-modified carbon nano tube.
Assembling the oxidation-modified fullerene and the oxidation-modified carbon nano tube in a solvent to obtain a carbon material composite dispersion liquid; the solvent is preferably one or more of methanol, ethanol, acetone, formamide and chloroform; the mixing time is preferably 6-14 h; in the present invention, the step is preferably embodied as follows: A1) dispersing the fullerene subjected to oxidation modification in a solvent to obtain fullerene dispersion liquid subjected to oxidation modification; dispersing the carbon nano tube subjected to oxidation modification in a solvent to obtain carbon nano tube dispersion liquid subjected to oxidation modification; A2) and mixing and assembling the oxidation-modified fullerene dispersion liquid and the oxidation-modified carbon nano tube dispersion liquid to obtain the carbon material composite dispersion liquid.
Dispersing the fullerene subjected to oxidation modification in a solvent to obtain fullerene dispersion liquid subjected to oxidation modification; the solvent is preferably one or more of methanol, ethanol, acetone, formamide and chloroform; the method of dispersion is preferably sonication; the power of the ultrasonic wave is preferably 100-200W, and more preferably 150W; the dispersing time is preferably 30-120 min, and more preferably 60-90 min; the concentration of the obtained oxidation-modified fullerene dispersion liquid is preferably 0.5-2.5 mg/ml, more preferably 1-2 mg/ml, and still more preferably 1-1.5 mg/ml.
Dispersing the carbon nano tube subjected to oxidation modification in a solvent to obtain carbon nano tube dispersion liquid subjected to oxidation modification; the solvent is preferably one or more of methanol, ethanol, acetone, formamide and chloroform; the method of dispersion is preferably sonication; the power of the ultrasonic wave is preferably 100-200W, and more preferably 150W; the dispersing time is preferably 30-120 min, and more preferably 60-90 min; the concentration of the obtained oxidation-modified carbon nanotube dispersion liquid is preferably 0.5 to 2.5mg/ml, more preferably 1 to 2mg/ml, and still more preferably 1 to 1.5 mg/ml.
Mixing and assembling the fullerene dispersion liquid subjected to oxidation modification and the carbon nano tube dispersion liquid subjected to oxidation modification to obtain a carbon material composite dispersion liquid; oxygen-containing groups are introduced to the surfaces of the fullerene and the carbon nano tube which are subjected to oxidation modification, so that the dispersibility in a solvent is enhanced, the van der Waals force between the fullerene and the carbon nano tube is enhanced, and the fullerene and the carbon nano tube can be assembled to form a stable carbon material complex with a three-dimensional bridge network structure; the mass ratio of the oxidation-modified carbon nanotube to the oxidation-modified fullerene is preferably 1: (0.1 to 10), more preferably 1: (0.2-5), and more preferably 1: (0.2 to 3), and most preferably 1: (0.3 to 1); in the present invention, it is preferable that the oxidation-modified fullerene dispersion is dropped into the oxidation-modified carbon nanotube dispersion under stirring, and the resultant is stirred, mixed and assembled to obtain a carbon material composite dispersion; the stirring speed is preferably 90-300 revolutions/min, more preferably 100-250 revolutions/min, and further preferably 150-200 revolutions/min; the dripping speed is preferably 2-4 drops/second, and the dripping position is preferably changed in the dripping process; the stirring and mixing time is preferably 6-14 h; or dropping the carbon nano tube dispersion liquid subjected to oxidation modification into the fullerene dispersion liquid subjected to oxidation modification under the condition of stirring, mixing and assembling to obtain a carbon material composite dispersion liquid; the stirring speed is preferably 90-300 revolutions/min, more preferably 100-250 revolutions/min, and further preferably 150-200 revolutions/min; the dripping speed is preferably 2-4 drops/second, and the dripping position is preferably changed in the dripping process; the stirring and mixing time is preferably 6-14 h.
Adding a thermoplastic resin to the carbon material composite dispersion liquid and mixing; the thermoplastic resin is preferably polyurethane; in the present invention, it is preferable to add a thermoplastic resin to the carbon material composite dispersion liquid under stirring; the stirring speed is preferably 90-300 revolutions/min, more preferably 100-250 revolutions/min, and further preferably 150-200 revolutions/min; the thermoplastic resin is preferably added to the carbon material composite dispersion liquid in a small amount and a plurality of times; in order to allow the thermoplastic resin to be more favorably entangled with the carbon material composite, the thermoplastic resin is preferably dissolved in a solvent and then added to the carbon material composite dispersion liquid; the mixing time is preferably 30-90 min, more preferably 40-80 min, and still more preferably 50-70 min.
After mixing, drying, preferably in a mold; the mould can be in different shapes such as round, rectangular and the like according to requirements; the material of the mould is preferably glass, stainless steel or polytetrafluoroethylene; the drying is preferably vacuum drying; the drying temperature is preferably 40-110 ℃, more preferably 40-100 ℃, and further preferably 60-80 ℃; the drying time is preferably 8-24 h.
The preparation method comprises the steps of respectively ultrasonically dispersing an oxidation-modified fullerene and an oxidation-modified carbon nano tube in a solvent, mixing, assembling by using van der Waals force to form a carbon material complex with a bridge structure, dissolving a thermoplastic resin in the solvent, and winding the thermoplastic resin on the carbon material complex by using a solution blending method, thereby obtaining the fullerene/carbon nano tube/thermoplastic resin composite film with photostimulation response.
The invention also provides application of the fullerene/carbon nano tube/thermoplastic resin composite film in the field of light-operated sensors.
In order to further illustrate the present invention, the following describes in detail a fullerene/carbon nanotube/thermoplastic resin composite film, a preparation method and applications thereof, with reference to the following examples.
The reagents used in the following examples are all commercially available.
Example 1
1.1 weigh 10 mg of carbon nanotube and 10 mg of fullerene with a precision electronic balance and place them in a three-neck flask. Respectively measuring 6 ml of concentrated H by using a measuring cylinder2SO4And 2 ml of concentrated HNO3The ratio of the two is V (H)2SO4):V(HNO3) Pouring the two acids into a beaker, mixing to prepare a mixed acid solution, and adding the mixed acid solution into a three-neck flask containing the carbon nano tube and the fullerene respectively. And standing, cooling to room temperature, putting the three-neck flask into an ultrasonic cell crusher, and ultrasonically dispersing for 50 minutes at room temperature by using an ultrasonic cell crusher at 150W. And after the ultrasonic treatment is finished, putting the three-neck flask into a constant-temperature heating magnetic stirrer, and stirring and acidifying at the constant temperature of 90 ℃ for 1 hour. After the stirring, the three-necked flask was taken out and placed in a fume hood for standing and cooling. When the temperature is reduced to room temperature, deionized water is added for multiple times of dilution, and when the solution is neutral, the oxidation modified carbon nano tube and the oxidation modification can be obtained by suction filtrationThe fullerene material of (4).
1.2 respectively measuring 8 milliliters of DMF, adding the DMF into two beakers, respectively weighing 8 milligrams of the oxidation modified carbon nano tube and the oxidation modified fullerene obtained in the step 1.1, respectively adding the oxidation modified carbon nano tube and the oxidation modified fullerene obtained in the step 1 into the beakers containing the DMF, carrying out ultrasonic treatment on the mixture for 1 hour by using an ultrasonic cell crusher 150W, and completely dissolving and uniformly dispersing the oxidation modified carbon nano tube and the oxidation fullerene materials subjected to ultrasonic treatment in a DMF solution to obtain 1mg/mL oxidation modified carbon nano tube dispersion liquid and 1mg/mL oxidation modified fullerene dispersion liquid.
1.3 respectively measuring 5 ml of the oxidation modified carbon nano tube dispersion liquid and the oxidation modified fullerene dispersion liquid obtained in the step 1.2, and magnetically stirring for 12 hours at 150 r/min. And weighing 1 g of polyurethane, dissolving the polyurethane in 1 ml of DMF, adding the solution into a small amount of the solution for many times, magnetically stirring the solution for 50 minutes at room temperature at the speed of 150 rpm, transferring the solution to a special polytetrafluoroethylene mold, and placing the special polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 80 ℃ for drying until a film is formed, thus obtaining the fullerene/carbon nano tube/polyurethane composite film.
The polyurethane film and the fullerene/carbon nanotube/polyurethane composite film obtained in example 1 were tested for light absorption, and ultraviolet and visible light absorption spectra thereof were obtained, as shown in fig. 1 and 2. Wherein, FIG. 1 is a UV-visible absorption spectrum of a pure polyurethane film; fig. 2 is an ultraviolet-visible light absorption spectrum of the fullerene/carbon nanotube/polyurethane composite film obtained in example 1. As can be seen from fig. 1, the light absorption of the composite film was tested because pure polyurethane has very poor light absorption and the composite film must have a certain light absorption in order to have light drivability. As shown in fig. 2, the fullerene/carbon nanotube/polyurethane composite film exhibits good light absorption in the wavelength range of 600-900 nm, and the addition of the oxidized and modified fullerene and the oxidized and modified carbon nanotube makes the composite film have light absorption compared with pure polyurethane.
The fullerene/carbon nanotube/polyurethane composite film obtained in example 1 was subjected to a light driveability test, and the film was placed at a distance of 25 cm from the light source of a xenon short-arc lamp, and the light source position was adjusted so that the film was located at the center of the light source. The power of the short-arc xenon lamp was set to 300 watts, the wavelength was 600 nm, the irradiation time was 3 minutes, and the change of the film during the light irradiation process was recorded using a camera, and a photograph was obtained as shown in fig. 3. The experimental result shows that the composite film is slowly deformed under the drive of illumination, and the raising angle of the film is 5 degrees after 3 minutes of illumination.
The photo-driven repeatability of the fullerene/carbon nanotube/polyurethane composite film obtained in example 1 was tested, and the results are shown in fig. 4.
Example 2
Unlike example 1, in this example, 7.5 ml of the carbon nanotube dispersion and 2.5 ml of the fullerene dispersion were measured in step 1.2.
The fullerene/carbon nanotube/polyurethane composite film obtained in example 2 was detected by raman spectroscopy, and the raman spectrum thereof was shown in fig. 5. As can be seen from fig. 5, both peaks D and G appear in the raman spectrum of the thin film, indicating that a certain conjugated structure of carbon atoms exists in the thin film.
The fullerene/carbon nanotube/polyurethane composite film obtained in example 2 was analyzed by a scanning electron microscope, and a scanning electron micrograph thereof is shown in fig. 6. As can be seen from fig. 6, the linear carbon nanotubes and the granular fullerenes are mixed alternately to form a bridge structure.
The fullerene/carbon nanotube/polyurethane composite film obtained in example 2 was subjected to a light driveability test, and the film was placed at a distance of 25 cm from the xenon short-arc light source, and the light source position was adjusted so that the film was located at the center of the light source. The power of the short-arc xenon lamp was set to 300 watts, the wavelength was 600 nm, the irradiation time was 3 minutes, and the change of the film during the light irradiation was recorded using a camera, and a photograph was obtained as shown in fig. 7.
Claims (10)
1. A fullerene/carbon nanotube/thermoplastic resin composite film is characterized by comprising a thermoplastic resin and carbon material composite body;
the carbon material composite is formed of an oxidation-modified fullerene and an oxidation-modified carbon nanotube.
2. The fullerene/carbon nanotube/thermoplastic resin composite film according to claim 1, wherein the mass of the oxidatively modified fullerene is 0.1% to 1.5% of the mass of the fullerene/carbon nanotube/thermoplastic resin composite film; the mass of the carbon nano tube modified by oxidation is 0.1-1.5% of that of the fullerene/carbon nano tube/thermoplastic resin composite film.
3. The fullerene/carbon nanotube/thermoplastic resin composite film according to claim 1, wherein the mass ratio of the oxidation-modified carbon nanotube to the oxidation-modified fullerene is 1: (0.1-10).
4. The fullerene/carbon nanotube/thermoplastic resin composite film according to claim 1, wherein the number of carbon atoms of the fullerene is 20 to 100; the carbon nano tube is a single-wall carbon nano tube and/or a multi-wall carbon nano tube; the diameter of the single-walled carbon nanotube is 0.6-2 nm; the diameter of the multi-walled carbon nanotube is 2-100 nm; the thermoplastic resin is polyurethane.
5. The fullerene/carbon nanotube/thermoplastic resin composite film according to claim 1, wherein the fullerene/carbon nanotube/thermoplastic resin composite film has a thickness of 8 to 150 μm.
6. A preparation method of a fullerene/carbon nanotube/thermoplastic resin composite film is characterized by comprising the following steps:
s1) assembling the oxidation-modified fullerene and the oxidation-modified carbon nanotube in a solvent to obtain a carbon material composite dispersion liquid;
s2) adding a thermoplastic resin to the carbon material composite dispersion liquid, mixing, and drying to obtain a fullerene/carbon nanotube/thermoplastic resin composite film.
7. The method according to claim 6, wherein the fullerene oxidatively modified in step S1) is formed by a first strong acid oxidatively modified fullerene; the oxidation-modified carbon nanotube is formed by oxidizing and modifying the carbon nanotube by a second strong acid; the first strong acid and the second strong acid are respectively and independently mixed acid of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1; the mass percent of the concentrated sulfuric acid is 95-98%; the mass percentage of the concentrated nitric acid is 65-68%; the time for oxidizing and modifying the fullerene by the first strong acid and the time for oxidizing and modifying the carbon nanotube by the second strong acid are respectively and independently 0.5-3 h;
the mixing speed in the step S2) is 90-300 r/min; the mixing time is 30-90 min; the drying is vacuum drying; the drying temperature is 40-110 ℃; the drying time is 8-24 h.
8. The preparation method according to claim 6, wherein the step S1) is specifically:
A1) dispersing the fullerene subjected to oxidation modification in a solvent to obtain fullerene dispersion liquid subjected to oxidation modification;
dispersing the carbon nano tube subjected to oxidation modification in a solvent to obtain carbon nano tube dispersion liquid subjected to oxidation modification;
A2) mixing and assembling the fullerene dispersion liquid subjected to oxidation modification and the carbon nano tube dispersion liquid subjected to oxidation modification to obtain a carbon material composite dispersion liquid;
the solvent is selected from one or more of methanol, ethanol, acetone, formamide and chloroform;
the concentrations of the oxidation-modified fullerene dispersion liquid and the oxidation-modified carbon nano tube dispersion liquid are respectively 0.5-2.5 mg/ml.
9. The preparation method according to claim 8, wherein A2) is specifically:
dropping the fullerene dispersion liquid subjected to oxidation modification into the carbon nanotube dispersion liquid subjected to oxidation modification under the condition of stirring, and stirring, mixing and assembling to obtain a carbon material composite dispersion liquid;
or dropping the carbon nano tube dispersion liquid subjected to oxidation modification into the fullerene dispersion liquid subjected to oxidation modification under the condition of stirring, mixing and assembling to obtain a carbon material composite dispersion liquid;
the dropping speed is 2-4 drops/second; the stirring speed is 90-300 r/min; the stirring and mixing time is 6-14 h.
10. The use of the fullerene/carbon nanotube/thermoplastic resin composite film according to any one of claims 1 to 5 or the fullerene/carbon nanotube/thermoplastic resin composite film prepared by the preparation method according to any one of claims 6 to 9 in the field of photo-controlled sensors.
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| CN202011084743.3A CN112126217B (en) | 2020-10-12 | 2020-10-12 | Fullerene/carbon nanotube/thermoplastic resin composite film, and preparation method and application thereof |
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