Method for improving extraction efficiency of single-chiral carbon nanotubes, reagent composition and application

Abstract

The present invention discloses a method for improving the extraction efficiency of single-chirality carbon nanotubes, a reagent composition and an application. The method comprises: mixing a reinforcing polymer, a chiral extracting polymer, a carbon nanotube raw material and a solvent, and then separating the obtained mixture to obtain a high-concentration single-chirality carbon nanotube solution. The method provided by the present invention greatly improves the concentration and separation efficiency of single-chirality carbon nanotubes while ensuring the purity of carbon nanotubes, and the improvement is about 10 times; at the same time, the method has universal applicability and is applicable to the extraction and separation of various carbon nanotubes such as (6, 5), (7, 5), (10, 5) and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of carbon nanotubes, and in particular relates to a method for improving the extraction efficiency of single-chirality carbon nanotubes, a reagent composition and an application thereof. Background Art

[0002] Single-walled carbon nanotubes have a unique one-dimensional structure, which greatly reduces the scattering encountered during carrier transmission, so it has ultra-high carrier mobility and ultra-long mean free path, which will give carbon nanotubes significant advantages in speed and power consumption in electronic device applications. The diameter, band gap and energy level distribution of carbon nanotubes have a great influence on the migration and transmission of carriers. Many high-end applications require carbon nanotubes with specific structures. Single-chirality carbon nanotubes have excellent properties of determined energy bands, uniform structure and uniform performance. Many attempts have been made to separate single-chirality carbon nanotubes in the early stage, such as ATPE under DNA or dispersant, gel chromatography, DGU, polymer separation method, etc. However, due to the low abundance of single-chirality carbon nanotube raw materials and very low extraction efficiency, the concentration of single-chirality carbon nanotube solutions is low and the price is expensive. Therefore, single-chirality carbon nanotubes have not been widely used. The existing technology can only achieve the concentration of semiconductor single-walled carbon nanotubes. When introducing the second polymer, it changes the original separation product. In the final product, different chirality results have changed. However, it is difficult to achieve the enhancement of a single chiral carbon nanotube. Therefore, improving the concentration and extraction efficiency of single chiral carbon nanotubes has always been a problem that people need to solve. Summary of the invention

[0003] The main purpose of the present invention is to provide a method, a reagent composition and an application for improving the extraction efficiency of single-chirality carbon nanotubes, so as to overcome the shortcomings of the prior art.

[0004] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0005] The embodiment of the present invention provides a method for improving the extraction efficiency of single-chirality carbon nanotubes, which comprises: mixing a reinforcing polymer, a chiral extracting polymer, a carbon nanotube raw material and a solvent, and then separating the obtained mixture to obtain a high-concentration single-chirality carbon nanotube solution.

[0006] An embodiment of the present invention also provides a reagent composition for improving the extraction efficiency of single-chirality carbon nanotubes, which comprises a reinforcing polymer and a chiral extractive polymer that can wrap, disperse and selectively extract single-chirality carbon nanotubes in a selected liquid environment; the reagent composition comprises a reinforcing polymer, a chiral extractive polymer and a solvent.

[0007] The embodiment of the present invention also provides a method for preparing a unichiral carbon nanotube film, which comprises:

[0008] The above method is used to prepare a high concentration of single-chirality carbon nanotube solution;

[0009] And, the single-chirality carbon nanotube solution is subjected to film-forming treatment to obtain a single-chirality carbon nanotube film.

[0010] Compared with the prior art, the present invention has the following beneficial effects:

[0011] (1) The method provided by the present invention greatly improves the concentration and separation efficiency of single-chirality carbon nanotubes while ensuring the purity of carbon nanotubes, with the improvement factor being about 10 times;

[0012] (2) The method for improving the extraction efficiency of single-chirality carbon nanotubes provided by the present invention is universal and applicable to various carbon nanotubes such as (6, 5), (7, 5), and (10, 5);

[0013] (3) The method for improving the extraction efficiency of single-chirality carbon nanotubes provided by the present invention greatly reduces the preparation cost of single-chirality carbon nanotubes;

[0014] (4) The high concentration of the single-chirality carbon nanotube solution in the present invention facilitates the preparation of the single-chirality carbon nanotube film. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0016] Figure 1 is a schematic diagram of a method for improving the extraction efficiency of single-chirality carbon nanotubes in a typical embodiment of the present invention;

[0017] Figure 2 is a spectrum of the (6,5) single-chirality carbon nanotubes obtained in Example 1 of the present invention;

[0018] Figure 3 is a spectrum of (7,5) single-chirality carbon nanotubes obtained in Example 2 of the present invention;

[0019] Figure 4 This is a spectrum diagram of the (10, 5) single-chirality carbon nanotubes obtained in Example 3 of the present invention. DETAILED DESCRIPTION

[0020] In view of the defects of the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The purpose of this application is to improve the concentration and separation efficiency of single-chirality carbon nanotubes through the synergistic effect of two polymers. While ensuring the purity of single-chirality carbon nanotubes, the concentration of single-chirality carbon nanotubes is improved. It mainly adds a polymer with chirality selectivity and a polymer with enhanced type and the carbon tube raw material required for chirality sorting into the solution at the same time to separate them. This method can greatly improve the concentration and separation efficiency of single-chirality carbon nanotubes.

[0021] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Specifically, as one aspect of the technical solution of the present invention, a method for improving the extraction efficiency of single-chirality carbon nanotubes involves: mixing a reinforcing polymer, a chiral extracting polymer, a carbon nanotube raw material and a solvent, and then separating the obtained mixture to obtain a high-concentration single-chirality carbon nanotube solution.

[0023] Specifically, the method for improving the extraction efficiency of single-chiral carbon nanotubes by synergistic action of dual polymers in the present application is as follows: Figure 1 As shown, the synergistic effect of the two polymers enhances the effect of single-chirality carbon nanotubes. The present application utilizes the mutual relationship between the polymers to ensure the purity of the single-chirality carbon nanotube solution while greatly improving the purity of the single-chirality carbon nanotube solution and its extraction efficiency. The two types of polymers and carbon tubes are added to the toluene solution at the same time, and the two polymers will wrap, depolymerize, and re-wrap with the carbon tubes, thereby achieving a high-concentration single-chirality carbon nanotube solution.

[0024] The present invention utilizes the strength of the binding force between the two polymers (the reinforcing polymer and the chiral extracting polymer) and the carbon nanotubes to greatly improve the separation efficiency of the single-chiral carbon nanotubes while ensuring their purity. When the two polymers are added at the same time for separation, due to the inherent weak interaction and strong dispersion ability between the reinforcing polymer and the carbon nanotubes, the two polymers disperse the carbon tube raw materials at the same time. Since the interaction force between the chiral extracting polymer and the carbon nanotubes is stronger than that between the reinforcing polymer and the carbon nanotubes, the chiral extracting polymer is replaced during the ultrasonic process. Finally, through separation operations such as centrifugation, the original separation purity is retained. The replaced reinforcing polymer is freed in the solution again, and the original carbon nanotubes are repeatedly dispersed, thereby enhancing the separation efficiency of the single-chiral carbon nanotubes.

[0025] In some preferred embodiments, the reinforcing polymer can at least increase the concentration of single-chirality carbon nanotubes in the obtained solution when single-chirality separation of the carbon nanotube solution is performed.

[0026] Specifically, when the reinforcing polymer and the chiral extracting polymer are used to separate the carbon nanotube solution, compared with simply using the chiral extracting polymer to separate the carbon nanotube solution, the simultaneous addition of the two greatly increases the separated carbon tube raw materials, and at the same time, the purity of the single chiral carbon nanotubes separated by the double polymers remains unchanged compared to the purity of the single chiral carbon nanotubes dispersed by the original single polymer.

[0027] Furthermore, the enhanced polymer includes any one of PFIID, PCz-PXX, PFO, and PCP, or a combination of two or more thereof, but is not limited thereto.

[0028] In some preferred embodiments, the chiral extraction polymer is a polymer that can obtain single-chiral carbon nanotubes with a chiral purity of more than 60% when separating carbon nanotubes.

[0029] Furthermore, the chiral extractable polymer includes any one of PFO-BPy, PFO, F8BT, PFP, PCP or a combination of two or more thereof, but is not limited thereto.

[0030] Furthermore, PFO-BPy preferentially sorts (7, 5) single-chirality carbon nanotubes; PFO preferentially sorts (6, 5) single-chirality carbon nanotubes; and F8BT preferentially sorts (10, 5) single-chirality carbon nanotubes.

[0031] In some preferred embodiments, in a chiral tube separation, the selected reinforcing polymer and the chiral extracting polymer are different from each other, but some polymers can serve as both reinforcing polymers and chiral extracting polymers.

[0032] In some preferred embodiments, the carbon nanotube raw material includes any one or a combination of two or more of CoMoCAT carbon nanotubes, HiPCO carbon nanotubes, laser evaporated carbon nanotubes, CVD tubes, Arc carbon nanotubes, plasma carbon nanotubes, and Tuball carbon nanotubes, and is not limited thereto.

[0033] Furthermore, the carbon nanotube raw material includes any one of CoMoCAT carbon nanotubes, HiPCO carbon nanotubes, and CVD tubes, or a combination of two or more thereof, but is not limited thereto.

[0034] In some preferred embodiments, the solvent includes any one or a combination of two or more of toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, cyclohexane, chloroform, and chlorobenzene, and is not limited thereto.

[0035] In some preferred embodiments, the mass ratio of the reinforcing polymer to the chiral extracting polymer is 1-10:2-40.

[0036] In some preferred embodiments, the mass ratio of the reinforced polymer to the carbon nanotube raw material is 1-10:2-40.

[0037] In some preferred embodiments, the mass volume ratio of the carbon nanotube raw material to the solvent is 1-10 mg: 2-40 mL.

[0038] In some preferred embodiments, the method specifically comprises: mixing and dispersing the reinforcing polymer, the chiral extracting polymer, the carbon nanotube raw material and the solvent, and then centrifuging the obtained mixture to separate the supernatant to obtain a high concentration of monochiral carbon nanotube solution.

[0039] In some preferred embodiments, the single-chirality carbon nanotubes contained in the single-chirality carbon nanotube solution include any one of (6, 5) single-chirality carbon nanotubes, (7, 5) single-chirality carbon nanotubes, (10, 5) single-chirality carbon nanotubes, (9, 8) single-chirality carbon nanotubes, and (10, 8) single-chirality carbon nanotubes, and are not limited thereto.

[0040] In some preferred embodiments, the purity of the single-chirality carbon nanotubes in the high-concentration single-chirality carbon nanotube solution is above 60%.

[0041] In the present invention, the relationship between polymers is utilized to classify polymers into enhanced polymers, chiral extractable polymers, and other types of polymers, and several enhanced polymers are selected, such as PFIID, PCz-PXX, PFO, etc.; the carbon tube raw materials used in the present invention are CoMoCAT and HiPCO, respectively, and the selected chiral extractable polymers are PFO-BPy, PFO, F8BT, etc. PFO-BPy preferentially sorts (7, 5) single-chirality carbon nanotubes; PFO preferentially sorts (6, 5) single-chirality carbon nanotubes; F8BT preferentially sorts (10, 5) single-chirality carbon nanotubes; the present invention adds a trace amount of reinforcing polymer, chiral extracting polymer and carbon nanotubes into a toluene solution at the same time, and adopts various separation methods to finally obtain a variety of enhanced single-chirality carbon nanotube solutions, such as (6, 5), (7, 5), (10, 5) (9, 8), (10, 8), etc.; the present invention conducts ultraviolet absorption spectrum test on the prepared single-chirality solution, and compares the absorbance with that of the single polymer system solution, and the absorbance intensity is increased by about 10 times.

[0042] Another aspect of an embodiment of the present invention also provides a reagent composition for improving the extraction efficiency of single-chirality carbon nanotubes, which comprises a reinforcing polymer and a chiral extractive polymer that can wrap, disperse and selectively extract single-chirality carbon nanotubes in a selected liquid environment; the reagent composition includes a reinforcing polymer, a chiral extractive polymer and a solvent.

[0043] In some preferred embodiments, the reinforcing polymer can at least increase the concentration of single-chirality carbon nanotubes in the obtained solution when single-chirality separation of the carbon nanotube solution is performed.

[0044] Furthermore, the enhanced polymer includes any one of PFIID, PCz-PXX, PFO, and PCP, or a combination of two or more thereof, but is not limited thereto.

[0045] In some preferred embodiments, the chiral extraction polymer is a polymer that can obtain single-chiral carbon nanotubes with a chiral purity of more than 60% when separating carbon nanotubes.

[0046] Furthermore, the chiral extractable polymer includes any one of PFO-BPy, PFO, F8BT, PFP, PCP or a combination of two or more thereof, but is not limited thereto.

[0047] In some preferred embodiments, when sorting a certain chiral tube, the selected reinforcing polymer and chiral extracting polymer are different, but some polymers can be used as both reinforcing polymers and chiral extracting polymers.

[0048] In some preferred embodiments, the solvent includes any one or a combination of two or more of toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, cyclohexane, chloroform, and chlorobenzene, and is not limited thereto.

[0049] In some preferred embodiments, the mass ratio of the reinforcing polymer to the chiral extracting polymer is 1-10:2-40.

[0050] Another aspect of the embodiments of the present invention further provides a method for preparing a unichiral carbon nanotube film, which comprises:

[0051] The above method is used to prepare a high concentration of single-chirality carbon nanotube solution;

[0052] And, the single-chirality carbon nanotube solution is subjected to film-forming treatment to obtain a single-chirality carbon nanotube film.

[0053] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments and drawings. This embodiment is implemented on the premise of the technical solution of the invention, and a detailed implementation method and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0054] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0055] Example 1

[0056] (1) PFO polymer, PFO-BPy polymer and CoMoCAT were weighed in a ratio of 5 mg: 15 mg: 20 mg, respectively, and added into 20 mL of toluene solution for ultrasonication. After the ultrasonication, centrifugation was performed immediately at a centrifugal force of 10,000-40,000 g for 0.5-2 hours, and finally 80% of the supernatant was taken out to obtain a high concentration of monochiral carbon nanotube solution.

[0057] (2) The supernatant was subjected to a UV absorption test to compare the absorption intensity between the single polymer and the double polymer. The test showed that the absorption intensity was enhanced by about 10 times.

[0058] The flow chart of using PFo polymer to enhance the concentration of (6,5) single-chirality carbon nanotube solution in this example is as follows: Figure 1 As shown; Figure 2 The spectrum of (6,5) single-chirality carbon nanotubes obtained in this example is shown in Figure 1. The purity of the enhanced (6,5) chirality carbon nanotubes is 88%, and the separation efficiency is 20-30%.

[0059] Example 2

[0060] (1) PCz-PXX polymer, PFO polymer and CoMoCAT were weighed in a ratio of 10 mg:15 mg:15 mg, respectively, and added into 40 mL of toluene solution for ultrasonication. After the ultrasonication, centrifugation was performed at a centrifugal force of 30,000-40,000 g for 0.5-2 hours, and finally 80% of the supernatant was taken out to obtain a high concentration of monochiral carbon nanotube solution.

[0061] (2) The supernatant was subjected to a UV absorption test to compare the absorption intensity between the single polymer and the double polymer. The test showed that the absorption intensity was enhanced by about 5 times.

[0062] The flow chart of using PCz-PXX polymer to enhance the concentration of (7,5) single-chirality carbon nanotube solution in this example is as follows: Figure 1 As shown; Figure 3 This is the spectrum of the (7, 5) single-chirality carbon nanotubes obtained in this example.

[0063] Example 3

[0064] (1) PCz-PXX polymer, F8BT polymer and HiPCO were weighed in a ratio of 5 mg: 10 mg: 30 mg, respectively, and added into 30 mL of toluene solution for ultrasonication. After the ultrasonication, centrifugation was performed immediately at a centrifugal force of 10,000-20,000 g for 0.5 to 2 hours, and finally 80% of the supernatant was taken out to obtain a high concentration of single-chiral carbon nanotube solution.

[0065] (2) The supernatant was subjected to a UV absorption test to compare the absorption intensity between the single polymer and the double polymer. The test showed that the absorption intensity was enhanced by about 5 times.

[0066] The flow chart of using PCz-PXX polymer to enhance the concentration of (10,5) single-chirality carbon nanotube solution in this example is as follows: Figure 1 As shown; Figure 4 This is the spectrum of the (10, 5) single-chirality carbon nanotubes obtained in this example.

[0067] Example 4

[0068] (1) PFIID polymer, PFO polymer and SG65i were weighed in a ratio of 3 mg: 3 mg: 5 mg, respectively, and added into 20 mL of toluene solution for ultrasonication. After the ultrasonication, centrifugation was performed immediately at a centrifugal force of 30,000-40,000 g for 0.5-2 hours, and finally 80% of the supernatant was taken out to obtain a high concentration of single-chiral carbon nanotube solution.

[0069] (2) The supernatant was subjected to a UV absorption test to compare the absorption intensity between the single polymer and the double polymer. The test showed that the absorption intensity was enhanced by about 5 times.

[0070] Example 5

[0071] PCz-PXX polymer, F8BT polymer and HiPCO were weighed at 1 mg: 2 mg: 2 mg respectively and added into 20 mL toluene solution for ultrasonication. After the ultrasonication, centrifugation was performed immediately at a centrifugal force of 10000-20000 g for 0.5 to 2 hours. Finally, 80% of the supernatant was taken out to obtain a high concentration of unichiral semiconductor carbon nanotube solution.

[0072] Example 6

[0073] PCz-PXX polymer, F8BT polymer and HiPCO were weighed at 5 mg: 10 mg: 20 mg respectively and added into 100 mL toluene solution for ultrasonication. After the ultrasonication, centrifugation was performed immediately at a centrifugal force of 10000-20000 g for 0.5 to 2 hours. Finally, 80% of the supernatant was taken out to obtain a high concentration of unichiral semiconductor carbon nanotube solution.

[0074] Example 7

[0075] (1) PFIID polymer, PFO polymer and SG65i were weighed in a ratio of 3 mg: 3 mg: 5 mg, respectively, and added into 20 mL of toluene solution for ultrasonication. After the ultrasonication, centrifugation was performed immediately at a centrifugal force of 30,000-40,000 g for 0.5-2 hours, and finally 80% of the supernatant was taken out to obtain a high concentration of single-chiral carbon nanotube solution.

[0076] (2) The supernatant was subjected to a UV absorption test to compare the absorption intensity between the single polymer and the double polymer. The test showed that the absorption intensity was enhanced by about 5 times.

[0077] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0078] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the protection scope of the present invention.

Claims

1. A method for improving the extraction efficiency of single-chiral carbon nanotubes, characterized in that include: The reinforcing polymer is PFO, the chiral extracting polymer is PFO-BPy, the carbon nanotube raw material and toluene are mixed and dispersed, and then the obtained mixture is centrifuged to separate the supernatant, thereby obtaining a high-concentration (6,5) single-chiral carbon nanotube solution; Alternatively, the reinforcing polymer is PCz-PXX, the chiral extracting polymer is PFO, the carbon nanotube raw material and toluene are mixed and dispersed, and then the obtained mixture is centrifuged to separate the supernatant, thereby obtaining a high-concentration (7,5) single-chiral carbon nanotube solution; Alternatively, the reinforcing polymer is PCz-PXX, the chiral extracting polymer is F8BT, the carbon nanotube raw material and toluene are mixed and dispersed, and then the obtained mixture is centrifuged to separate the supernatant, thereby obtaining a high-concentration (10,5) single-chiral carbon nanotube solution; The enhanced polymer has a weak interaction force with the carbon tubes and a strong dispersion ability, and the interaction force between the chiral extraction polymer and the carbon tubes is stronger than that of the enhanced polymer; when the carbon nanotube solution is subjected to single chirality separation, the enhanced polymer can at least increase the concentration of single chiral carbon nanotubes in the obtained solution; the mass ratio of the enhanced polymer to the chiral extraction polymer is 1~10:2~40; the mass ratio of the enhanced polymer to the carbon nanotube raw material is 1~10:2~40.

2. The method according to claim 1, characterized in that: The carbon nanotube raw material is selected from any one or a combination of two or more of CoMoCAT carbon nanotubes, HiPCO carbon nanotubes, laser evaporated carbon nanotubes, CVD tubes, Arc carbon nanotubes, plasma carbon nanotubes, and Tuball carbon nanotubes.

3. The method according to claim 2, characterized in that: The carbon nanotube raw material is selected from any one of CoMoCAT carbon nanotubes, HiPCO carbon nanotubes, and CVD tubes, or a combination of two or more thereof.

4. The method according to claim 1, characterized in that: The mass volume ratio of the carbon nanotube raw material to toluene is 1-10 mg: 2-40 mL.

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