CN109517345B - Multi-walled carbon nanotube bonded poly (3-hexylthiophene) material and preparation method thereof - Google Patents
Multi-walled carbon nanotube bonded poly (3-hexylthiophene) material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon nano tube bonded poly (3-hexylthiophene) material and a preparation method thereof, wherein the method comprises the following steps: after being tiled, the poly-3-hexylthiophene and the carbon nanotube array are placed in a protective gas atmosphere for primary ultraviolet irradiation treatment, so that the poly-3-hexylthiophene and the carbon nanotube array are subjected to graft polymerization reaction to obtain a modified carbon nanotube; mixing the modified carbon nano tube and poly-3-hexylthiophene, dissolving in a solvent, removing the solvent after ultrasonic treatment, and drying to obtain a multi-walled carbon nano tube-poly-3-hexylthiophene mixture; and spreading the multi-wall carbon nanotube-poly 3-hexylthiophene mixture on a substrate, then placing the substrate in a protective gas atmosphere for secondary ultraviolet irradiation treatment, and cooling to obtain the carbon nanotube bonded poly 3-hexylthiophene material. The invention solves the problem that poly-3-hexylthiophene is not stable enough and cannot be applied to micro-nano-scale products.
Description
Technical Field
The invention relates to the technical field of carbon nanotubes and polythiophene compounds, in particular to a multiwalled carbon nanotube bonded poly (3-hexylthiophene) material and a preparation method thereof.
Background
Polythiophene polymers, especially poly 3-hexylthiophene, have been an important and commonly used electroactive compound, and are often used in polymer LEDs, organic transistors, solar cells, photo-resistors, antistatic coatings, and photo-detectors. However, the process for manufacturing the micro-nano-scale product must include an ultraviolet or electron beam irradiation process, and the irradiation process often causes photodegradation of the polythiophene polymer, which in turn causes deterioration and even rejection of the whole product performance.
The carbon nano tube is a nano-scale tubular carbon molecule, has many excellent physicochemical properties, such as ultrahigh elastic modulus, conductivity exceeding metal in the tube length direction, flexibility and insulativity in the radial direction and the like, determines the important position of the carbon nano tube in the fields of nano electronics and biochemical detectors, also indicates that the stability of the poly-3-hexylthiophene can be enhanced by combining the carbon nano tube with the poly-3-hexylthiophene, and simultaneously utilizes the excellent physicochemical properties of the carbon nano tube. However, the carbon nanotubes are stable, so that it is difficult to combine poly-3-hexylthiophene with the carbon nanotubes, i.e., the carbon nanotubes cannot be successfully combined with poly-3-hexylthiophene to enhance the stability of poly-3-hexylthiophene.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a multi-walled carbon nanotube bonded poly-3-hexylthiophene material and a preparation method thereof, and aims to solve the problem that poly-3-hexylthiophene in the prior art is not stable enough, so that the poly-3-hexylthiophene cannot be applied to micro-nano-scale products.
The technical scheme of the invention is as follows:
a preparation method of a multi-walled carbon nanotube bonded poly (3-hexylthiophene) material comprises the following steps:
after being tiled, the poly-3-hexylthiophene and the multi-walled carbon nanotube array are placed in a protective gas atmosphere for primary ultraviolet irradiation treatment, so that the poly-3-hexylthiophene and the multi-walled carbon nanotube array are subjected to graft polymerization reaction, and a modified multi-walled carbon nanotube is obtained;
mixing the modified multi-walled carbon nanotube and poly-3-hexylthiophene, dissolving in a solvent, removing the solvent after ultrasonic treatment, and drying to obtain a multi-walled carbon nanotube-poly-3-hexylthiophene mixture;
and spreading the multi-walled carbon nanotube-poly 3-hexylthiophene mixture on a substrate, then placing the substrate in a protective gas atmosphere for secondary ultraviolet irradiation treatment, and cooling to obtain the multi-walled carbon nanotube bonded poly 3-hexylthiophene material.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material comprises the step of preparing a solvent, wherein the solvent is chloroform.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material is characterized in that the thickness of the multi-walled carbon nanotube-poly-3-hexylthiophene mixture after being tiled is less than or equal to 2 mm.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material comprises the following steps of carrying out primary ultraviolet irradiation treatment on the multi-walled carbon nanotube bonded poly-3-hexylthiophene material, wherein the wavelength of ultraviolet rays is 218nm, and the wavelength of ultraviolet rays is 196 nm.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material comprises the following steps of (1) performing primary ultraviolet irradiation treatment at a power of 20-50 mW for 2-10 mins; the power of the secondary ultraviolet irradiation treatment is 20-50 mW, and the time is 20-50 mins.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material comprises the following step of preparing a multi-walled carbon nanotube bonded poly-3-hexylthiophene material, wherein the protective gas is nitrogen or inert gas.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material comprises the step of controlling protective gas to continuously flow when ultraviolet irradiation treatment is carried out.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material comprises the following steps of preparing a multi-walled carbon nanotube array, wherein the average length of the multi-walled carbon nanotube array is 700-800 mu m, and the diameter of the multi-walled carbon nanotube is 10-15 nm.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material comprises the following steps of carrying out ultrasonic treatment at the frequency of 26kHz and carrying out ultrasonic treatment for 20-50 mins.
The preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material comprises the step of mixing the modified multi-walled carbon nanotube and the poly-3-hexylthiophene according to the mass ratio of 1: 19-1: 49, and dissolving the mixture in chloroform.
A multiwalled carbon nanotube bonded poly-3-hexylthiophene material, which is prepared by the method of any one of claims 1 to 9.
Has the advantages that: according to the invention, poly-3-hexylthiophene and the surface of a multi-walled carbon nanotube array are subjected to graft polymerization reaction through ultraviolet irradiation to complete modification of the multi-walled carbon nanotube, then the modified multi-walled carbon nanotube and the poly-3-hexylthiophene are mixed and dissolved in a solvent to prepare a multi-walled carbon nanotube-poly-3-hexylthiophene mixture, and the mixture is subjected to ultraviolet irradiation treatment, so that the poly-3-hexylthiophene and the multi-walled carbon nanotube are chemically combined to prepare a multi-walled carbon nanotube bonded poly-3-hexylthiophene material, and the photochemical stability of the poly-3-hexylthiophene is greatly enhanced.
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FIG. 1 is a schematic flow chart of a preferred embodiment of a method for preparing a multiwalled carbon nanotube-bonded poly (3-hexylthiophene) material according to the present invention;
FIG. 2 is a scanning electron microscope image of a modified multi-walled carbon nanotube according to the present invention;
FIG. 3 is a spectral analysis of multi-walled carbon nanotube-bonded poly 3-hexylthiophene material NP1 after ultraviolet irradiation;
FIG. 4 is a spectral analysis of the multi-walled carbon nanotube-bonded poly 3-hexylthiophene material NP2 after ultraviolet irradiation;
FIG. 5 is a spectral analysis of multi-walled carbon nanotube-bonded poly 3-hexylthiophene material NP3 after ultraviolet irradiation;
FIG. 6 is a spectral analysis of the multi-walled carbon nanotube-bonded poly 3-hexylthiophene material NP4 after ultraviolet irradiation.
Detailed Description
The invention provides a multi-walled carbon nanotube bonded poly-3-hexylthiophene material and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method of the multi-walled carbon nanotube bonded poly (3-hexylthiophene) material disclosed by the invention comprises the following steps of:
s1, placing the tiled poly-3-hexylthiophene and the multi-walled carbon nanotube array in a protective gas atmosphere for primary ultraviolet irradiation treatment to enable the poly-3-hexylthiophene and the multi-walled carbon nanotube array to perform graft polymerization reaction to obtain modified multi-walled carbon nanotubes;
s2, mixing the modified multi-walled carbon nanotube and poly-3-hexylthiophene, dissolving in a solvent, removing the solvent after ultrasonic treatment, and drying to obtain a multi-walled carbon nanotube-poly-3-hexylthiophene mixture;
s3, spreading the multi-walled carbon nanotube-poly 3-hexylthiophene mixture on a substrate, then placing the substrate in a protective gas atmosphere for secondary ultraviolet irradiation treatment, and cooling to obtain the multi-walled carbon nanotube bonded poly 3-hexylthiophene material.
In step S1, the multi-walled carbon nanotube array and the poly-3-hexylthiophene are required to be provided, and the commercially available pure poly-3-hexylthiophene can be used. Then respectively tiling poly-3-hexylthiophene and multi-walled carbon nanotube arrays, placing the poly-3-hexylthiophene and the multi-walled carbon nanotube arrays side by side in a protective gas atmosphere, then carrying out primary ultraviolet irradiation treatment, wherein the irradiation effect of ultraviolet light is favorable for providing the heat effect of a reaction system, the system is in a gas state formed by the poly-3-hexylthiophene when the temperature is raised, the system moves to the surface of the multi-walled carbon nanotube array under the action of protective gas flow to carry out graft polymerization reaction with the multi-walled carbon nanotube array, meanwhile, the ultraviolet irradiation can open C ═ C double bonds on the surface of the multi-walled carbon nanotube to generate dangling bonds, the poly-3-hexylthiophene can be partially broken to form free radicals, and after the free radicals and the dangling bonds on the surface of the multi-walled carbon nanotube, the bonds can be formed, so that the poly-3-hexylthiophene, the modified multi-walled carbon nano-tube is obtained and is activated by ultraviolet irradiation, which is beneficial to being combined with poly 3-hexylthiophene; meanwhile, a layer of poly-3-hexylthiophene is grafted on the surface of the modified multi-walled carbon nanotube, so that more binding sites are provided for further binding with the poly-3-hexylthiophene, and more poly-3-hexylthiophene can be bound.
The wavelength of the ultraviolet light used in the primary ultraviolet irradiation treatment is 218nm, the multi-wall carbon nano tube and the poly-3-hexylthiophene cannot be effectively activated when the wavelength is too long, and the self structure of the multi-wall carbon nano tube array is easily damaged when the wavelength is too short, so that the multi-wall carbon nano tube is damaged, and the poly-3-hexylthiophene is also degraded.
The power of the primary ultraviolet irradiation treatment is 20-50 mW, and the time is 2-10 mins. Preferably, the power of the primary ultraviolet irradiation treatment is 35mW, the time is 5mins, and the excessive treatment time can cause the degradation of the poly-3-hexylthiophene.
Preferably, the thickness of the tiled poly-3-hexylthiophene is controlled within the range of 1-3mm, so that the poly-3-hexylthiophene is uniformly activated by ultraviolet light.
Preferably, the multi-walled carbon nanotube array has an average length of 700-800 μm and a diameter of 10-15 nm. More preferably, the controlled multi-walled carbon nanotube array has an average length of 760 μm. The preparation method of the multi-wall carbon nanotube array comprises the following steps: depositing a catalyst layer on a substrate, placing the substrate in a chemical vapor deposition reaction furnace, heating to 650 ℃ through protective gas, introducing carbon source gas, controlling the flow at 2L/min, and reacting for 25min, thereby generating a multi-walled carbon nanotube array with the average length of 700-800 mu m and the diameter of 10-15 nm on the substrate.
In the step S2, the modified multi-walled carbon nanotube and the poly-3-hexylthiophene are mixed and dissolved in a solvent, the solvent is removed by reduced pressure distillation after ultrasonic treatment, and then the mixture is dried to obtain the multi-walled carbon nanotube-poly-3-hexylthiophene mixture. The steps can not only further activate the modified multi-walled carbon nanotube to form the multi-walled carbon nanotube, thereby providing a larger contact area and more contact sites for the grafting reaction with the poly-3-hexylthiophene, but also fully and uniformly mixing the modified multi-walled carbon nanotube with the poly-3-hexylthiophene, and facilitating the subsequent grafting reaction. Among them, the solvent is preferably chloroform.
Preferably, the ultrasonic treatment frequency is 26kHz, and the ultrasonic time is 20-50 mins. The multi-walled carbon nanotube cannot be formed when the ultrasonic frequency is too low, and the modified film layer on the surface of the modified multi-walled carbon nanotube can be damaged when the ultrasonic power is too high. Preferably, the ultrasound time is 35mins, i.e., the activation process is completed and multi-walled carbon nanotubes are formed.
In the step S2, the modified multi-walled carbon nanotubes and the poly-3-hexylthiophene are mixed and dissolved in chloroform according to the mass ratio of 1: 19-1: 49. When the content of the modified multi-walled carbon nanotube is too low, the poly-3-hexylthiophene cannot be grafted effectively, namely the inhibition effect on the photodegradation of the poly-3-hexylthiophene cannot be realized; when the content of the multi-wall carbon nano-tube is too high, the realization of the function of the poly-3-hexylthiophene is influenced, and the cost is wasted.
In the step S3, the multi-walled carbon nanotube-poly 3-hexylthiophene mixture is laid on the substrate with a thickness less than 2mm, then placed in a protective gas atmosphere for secondary ultraviolet irradiation treatment, and cooled to room temperature, so as to prepare the multi-walled carbon nanotube bonded poly 3-hexylthiophene material. Similarly, the irradiation effect of ultraviolet light is favorable for providing the heat effect of a reaction system, so that a C ═ C double bond on the surface of the multi-wall carbon nanotube is opened to generate a dangling bond, and part of the poly-3-hexylthiophene is broken to form a free radical, and the free radical can form a bond after being bonded with the dangling bond on the surface of the multi-wall carbon nanotube, so that the poly-3-hexylthiophene is grafted to the surface of the multi-wall carbon nanotube, meanwhile, the originally grafted layer of poly-3-hexylthiophene on the surface of the multi-wall carbon nanotube can also be partially broken to form a free radical, and the free radical is further combined with the poly-3-hexylthiophene, so that more poly-3-hexylthiophene can be combined, and finally the multi-wall carbon nanotube-poly.
Wherein the ultraviolet wavelength of the secondary ultraviolet irradiation treatment is 196 nm; the power of the secondary ultraviolet irradiation treatment is 20-50 mW, and the time is 20-50 mins.
In the preparation method of the multi-walled carbon nanotube bonded poly-3-hexylthiophene material, the protective gas is nitrogen or inert gas, the protective gas is controlled to continuously flow when ultraviolet irradiation treatment is carried out, and the poly-3-hexylthiophene is arranged in the direction of the air inlet, so that the continuously flowing protective gas can accelerate the poly-3-hexylthiophene to move to the surface of the multi-walled carbon nanotube array and the multi-walled carbon nanotube array, and the poly-3-hexylthiophene and the multi-walled carbon nanotube array are subjected to graft polymerization reaction.
The invention also provides a multi-walled carbon nanotube bonded poly-3-hexylthiophene material, which is prepared by the method.
The invention also provides a specific preparation method of the poly-3-hexylthiophene, which comprises the following steps:
dissolving 3-dodecyl thiophene in tetrahydrofuran, slowly adding N-bromosuccinimide (for more than 5 mins), wherein the molar ratio of the 3-dodecyl thiophene to the N-bromosuccinimide is controlled to be 1: 2-1: 3, reacting to obtain a mixed solution containing 2, 5-dibromo-3-dodecyl thiophene, uniformly stirring the mixed solution containing 2, 5-dibromo-3-dodecyl thiophene, carrying out primary reduced pressure distillation to remove a tetrahydrofuran solvent, then adding hexane to remove succinimide, carrying out secondary reduced pressure distillation to remove hexane, and distilling at 120 ℃ and 0.016T by using a Kugelrohr distillation method to obtain colorless transparent oily high-purity 2, 5-dibromo-3-dodecyl thiophene;
dissolving 2, 5-dibromo-3-dodecyl thiophene in tetrahydrofuran, adding methyl magnesium bromide, preheating at 120-150 ℃ for 1h, and adding Ni (dppp) Cl according to 1mol percent2The catalyst reacts for 2 hours, and after the reaction, the reaction solution is injected into an alcohol solvent, so that the catalyst, byproduct salt and unreacted monomer substances are removed by the alcohol solvent; and then adding hexane to remove the copolymer to obtain a mixed solution, performing Soxhlet filtration on the mixed solution by using chloroform, taking a chloroform layer in the mixed solution, performing rotary evaporation and concentration on the chloroform layer until a purple membrane is generated, and performing vacuum filtration for 3 hours to obtain pure poly-3-hexylthiophene. Wherein the alcohol solvent is methanol, ethanol and the like, and the methylmagnesium bromide is added into tetrahydrofuran dissolved with 2, 5-dibromo-3-dodecylthiophene in the form of butyl methyl ether solution.
Based on the method, the invention also provides a modified multi-wall carbon nanotube, wherein the modified multi-wall carbon nanotube is modified by the modification method.
The present invention will be described in detail below with reference to examples.
Example 1
Preparation of modified multiwalled carbon nanotubes
(1) Preparing multi-wall carbon nanotube powder: depositing a catalyst layer on a substrate, placing the substrate in a chemical vapor deposition reaction furnace, heating the substrate to 650 ℃ through protective gas, introducing carbon source gas, controlling the flow at 2L/min, and reacting for 25min, thereby generating the multi-walled carbon nanotube array on the substrate. The multi-walled carbon nanotube array is a multi-walled carbon nanotube array, the number average length is 760 micrometers, and the diameter of the multi-walled carbon nanotube is 10-15 nm;
(2) preparing a multi-wall carbon nanotube-poly (3-hexylthiophene) nano compound (namely the modified multi-wall carbon nanotube): preparing the prepared multi-walled carbon nanotube array together with a substrate; preparing another substrate, flatly laying the prepared film poly (3-hexylthiophene) on the substrate, and keeping the thickness of the film within the range of 1-3 mm; placing two substrates in parallel under a high-energy ultraviolet lamp with the irradiation power of 35mW and the wavelength of 218nm, controlling the distance between an ultraviolet lamp light source and a sample on the substrates to be 25mm, and controlling the irradiation time of the ultraviolet light to be 5 min; and then closing the ultraviolet light assembly, and exposing the multi-wall carbon nano tube array to the nitrogen atmosphere until the multi-wall carbon nano tube array is naturally cooled to obtain the surface modified multi-wall carbon nano tube array.
Scanning electron microscope experiments are carried out on the prepared modified multi-walled carbon nano-tube, and the result is shown in figure 2, the surface of the multi-walled carbon nano-tube is covered with a layer of poly (3-hexylthiophene) film, and the multi-walled carbon nano-tube is more easily dispersed in the poly (3-hexylthiophene) by the film.
Example 2
The modified multi-walled carbon nanotubes prepared in example 1 were mixed with poly 3-hexylthiophene (powder) in a weight ratio of 1: 99, and dissolving in chloroform to form a mixed solution; performing ultrasonic treatment on the mixed solution for 30 minutes by using ultrasonic waves (200W, 26kHz), then removing chloroform by reduced pressure distillation, and drying to obtain a well-uniformly mixed multi-walled carbon nanotube-poly (3-hexylthiophene) mixture;
uniformly spreading the multi-walled carbon nanotube-poly 3-hexylthiophene mixture on a substrate with the thickness of 1mm, placing the substrate under a high-strength ultraviolet lamp with the power of 38mW and the irradiation wavelength of 196nm for ultraviolet irradiation treatment, controlling the distance between the light source of the ultraviolet lamp and the sample to be 5mm, and controlling the irradiation time to be 35 min; and after the ultraviolet light is turned off, exposing the substrate to the nitrogen atmosphere until the substrate is naturally cooled, and obtaining the multi-walled carbon nanotube bonded poly 3-hexylthiophene material NP 1.
Example 3
The modified multi-walled carbon nanotubes prepared in example 1 were mixed with poly 3-hexylthiophene (powder) in a weight ratio of 1:49 and dissolving in chloroform to form a mixed solution; performing ultrasonic treatment on the mixed solution for 30 minutes by using ultrasonic waves (200W, 26kHz), then removing chloroform by reduced pressure distillation, and drying to obtain a well-uniformly mixed multi-walled carbon nanotube-poly (3-hexylthiophene) mixture;
uniformly spreading the multi-walled carbon nanotube-poly 3-hexylthiophene mixture on a substrate with the thickness of 1mm, placing the substrate under a high-strength ultraviolet lamp with the power of 38mW and the irradiation wavelength of 196nm for ultraviolet irradiation treatment, controlling the distance between the light source of the ultraviolet lamp and the sample to be 5mm, and controlling the irradiation time to be 35 min; and after the ultraviolet light is turned off, exposing the substrate to the nitrogen atmosphere until the substrate is naturally cooled, and obtaining the multi-walled carbon nanotube bonded poly 3-hexylthiophene material NP 2.
Example 4
The modified multi-walled carbon nanotubes prepared in example 1 were mixed with poly 3-hexylthiophene (powder) in a weight ratio of 1: 27.6, and dissolving in chloroform to form a mixed solution; performing ultrasonic treatment on the mixed solution for 30 minutes by using ultrasonic waves (200W, 26kHz), then removing chloroform by reduced pressure distillation, and drying to obtain a well-uniformly mixed multi-walled carbon nanotube-poly (3-hexylthiophene) mixture;
uniformly spreading the multi-walled carbon nanotube-poly 3-hexylthiophene mixture on a substrate with the thickness of 1mm, placing the substrate under a high-strength ultraviolet lamp with the power of 38mW and the irradiation wavelength of 196nm for ultraviolet irradiation treatment, controlling the distance between the light source of the ultraviolet lamp and the sample to be 5mm, and controlling the irradiation time to be 35 min; and after the ultraviolet light is turned off, exposing the substrate to the nitrogen atmosphere until the substrate is naturally cooled, and obtaining the multi-walled carbon nanotube bonded poly 3-hexylthiophene material NP 3.
Example 5
The modified multi-walled carbon nanotubes prepared in example 1 were mixed with poly 3-hexylthiophene (powder) in a weight ratio of 1:19, and dissolving the mixture in chloroform to form a mixed solution; performing ultrasonic treatment on the mixed solution for 30 minutes by using ultrasonic waves (200W, 26kHz), then removing chloroform by reduced pressure distillation, and drying to obtain a well-uniformly mixed multi-walled carbon nanotube-poly (3-hexylthiophene) mixture;
uniformly spreading the multi-walled carbon nanotube-poly 3-hexylthiophene mixture on a substrate with the thickness of 1mm, placing the substrate under a high-strength ultraviolet lamp with the power of 38mW and the irradiation wavelength of 196nm for ultraviolet irradiation treatment, controlling the distance between the light source of the ultraviolet lamp and the sample to be 5mm, and controlling the irradiation time to be 35 min; and after the ultraviolet light is turned off, exposing the substrate to the nitrogen atmosphere until the substrate is naturally cooled, and obtaining the multi-walled carbon nanotube bonded poly 3-hexylthiophene material NP 4.
Example 6
UV-visible spectra (UV-visible spectrophotometry) analysis was performed on each of NP 1-NP 4: the samples were exposed to UV light and the spectra were recorded every 1 minute, with the results shown in FIGS. 3-6.
As can be seen from FIG. 3, when the content of the multi-walled carbon nanotubes is small (such as NP1), almost all of the poly-3-hexylthiophene is degraded after the ultraviolet irradiation for a long period of 24 minutes, the change is obvious, and the degradation speed is high; when the content of the multi-wall carbon nano-tube is slightly increased (such as NP2), as can be seen from FIG. 4, although the poly-3-hexylthiophene is still completely degraded finally, the degradation speed is much slower than that of NP 1; as can be seen from FIG. 5, when the content of the multi-walled carbon nanotubes is increased to a sufficient weight ratio (such as NP3), it is found that poly-3-hexylthiophene is hardly degraded, and excellent stability is exhibited; as can be seen from FIG. 6, when the content of the multi-walled carbon nanotubes is increased beyond the proper mass ratio (such as NP4), the total poly-3-hexylthiophene is slightly degraded, and a slight amount of blue shift is generated. It can be seen that when the modified multi-walled carbon nanotubes are mixed with the poly 3-hexylthiophene powder, the ratio of the mixture to the powder is 1: 27.6 by weight ratio, the photodegradation of poly-3-hexylthiophene can be suppressed well by the treatment method of the present invention.
In conclusion, the multi-walled carbon nanotube bonding poly-3-hexylthiophene material provided by the invention, the poly-3-hexylthiophene and the surface of the multi-walled carbon nanotube array are subjected to graft polymerization reaction through ultraviolet irradiation to complete the modification of the multi-walled carbon nanotube, then the modified multi-walled carbon nano-tube and poly-3-hexylthiophene are mixed and dissolved in a solvent to prepare a multi-walled carbon nano-tube-poly-3-hexylthiophene mixture, the mixture is irradiated by ultraviolet rays, so that the poly-3-hexylthiophene and the multi-walled carbon nano-tube are chemically combined to prepare the multi-walled carbon nano-tube bonded poly-3-hexylthiophene material, the photochemical stability of the poly-3-hexylthiophene is greatly enhanced, thereby solving the problem that the poly-3-hexylthiophene is not stable enough and can not be applied to micro-nano products.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a multi-walled carbon nanotube bonded poly (3-hexylthiophene) material is characterized by comprising the following steps:
after being tiled, poly (3-hexylthiophene) and a multi-walled carbon nanotube array are placed in a protective gas atmosphere for primary ultraviolet irradiation treatment, so that the poly (3-hexylthiophene) and the multi-walled carbon nanotube array are subjected to graft polymerization reaction to obtain a modified multi-walled carbon nanotube;
mixing the modified multi-walled carbon nanotube and powdered poly (3-hexylthiophene), dissolving in a solvent, removing the solvent after ultrasonic treatment, and drying to obtain a multi-walled carbon nanotube-poly (3-hexylthiophene) mixture;
spreading a multi-walled carbon nanotube-poly (3-hexylthiophene) mixture on a substrate, then placing the substrate in a protective gas atmosphere for secondary ultraviolet irradiation treatment, and cooling to obtain a multi-walled carbon nanotube bonded poly (3-hexylthiophene) material;
mixing and dissolving modified multi-walled carbon nanotubes and powdered poly (3-hexylthiophene) in a solvent, wherein the mass ratio of the modified multi-walled carbon nanotubes to the powdered poly (3-hexylthiophene) is 1: 19-1: 49;
the power of the primary ultraviolet irradiation treatment is 20-50 mW, and the time is 2-10 mins; the power of the secondary ultraviolet irradiation treatment is 20-50 mW, and the time is 20-50 mins.
2. The method of claim 1, wherein the solvent is chloroform.
3. The method for preparing multi-walled carbon nanotube-bonded poly (3-hexylthiophene) material according to claim 1, wherein the ultraviolet wavelength of the first ultraviolet irradiation treatment is 218nm and the ultraviolet wavelength of the second ultraviolet irradiation treatment is 196 nm.
4. The method of claim 1, wherein the shielding gas is nitrogen or an inert gas.
5. The method of claim 1, wherein the flow of the shielding gas is controlled during the UV irradiation.
6. The method for preparing the multi-walled carbon nanotube bonded poly (3-hexylthiophene) material according to claim 1, wherein the multi-walled carbon nanotube array has an average length of 700 to 800 μm and a diameter of 10 to 15 nm.
7. The preparation method of the multi-walled carbon nanotube bonded poly (3-hexylthiophene) material according to claim 1, wherein the ultrasonic treatment frequency is 26kHz, and the ultrasonic time is 20-50 mins.
8. A multiwalled carbon nanotube-bonded poly (3-hexylthiophene) material, characterized by being prepared by the method of any one of claims 1 to 7.
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| CN104774432A (en) * | 2015-04-15 | 2015-07-15 | 华中科技大学 | Poly-3-hexylthiophene/carbon nanotube composite material and preparation method thereof |
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| Enhancing the Photostability of Poly(3-hexylthiophene) by Preparing Composites with Multiwalled Carbon Nanotubes;Prasanta J. Goutam, et al.;《The Journal of Physical Chemistry B》;20110111;919-924 * |
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