CN108545717B - Method for modifying surface of carbon nano tube and modified carbon nano tube - Google Patents

Method for modifying surface of carbon nano tube and modified carbon nano tube Download PDF

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CN108545717B
CN108545717B CN201810490900.7A CN201810490900A CN108545717B CN 108545717 B CN108545717 B CN 108545717B CN 201810490900 A CN201810490900 A CN 201810490900A CN 108545717 B CN108545717 B CN 108545717B
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张笑晴
程相天
何焯健
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Guangdong University of Technology
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
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    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025—Polyphosphazenes
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    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data

Abstract

The application belongs to the technical field of composite materials, and particularly relates to a method for modifying the surface of a carbon nano tube and a modified carbon nano tube. The method provided by the invention comprises the following steps: ultrasonically dispersing a carbon nano tube in a reaction solvent to obtain a first solution; dissolving hexachlorocyclotriphosphazene and a first compound in a reaction solvent to obtain a second solution; adding an acid-binding agent into the first solution, slowly adding the second solution into the first solution, and reacting to obtain a modified carbon nanotube; wherein the first compound is: hexa- (4-aminophenoxy) cyclotriphosphazene, or is: a composition comprising hexa- (4-aminophenoxy) cyclotriphosphazene. The invention adopts an in-situ precipitation polycondensation method to uniformly coat a polymer layer rich in a large number of high-activity reaction groups on the surface of the original carbon nanotube, and the modification method is a one-pot method, so that the operation is convenient, the reaction condition is mild, and the implementation is easy.

Description

Method for modifying surface of carbon nano tube and modified carbon nano tube
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a method for modifying the surface of a carbon nano tube and a modified carbon nano tube.
Background
Since s.iijima discovered Carbon Nanotubes (CNTs) in 1991, CNTs have attracted much attention due to their unique structural features, excellent physicochemical properties, and potential application values in future high-tech fields, and are rapidly becoming the leading and hot point of research in the fields of physics, chemistry, biology, materials, medicine, etc. CNTs not only have the quantum effect of common nanoparticles, but also have the characteristics of large specific surface area, high mechanical strength, high conductivity, good heat resistance and the like, so that the CNTs have special physical and chemical properties and have wide application prospects in the fields of electronics, communication, chemical industry, aviation, aerospace and the like. At present, a great deal of research results are obtained in the aspects of preparation, purification, functionalization, performance application and the like of the CNTs at home and abroad. With the increasing maturity of the preparation technology of CNTs in large quantities and the further research on the technology, people now pay more attention to the practical application of CNTs, especially to the polymer composite material using CNTs as reinforcement.
However, CNTs tend to aggregate into bundles or entanglements, and their surfaces are relatively "inert" compared to other nanoparticles, and the dispersibility in common organic solvents is low, which greatly limits the research of their application properties. Furthermore, the compatibility and wettability of CNTS and the matrix are poor, and the interfacial bonding and the performance of the carbon nanotube composite material are seriously influenced. At present, people find that the dispersion performance of the carbon nano tube can be improved by effectively modifying the surface of the carbon nano tube, and the compatibility and the wettability of the carbon nano tube and a matrix material are improved, so that a good bonding interface can be generated between the carbon nano tube and the matrix material, and the performance of the carbon nano tube composite material is improved. In addition, the surface modification can also endow the carbon nano tube with new performance, realize the molecular assembly of the carbon nano tube, obtain nano materials with various excellent performances and have wide application prospect in the aspects of molecular electronics, nano biomolecular science and the like. Therefore, the surface modification of the carbon nanotubes has become a hot spot in the research of the carbon nanotubes, and the modification of the CNTs is a premise and a basis for realizing the application value of the CNTs.
The surface modification of the carbon nano tube is to change the state and the structure of the surface of the CNTs by physical and chemical methods, improve the surface activity of the CNTs, improve the dispersibility of the CNTs and increase the compatibility of the CNTs and other substances. The chemical method generally adopts strong acid and strong oxidant to pretreat, so that the surface of the carbon nano tube is provided with functional groups such as carboxyl and the like, and then the polymer is grafted on the surface of the carbon nano tube through reactions such as amidation, esterification and the like, so that the dispersity of the carbon nano tube is improved. However, the chemical method destroys the sp2 hybrid structure of the carbon nanotube through covalent bond, and has a certain influence on the mechanical and electrical properties of the carbon nanotube.
Chinese patent CN103803523A reports that after a carbon nanotube is treated with a mixed solution of strong base and hydrogen peroxide, the carbon nanotube reacts with tannic acid, and the carbon nanotube after surface modification treatment is uniformly dispersed in water and organic solvent and has high stability. However, the carbon nanotube pretreated by strong alkali and hydrogen peroxide can damage the original chemical structure of the carbon nanotube, and the surface functional group of the carbon nanotube modified by the method is few and single, so that the further modification and the multiple functions of the carbon nanotube are limited.
Chinese patent CN102442660A reports that the surface of a carbon nanotube is grafted with a terminated hyperbranched polysiloxane in the form of a chemical bond. According to the method, a large amount of carboxyl is introduced by treating the carbon nano tube with nitric acid, so that the carbon nano tube reacts with hyperbranched polysiloxane containing a phosphaphenanthrene structure and epoxy groups, and a large amount of active reaction groups such as epoxy groups and hydroxyl groups are grafted on the modified carbon nano tube, so that very favorable conditions are provided for the carbon nano tube to obtain good dispersibility and compatibility in a resin matrix. Meanwhile, the modified CNT surface simultaneously contains a phosphaphenanthrene structure and a polysiloxane structure, so that a flame-retardant synergistic effect can be generated. However, strong acid treatment also damages the structure of the carbon nanotubes, and hyperbranched polymers all have structural defects of different degrees, which limits the application range of the hyperbranched polymers.
The physical method mainly comprises a non-covalent bond coating method, does not need to acidify the surface of the carbon nano tube, does not damage the internal structure of the carbon nano tube, and belongs to the physical modification process. Journal of American chemistry society reported in 2006, volume 128, 1692 and 1699: the non-covalent bond coating method is characterized in that active amino groups are introduced to the surface of the carbon nano tube by means of weak pi-pi accumulation between small molecules or polymers with aromatic rings and the graphite structure of the carbon nano tube. However, the weak pi-pi bond formed between the polymer and the carbon nanotube by this method is easily detached, has poor interfacial bonding properties, and cannot be stably dispersed uniformly in a solution or a matrix resin. In view of the shortcomings of the prior art methods for modifying the surface of carbon nanotubes, it is necessary to further develop a novel method for modifying the surface of carbon nanotubes.
Disclosure of Invention
In view of the above, the present invention provides a method for modifying a surface of a carbon nanotube and a modified carbon nanotube, and the specific technical solution thereof is as follows:
a method of carbon nanotube surface modification comprising:
ultrasonically dispersing a carbon nano tube in a reaction solvent to obtain a first solution;
dissolving hexachlorocyclotriphosphazene and a first compound in a reaction solvent to obtain a second solution;
adding an acid-binding agent into the first solution, slowly adding the second solution into the first solution, and reacting to obtain a modified carbon nanotube;
wherein the first compound is: one or more of hexa- (4-aminophenoxy) cyclotriphosphazene, a difunctional compound and a trifunctional compound.
Preferably, the molar ratio of the hexachlorocyclotriphosphazene to the first compound is 1.0 (1.05-1.5) by functionality;
the mass ratio of the sum of the hexachlorocyclotriphosphazene and the first compound to the carbon nanotube is (1-3): 1.
Preferably, the reaction temperature is 40-60 ℃ and the reaction time is 5-48 h;
the molar ratio of the acid-binding agent to the hexachlorocyclotriphosphazene is (1-2): 1.
Preferably, the mass percentage concentration of the carbon nanotubes in the first solution is 0.1-3%.
Preferably, the difunctional compound is selected from NH2-R-OH、NH2-R-NH2One or more of HOOC-R-OH and HO-R-OH;
wherein R is- (C)6H4) -or- (CH)2)n-，n＝1～10。
Preferably, the trifunctional compound is selected from melamine and/or cyanuric acid.
Preferably, the reaction solvent is selected from dimethyl sulfoxide, dimethylformamide or dimethylacetamide;
the acid-binding agent is triethylamine, potassium carbonate, sodium acetate or sodium hydroxide.
Preferably, the preparation method of the hexa- (4-aminophenoxy) cyclotriphosphazene comprises the following steps:
reacting hexachlorocyclotriphosphazene with p-acetaminophenol under the conditions of a third solvent and a catalyst to obtain hexa- (4-acetaminophenoxy) cyclotriphosphazene; dissolving the hexa- (4-acetaminophenoxy) cyclotriphosphazene in a fourth solvent, and adding concentrated sulfuric acid or sodium hydroxide for deprotection to obtain the hexa- (4-acetaminophenoxy) cyclotriphosphazene;
the molar ratio of the hexa- (4-acetamidophenoxy) cyclotriphosphazene to the concentrated sulfuric acid or the sodium hydroxide is 1 (100-200).
More preferably, the molar ratio of the hexachlorocyclotriphosphazene to the acetaminophen to the catalyst is 1 (6.6-7.2) to (9.9-10.8);
the catalyst is anhydrous potassium carbonate;
the third solvent is acetone;
the fourth solvent is methanol.
The invention also provides a modified carbon nano tube obtained by the method.
The invention has the beneficial effects that:
1) according to the invention, hexachlorocyclotriphosphazene and a polyfunctional compound are adopted as reaction monomers, and a polymer layer rich in a large number of high-activity reaction groups is uniformly coated on the surface of a carbon nano tube by using an in-situ precipitation polycondensation method; the modification method is a one-pot method, is convenient to operate, has mild reaction conditions and is easy to implement;
2) compared with the existing compound or polymer which is non-covalently adsorbed on the surface of the carbon nano tube, the polymer layer coated on the surface of the carbon nano tube is a highly ring cross-linked structure, is similar to a three-dimensional network structure like a yarn winding ball, and can be uniformly, stably and tightly coated on the surface of the carbon nano tube; under the condition of not damaging the original structure and performance of the carbon nano tube, the modified carbon nano tube is beneficial to uniformly and stably dispersing in solution or matrix resin;
3) the thickness of the polyphosphazene polymer layer coated on the surface of the modified carbon nano tube can be controlled by the dosage ratio between the carbon nano tube and the reaction monomer so as to adapt to the regulation and control of different properties of materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an infrared spectrum of a carbon nanotube and a polymer-coated carbon nanotube;
fig. 2 is a projection electron microscope (TEM) image of the carbon nanotubes coated with the polymer.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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.
Example 1
The method for synthesizing hexa- (4-aminophenoxy) cyclotriphosphazene (HACP) provided in this example includes:
1. 10.8g of anhydrous potassium carbonate (K)2CO3) Grinding into powder, adding into 80mL acetone together with 7.8g paracetamol; after magnetic stirring at room temperature for 30min, high-purity nitrogen gas is introduced, 2.5g Hexachlorocyclotriphosphazene (HCCP) is added, and then the reaction is carried out for 24h under magnetic stirring at 70 ℃.
After the reaction is finished, cooling the solution to room temperature, carrying out vacuum filtration, and taking filtrate; and (3) carrying out rotary evaporation on the filtrate to form a sticky state, adding excessive deionized water, and carrying out freeze drying to obtain white powder, namely the hexa- (4-acetaminophenoxy) cyclotriphosphazene.
2. 9g of hexa- (4-acetamidophenoxy) cyclotriphosphazene are dissolved in 180mL of methanol, then 108mL of concentrated sulfuric acid are slowly poured in, and the reaction is stirred under reflux at 80 ℃ for 4 h.
After the reaction is finished, cooling the solution to room temperature, dropwise adding dilute ammonia water into the solution in an ice salt bath environment until the pH value of the solution is 8, then carrying out vacuum filtration on the solution, pouring the filtrate into a waste liquid barrel, washing the solid on the filter paper with a large amount of deionized water, and then carrying out vacuum drying at 50 ℃ for 48h to obtain an off-white solid, namely the hexa- (4-aminophenoxy) cyclotriphosphazene (HACP).
1H NMR(DMSO-d6,ppm,600Hz):6.42–6.53(4H,dd,Ar-H),4.91(2H,Ar-NH2)。
FTIR: at 3438 and 3338cm-1In the presence of-NH2Is suckedCollecting peaks; at 1507 and 1621cm-1An aromatic ring C-C stretching vibration peak exists; at 1256, 1178 and 952cm-1And the peaks respectively correspond to characteristic peaks of P-O-Ph, P-N-P and P-O-C.
The chemical structure of hexa- (4-aminophenoxy) cyclotriphosphazene is as follows:
Figure BDA0001667703490000051
example 2
The embodiment provides a method for modifying the surface of a carbon nano tube, which comprises the following steps:
1. dissolving 100mg of carbon nano tube in 50mLDMSO, and performing ultrasonic treatment for 1h in a cell crusher to obtain a first solution for later use;
2. dissolving 0.035g HCCP and 0.083g HACP in 50mLDMSO, mixing uniformly to obtain a second solution for standby;
3. adding 2mL of acid-binding agent triethylamine into the first solution, and then slowly dripping the second solution into the first solution through a constant-pressure funnel for about 1 h; then magnetically stirring and reacting for 10 hours at the temperature of 60 ℃, then carrying out vacuum filtration, and collecting filter residues; and respectively ultrasonically washing the carbon nano tube for 2-3 times by using ethanol and deionized water at normal temperature, and drying the carbon nano tube in a vacuum box to obtain the modified carbon nano tube with the coating layer being about 10nm in thickness.
In the invention, the carbon nano tube, the two reaction monomers and the acid-binding agent can be directly and uniformly mixed in the reaction solvent theoretically and then reacted. However, in the actual development process, such operation may cause the problem of too fast reaction rate to form the cluster, which is not favorable for the coating modification for forming the single carbon nanotube. In order to overcome the problem, the inventor finds that the reaction rate can be slowed down and coating modification of a single carbon nanotube can be favorably formed by the method through multiple times of optimized screening.
In the present invention, the acid-binding agent may also replace other substances such as: potassium carbonate, sodium acetate or sodium hydroxide. In the reaction process of the triethylamine adopted in the embodiment, no water is generated, so that the triethylamine is adopted as the optimal choice.
Example 3
The present embodiment provides a method, which is different from embodiment 2 in that: HCCP 0.087 g; HACP0.021g; the thickness of the obtained coating layer was 60 nm.
The rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Example 4
The present embodiment provides a method, which is different from embodiment 2 in that: 1g of carbon nano tube; HCCP0.70g; 1.7g of HACP; the thickness of the resulting coating was 130 nm.
The rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Example 5
The present embodiment provides a method, which is different from embodiment 2 in that: HCCP 0.052 g; 0.083g HACP to 0.050g hydroquinone; the thickness of the obtained coating layer was 30 nm.
The rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Example 6
The present embodiment provides a method, which is different from embodiment 2 in that: HCCP 0.070 g; 0.083g HACP was replaced with 0.065g p-phenylenediamine; the thickness of the obtained coating layer was 50 nm.
The rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Example 7
The present embodiment provides a method, which is different from embodiment 2 in that: HCCP 0.10 g; 0.083g hacp is replaced by 0.075g melamine; the thickness of the obtained coating layer was 68 nm.
The rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Example 8
The present embodiment provides a method, which is different from embodiment 2 in that: HCCP 0.10 g; 0.083g HACP is replaced by 0.21g HACP and 0.010g p-phenylenediamine; the thickness of the resulting coating was 66 nm.
The rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Example 9
The present embodiment provides a method, which is different from embodiment 2 in that: HCCP 0.10 g; 0.083g HACP is replaced by HACP 0.21g and melamine 0.011 g; the thickness of the resulting coating was 61 nm.
The rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Example 10
The present embodiment provides a method, which is different from embodiment 2 in that: HCCP 0.10 g; 0.083g HACP is replaced by HACP 0.21g, p-phenylenediamine 0.005g and melamine 0.005 g; the thickness of the obtained coating layer was 65 nm.
The rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Example 11
1. Taking a proper amount of carbon nano tubes and the carbon nano tubes coated by the polymer, and carrying out infrared spectrum detection. The infrared spectrum is shown in figure 1.
As shown, 1500cm-1And 1160cm-1And obvious absorption peaks appear at the positions, which respectively correspond to the characteristic peak of a benzene ring and the characteristic peak of a P ═ N bond, and prove that the surface of the carbon nano tube is successfully coated with the phosphazene polymer layer.
2. A proper amount of the carbon nanotubes coated by the polymer are taken and scanned by a Transmission Electron Microscope (TEM), and the TEM image is shown in FIG. 2.
As can be seen from the electron microscope image in fig. 2, a darker thin layer appears on the surface of the carbon nanotube, and it can be seen from fig. 1 that the thin layer is the phosphazene polymer layer coated on the surface of the carbon nanotube.

Claims (7)

1. A method for modifying the surface of a carbon nanotube, comprising:
ultrasonically dispersing a carbon nano tube in a reaction solvent to obtain a first solution;
dissolving hexachlorocyclotriphosphazene and a first compound in a reaction solvent to obtain a second solution;
adding an acid-binding agent into the first solution, slowly adding the second solution into the first solution, and reacting to obtain a modified carbon nanotube;
wherein the first compound is: hexa- (4-aminophenoxy) cyclotriphosphazene;
the molar ratio of the hexachlorocyclotriphosphazene to the first compound is 1.0 (1.05-1.5);
the mass ratio of the sum of the hexachlorocyclotriphosphazene and the first compound to the carbon nanotube is (1-3): 1.
2. The method of claim 1, wherein the reaction temperature is 40 ℃ to 60 ℃ and the reaction time is 5h to 48 h;
the molar ratio of the acid-binding agent to the hexachlorocyclotriphosphazene is (1-2): 1.
3. The method of claim 1, wherein the mass percent concentration of the carbon nanotubes in the first solution is between 0.1% and 3%.
4. The process according to claim 1, wherein the reaction solvent is selected from dimethyl sulfoxide, dimethylformamide or dimethylacetamide;
the acid-binding agent is triethylamine, potassium carbonate, sodium acetate or sodium hydroxide.
5. The method of claim 1, wherein the method of preparing the hexa- (4-aminophenoxy) cyclotriphosphazene comprises:
reacting hexachlorocyclotriphosphazene with p-acetaminophenol under the conditions of a third solvent and a catalyst to obtain hexa- (4-acetaminophenoxy) cyclotriphosphazene; dissolving the hexa- (4-acetaminophenoxy) cyclotriphosphazene in a fourth solvent, and adding concentrated sulfuric acid or sodium hydroxide to obtain the hexa- (4-acetaminophenoxy) cyclotriphosphazene;
the molar ratio of the hexa- (4-acetamidophenoxy) cyclotriphosphazene to the concentrated sulfuric acid or the sodium hydroxide is 1 (100-200).
6. The method of claim 5, wherein the molar ratio of hexachlorocyclotriphosphazene, acetaminophen and catalyst is 1 (6.6-7.2) to (9.9-10.8);
the catalyst is anhydrous potassium carbonate;
the third solvent is acetone;
the fourth solvent is methanol.
7. Modified carbon nanotubes obtainable by the process of any one of claims 1 to 6.
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CN109775689A (en) * 2018-12-12 2019-05-21 深圳烯湾科技有限公司 Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application
CN109971125B (en) * 2019-03-01 2021-11-19 广东工业大学 Self-repairing carbon fiber/epoxy resin composite material and preparation method and application thereof
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CN110591157B (en) * 2019-08-30 2021-03-30 厦门大学 Preparation method and application of polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses
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