TWI506652B - A conductive thin film of silver and carbon nanotubes, silver/carbon nanotube composites, and method for distributing cnt - Google Patents

Description

Conductive film containing silver and carbon nanotubes, silver/nanocarbon tube composite, and a kind of dispersed naphthalene Method of carbon tube

The present invention relates to a carbon nanotube dispersed with a polyamine and a metal composite thereof. The composite has good conductivity and can be applied to high value-added products such as antibacterial materials, functional textiles, coatings, medical materials, nano-conductive silver tubes, carbon tubes/silver pastes, and composite materials.

In recent years, nanocarbon tubes and nano-silver particles have been one of the important research and development topics in applications such as conductivity, antibacterial, medical, and coatings. However, both of them are in great need of improvement in terms of reduction reaction and dispersibility.

One of the main methods for enhancing the dispersibility of carbon nanotubes in solution is chemical modification or chemical functionalization. A strong acid is used as an oxidizing agent to form an oxygen-containing functional group at the wall or end of the carbon tube. By cutting the carbon tube into a short carbon tube, the functionalized carbon tube can be effectively dispersed in an aqueous solution and an organic solvent. The atomic transfer radical polymerization (ATRP) and ring-opening polymerization can be used to covalently graft long-chain organic molecules to enhance the dispersibility of the carbon nanotubes. However, the surface modification process will destroy the sp ² structure and length of the carbon nanotubes, and reduce the original characteristics, which is not conducive to the application effect.

Another method is physisorption or a non-covalent modification. The surfactant is used as a dispersing agent, or a polymer having a polar side chain is wound around the carbon tube. A carbon nanotube composite is formed by external force (such as ultrasonic vibration or grinding, etc.) or solvent assist, wherein the polar segment and the solution form a stable dispersion.

The amine group has a special physical adsorption for CNTs. Therefore, an amine-based surfactant is used to enhance the dispersibility of the CNT, and the surfactant molecule chain contains aromatic segments, polar groups or long-chain alkyl chains. The alkyl segments can enhance the adsorption capacity of the surfactant to the CNTs.

In addition, recent studies have found that an Ag/CNT composite can be obtained by adding a carbon tube to silver particles. This novel complex has special properties in terms of catalysis, electrical, optical and biomedical, and these effects are related to the size and stability of the silver particles. Silver particles are prone to aggregation, so how to stably modify the nano silver particles to the surface of the carbon nanotubes, and then synthesize the Ag/CNT composite is very important. Related art and references include: thermal cracking ( J. Mater. Chem. 2001, 11 , 2378), vapor deposition ( Carbon 2005, 43 , 1259); surface chemical reduction ( Carbon 2006, 44 , 381), Silver particles of 17 nm, 3-8 nm, <50 nm and 25 nm were modified by γ-irradiation on carbon nanotubes ( Mater. Lett. 2005, 59 , 1121). In addition, the surface of the chemically modified carbon tube is used to have an acid or amine functional group on the surface thereof, thereby sequestering silver ions, and then reducing ions into particles by dimethylformamide (DMF). ( Car 2008, 46 , 1497 and J. Phys. Chem. C 2007, 111 , 2416).

Due to the chemical treatment, the carbon nanotubes are easily broken and the characteristics are lowered. However, the Ag/CNT synthesized by other methods can stably modify the silver particles on the carbon nanotubes, and the process operation is tedious and complicated, and is not suitable for mass production. Accordingly, the present invention seeks a highly efficient and gentle process for preparing Ag/CNT composites.

The main object of the present invention is to provide a conductive film or metal/nanocarbon tube composite containing silver and carbon nanotubes and a method for producing the same.

Another object of the present invention is to uniformly disperse carbon nanotubes (CNTs) in a simple manner.

A further object of the present invention is to make the metal/carbon nanotube composite in a single or thin film form or to mix it with a polymer material in a simple manner to enhance its conductivity.

The conductive film containing silver and carbon nanotubes of the present invention comprises: a substrate which is rigid or flexible, and is heat resistant to at least 100-600 ° C (at least 330-450 ° C); carbon nanotube (CNT) a diameter of about 20-80 nm, a length of about 0.1-20 μm, and attached to the substrate; and silver particles, with a diameter of about 5-500 nm (preferably 20-30 nm) of nano-silver particles ( A silver nanoparticles, AgNP) type, or a stacked layer having an average thickness of about 0.05 to 5 μm (preferably 0.3 to 5.0 μm), is attached to the surface of the carbon nanotube and/or substrate. The weight ratio of the carbon nanotube to the silver is 1/3 to 1/40, preferably 1/5-1/20, more preferably 1/10 to 1/15. The carbon nanotubes are preferably multi-walled carbon nanotubes having a diameter of preferably about 40-60 nm and a length of preferably about 0.5-10 μm. The substrate is preferably glass or polyimide (PI). The sheet resistance of the electroconductive film is about 1.0 × 10 ^{-3 -} 1.0 × 10 ^-1 Ω / sq.

The silver/nanocarbon tube composite of the present invention comprises: a carbon nanotube (CNT) in a single root dispersion state, and silver particles. The silver particles may be modified on the surface of a single carbon nanotube by a type of silver nanoparticles (AgNP) having a diameter of about 20-30 nm, or stacked on the surface of the carbon nanotube.

The silver/nanocarbon tube composite may include a polyamine having a molecular weight ranging from 2,000 to 200,000 g/mol, which has a benzene ring functional group capable of generating π-π interaction with a carbon nanotube and A lone pair electrons functional group, and a lone pair of electronic functional groups capable of adsorbing and dispersing nano silver particles on the surface of the carbon nanotubes. The polyamine preferably has an imide and a poly(oxyethylene) functional group, and may have a poly(oxypropylene) functional group; the structural formula of the polyamine may be The POE is a poly(oxyethylene) segment.

The method for dispersing a carbon nanotube of the present invention comprises at least the following steps: (a) mixing a polyetheramine with a monoanhydride or a dianhydride compound to synthesize a polyamine having an imide functional group, and the reaction temperature is 50- 320 ° C, the molecular weight of the polyetheramine is about 200-5,500, the molecular weight of the polyamine ranges from 2,000 to 200,000 g / mol; and (b) the polyamine and the carbon nanotubes are mixed in a solvent to form a polymerization Amine/nanocarbon tube dispersion.

In the above step (a), the polyetheramine is preferably hydrophilic, and the type is preferably a polyvinyl ether diamine, for example, having the following structural formula: Where x+z=-6 and y=-39.

If a monoanhydride compound is used, TMA is preferred; and if a dianhydride compound is used, ODPA is preferred. The reaction temperature of the polyetheramine with the monoanhydride or dianhydride compound is preferably from 100 to 270 ° C, more preferably from 120 to 250 ° C. The molar ratio of the polyetheramine to the monoanhydride or dianhydride may be from 1:10 to 10:1, preferably from 1:5 to 5:1, more preferably from 1:2 to 2:1.

In the above step (b), the carbon nanotubes are preferably multi-walled carbon nanotubes, but may also be single-walled carbon nanotubes. The weight ratio of the carbon nanotubes to the polyamine may be from 0.01:1 to 0.25:1, preferably from 0.02:1 to 0.1:1, more preferably about 0.05:1. The solvent may be a solvent having a structure of a lone pair of electrons, for example, N-methyl pyrrolidone (NMP), dimethylformamide (DMF), N, N-dimethyl Dimethylacetamide (DMAc), dimethyl pyrrolidone, tetrahydrofuran (THF), methyl ethyl ketone (MEK) or water, preferably DMF. The carbon nanotubes and the polyamine can be separately dissolved in a solvent and mixed.

The above method may further comprise the steps of: (c) mixing the metal ion with the polyamine/carbon nanotube dispersion, fixing the metal ion on the surface of the carbon nanotube by chelation of the polyamine, and then polymerizing The reduction of the amine reduces the metal ion to nano metal particles and uniformly disperses on the surface of the carbon nanotube to obtain a metal/polyamine/nanocarbon tube composite.

In step (c), the metal may be gold, silver, copper, platinum or iron, preferably silver. The silver ions may be provided by AgNO ₃ and the weight ratio of polyamine to AgNO ₃ may be from 0.1:1 to 10:1, preferably from 0.5:1 to 2:1, more preferably about 1:1.

The above method may further comprise the following steps: (d) adding the above solvent to the polyamine/nano metal/nanocarbon tube composite and then centrifuging to remove polyamine and silver silver particles not on the carbon tube to obtain a surface. A polyamine/nano metal/nanocarbon nanotube composite that combines a single root form of the nano metal particles.

Alternatively, (d) the polyamine/nano metal/nanocarbon tube composite solution is placed on a substrate, and the surface metal is melted by heat treatment to form a conductive film. The heat treatment temperature may be from 100 to 400 ° C, preferably from 170 to 200 ° C, or gradually increased from 100 ° C to 400 ° C.

The materials used in the embodiments and application examples of the present invention include:

1. Multi-wall carbon nanotubes: MWCNTs, available from Seedchem Company Pty., Ltd.

2. Polyetheramines: poly(oxyalkylene)-amines, including monoamines, diamines, triamines, and synthetic multi-segment polyetheramines, available from Huntamine Chemical Co., Jeffamine® Series products (as shown in Annex 1).

3. N-methylpyridinone: N-methyl pyrrolidone (NMP) as a solvent.

4. 4,4'-oxydiphthalic anhydride: 4,4'-Oxydiphthalic dianhydride (ODPA), as a linker compound, other dianhydride series of linkers are shown in Annex 2.

5. 1,2,4-Benzene tricarboxylic anhydride: 1,2,4-benzenetricarboxylic anhydride (or trimellitic anhydride, TMA), a monoanhydride connector.

6. Dimethylformamide: N,N-Dimethylformamide (DMF), as a solvent and a weak reducing agent for silver ions.

7. Polyethylene glycol diglycidyl ether: Poly(ethylene glycol) diglycidyl ether (PEGDE), as a linker compound, other epoxy resin series connecting agent is shown in Annex 3.

8. Silver nitrate: AgNO ₃ (99.8%), available from Aldrich Chemical Co. Other silver salts such as AgI, AgBr, AgCl and silver pentafluoropropionate may also be used.

9. Tetrahydrofuran: Tetrahydrofuran (THF) as a solvent.

General description of the experimental steps:

Example 1 Dispersing a carbon nanotube and reducing silver with a polyamine (POE-imide) Step (a-1): Preparation of polyamine (POE-ED-2003/ODPA) dispersant

POE-ED-2003 (10 g, 0.005 mol) was dissolved in THF (10 ml) in a 100 ml three-necked flask. Then ODPA (1.3 g, 0.0042 mol) was added to make the MOE ratio of POE-ED-2003/DA 6:5. The mixture was mechanically stirred, nitrogen was purged throughout, and the temperature was controlled at 150 ° C for 3 hours. The reaction was monitored by IR spectroscopy and samples were taken at intervals until the anhydride characteristic functional groups disappeared in the FT-IR spectrum and the imide functional groups were formed. The excess THF was then removed by suction filtration to give the product as a pale yellow viscous solid POE-imide (POE-ED-2003/ODPA) having a molecular weight of from 10,000 to 100,000 g/mol . The reaction is shown in Figure 1. Annex 4 shows the solubility of POE-imide obtained in this example with other ratios in different solvents.

Step (a-2): Dispersing the carbon nanotubes with polyamine (POE-imide)

In a round bottom flask, a carbon nanotube (CNT, 0.025 g) was dissolved in DMF (5 g) and uniformly dispersed by stirring with a magnet. POE-ED-2003/ODPA (0.5 g) was dissolved in water (5 g) to make the dispersion uniform. The two solutions were mixed to obtain a polyamine/nanocarbon tube solution having a CNT/POE-imide weight ratio of 0.05/1.

Figure 2 compares the UV absorbance of the CNT solution at 550 nm with time when POE-imide is added. As shown in the figure, the stability and dispersibility of CNTs added to POE-imide in Figure (a) are good, and can continue to stand even for more than 6 months, because the imide functional group of POE-imide can coat CNTs and stably disperse CNTs. In water or organic solvent; Figure (b) did not add POE-imide, but the CNT dispersion after ultrasonic vibration was second, and the stability decreased significantly after 2 days; Figure (c) did not add POE-imide, nor The dispersion of CNTs that have been ultrasonically oscillated is quite poor at first. Figure 3 compares TEM images of CNTs and CNT/POE-imide with ultrasonic oscillations. As shown in the figure, the CNTs added to POE-imide in Figure (a) have good dispersibility; in Figure (b), POE-imide is not added, but the ultrasonically oscillated CNTs have poor dispersibility and particles accumulate on the tube wall.

Step (b): Reducing silver ions with polyamine/carbon nanotubes and DMF

AgNO ₃ (0.5 g) was completely dissolved in the polyamine/nanocarbon tube solution, and the silver ions were reduced into nano silver particles (AgNPs) by DMF and EO segments. As the concentration of AgNPs increased, the solution turned from black to dark brown. Analysis by UV spectrometer showed characteristic absorption of AgNPs at a wavelength of 420 nm, demonstrating that nano-silver particles have been generated, as shown in Figure 4. The weight ratio of the product silver/polyamine/nanocarbon tube composite was 0.05/1/1.

Fig. 5 is a TEM image after completion of the reaction, showing that the dispersibility of the carbon nanotubes and the nano-silver particles is good. Because POE-imide has imide, multiple amines, and imidoamine functional groups, it can chelate with silver to stably distribute silver in water or organic solvents. Figure 6 shows the particle size distribution of nano-silver particles with a range of about 8-30 nm and an average of 15.6 nm.

Example 2-3

The procedure was the same as in Example 1, except that the molar ratio of POE-ED-2003/OPDA in step (a-1) was changed to 3:2 and 2:1, respectively, and the product was a pale yellow viscous solid POE-imide (POE- ED-2003/ODPA), molecular weight 10,000-70,000 g/mol . Annex 4 shows the solubility of the POE-imide obtained in the reaction in different solvents.

Example 4 dispersing carbon nanotubes and reducing silver with polyetheramine-amine-imide (POE-amide-imide) Step (a-1): Preparation of polyetheramine-guanamine-imine (POE-ED-2003/TMA) dispersant

POE-ED-2003 (10 g, 0.005 mol) was dissolved in THF (10 ml) in a 100 ml three-necked flask. Next, TMA (0.8 g, 0.0042 mol) was added to give a POE-ED-2003/TMA molar ratio of 6:5. The mixture was mechanically stirred, and the whole process was filled with nitrogen. The temperature was controlled at 220 ° C and the reaction was continued for 2 hours. The reaction was monitored by IR spectroscopy and samples were taken at intervals until the anhydride characteristic functional groups disappeared in the FT-IR spectrum, and the amide and imide functional groups were formed and no longer increased. The excess THF is then removed by suction filtration to give the product as a pale brown viscous solid (POE-ED-2003/TMA) with a molecular weight of up to 20,000. g/mol. The reaction is shown in Figure 7.

Step (a-2): dispersing the carbon nanotubes with polyetheramine-melamine-niminoimine

The procedure is the same as in Example 1. The CNTs can also be dispersed, but the dispersion effect is still better with POE-imide.

Step (b): Reducing silver ions with polyamine/carbon nanotubes (CNT/POE-amide-imide) and DMF

The procedure is the same as in Example 1. Finally, the product silver/polyamine/imide/CNT can also be dispersed in water or an organic solvent.

Example 5 Dispersing a carbon nanotube and reducing silver with a polyamine (POE-imide) Step (a): Preparation of polyamine (POE-ED-2003/ODPA) dispersant

POE-ED-2003 (10 g, 0.005 mol) was dissolved in THF (15 ml) in a 100 ml three-necked flask. Then, ODPA (1.29 g, 0.0042 mol) dissolved in THF (10 ml) was added dropwise to give a molar ratio of POE-ED-2003/DA of 6:5. Strong stirring is required during the addition, the temperature is controlled at 150 ° C, and the reaction is continued for 3 hours. The reaction was monitored by IR spectroscopy and samples were taken at intervals until the anhydride characteristic functional groups disappeared in the FT-IR spectrum and the imide functional groups were formed. The reacted mixture was rotary evaporated under reduced pressure to give the product as a pale yellow viscous solid POE-imide (POE-ED-2003/ODPA).

Step (b): reducing silver and dispersing carbon nanotubes with polyamine (POE-imide)

A carbon nanotube (CNT, 0.025 g) was ultrasonically dispersed in DMF (5 ml) at room temperature, and as a result, a black CNT/DMF dispersion having a slight precipitate at the bottom was obtained. In another glass vessel, POE-imide (0.5 g) and AgNO ₃ (0.5 g, 0.003 mole) were dissolved in deionized water (5 ml, resistance value 18.2 MΩ/cm ² ) and poured into CNT/ In the DMF dispersion, the weight ratio of CNT/AgNO ₃ /POE-imide was 1/20/20. By the adsorption reduction reaction, a silver/polyamine/nanocarbon tube solution in which CNTs are uniformly dispersed can be obtained, wherein the weight ratio of CNT/Ag/POE-imide is 1/12.7/20. The silver/polyamine/nanocarbon tube solution was continuously stirred for several days, and its color was observed to change from black to dark brown.

Example 6-7

The procedure was the same as in Example 5 except that the ratio of the reactants was changed so that the weight ratio of CNT/AgNO ₃ /POE-imide was 1/10/10 and 1/40/40. By the adsorption reduction reaction, a silver/polyamine/nanocarbon tube solution having a weight ratio of CNT/Ag/POE-imide of 1/6.4/10 and 1/25.4/40 can be obtained.

Comparative Example 1 Dispersing a carbon nanotube with a polyetheramine-nonylamine (POE-amide)

The operation procedure is the same as (a-1) and (a-2) of the first embodiment, but the reaction temperature of the step (a-1) is controlled at 30 ° C, and the reaction is as shown in Fig. 8, and the product is guanamine (POE-amide). ), the solubility is shown in Annex 4. At the end of step (a-2), a large amount of carbon tube precipitate was found at the bottom of the bottle.

Comparative Example 2 Dispersing a carbon nanotube with a polyetheramine (POE)

The procedure was the same as in the example (a-2) except that the unreacted polyvinyl ether amine (ED-2003) was used as a dispersing agent, and finally a large amount of carbon tube precipitate was found at the bottom of the bottle body.

Comparative Example 3 Reduction of Silver Ions by DMF and Carbon Tubes

AgNO ₃ (0.5 g) was completely dissolved in a DMF (5 g) solution containing carbon nanotubes (0.025 g), and silver ions were reduced by DMF to finally obtain precipitated carbon tube aggregates and silver mirror phenomenon.

Application Example 1 Preparation of Single Root Type Silver/Polyamine/Nano Carbon Tube Composite

The silver/polyamine/nanocarbon nanotube composite of a single root type can be obtained by centrifugation and solvent cleaning of the silver/polyamine/nanocarbon tube composite solution of Example 1. As shown in the TEM image of Fig. 9, nano silver particles having a diameter of about 20-30 nm are modified on the surface of a single carbon nanotube. The silver/polyamine/nanocarbon tube composite can be redispersed back into the solvent and cosolvent.

Application Example 2 Preparation of Film Type Silver/Polyamine/Nano Carbon Tube Composite

The silver/polyamine/nanocarbon tube composite solution of Example 1 was dropped on a glass substrate and dried at 170 °C. From the TM-AFM chart of Fig. 10, silver in the molten state of the film surface was observed. The conductivity of the film was measured by a four-point probe to be 10 ³ S/cm. The film can be re-dispersed into a stable dispersion via a variety of solvents. The substrate may also be PE, PET, PI, epoxy resin, nylon (Nylon), polypropylene (PP), acrylonitrile butadiene styrene (ABS), polystyrene. A film-forming polymer such as polystyrene (PS) or polyaniline (PANI), or an inorganic substrate such as mica, glass, germanium wafer or aluminum disk.

Application Example 3 Preparation of Polyamine/Nano Carbon Tube/PEGDE Composite

T-403 (0.53 g, 0.0012 mol) and PEGDE (1.92 g, 0.0037 mol) were uniformly mixed and mixed with the polyamine/nanocarbon tube solution of Example 1. A polyamine/nanocarbon tube/PEGDE film or block can be obtained at room temperature to 120 °C. It can be seen from the appearance that the polyamine/carbon nanotube composite is uniformly dispersed in the epoxy resin. This composite material has mechanical and electrical properties, an environmentally friendly product that improves energy efficiency and carbon dioxide balance, and can be applied to blades for wind turbines.

Application Example 4 Preparation of Silver/Polyamine/Nano Carbon Tube/PEGDE Composite

T403 (0.53 g, 0.0012 mol) and PEGDE (1.92 g, 0.0037 mol) were uniformly mixed and mixed with the silver/polyamine/nanocarbon tube composite solution of Example 1. A silver/polyamine/nanocarbon tube/PEGDE film or block can be obtained at room temperature to 120 °C. It is known from the appearance that the silver/polyamine/nanocarbon tube composite is uniformly dispersed in the epoxy resin. This composite has conductive properties and can be used in the energy industry.

Application Example 5 Preparation of Film Type Silver/Nano Carbon Tube Composite

The silver/polyamine/nanocarbon tube composite solution (0.5 g) of Example 5-7 was dropped on a separate polyimide (PI) substrate (2 cm × 2 cm), and the substrate was not particularly limited and may be rigid or Elastic material, preferably heat resistant at least 100-600 ° C. The substrate and solution were at 110 ° C (20 points) Clock), 160 ° C (20 minutes), 170 ° C (20 minutes), 300 ° C (20 minutes) and 350 ° C (20 minutes) programmed to dry, the color changes from dark brown to gold, and finally milky white elastic conductive film. Taking the film of Example 5 as an example, Figure 11 is a heating to 350 ° C. The surface of the film is observed by TM-AFM image. The silver concentration in the molten state of the CNT surface is more obvious, and many voids appear because of the combustion of organic components. Relationship. That is, when heated to 350 ° C, a film type silver/nanocarbon tube composite can be obtained. The silver particles were attached to the surface of the carbon nanotubes and/or the substrate in a stacked layer having an average thickness of about 0.5 μm as observed by FE-SEM and TM-AFM.

The sheet resistance of the different solutions on the PI substrate was measured by a four-point probe. The results are shown in Annex 5, where:

(1) POE-imide has a function of stably dispersing CNT/Ag, and the effect of film formation is not good without adding POE-imide.

(2) Temperature has a great influence on conductivity, especially at 160 °C to 170 °C. Taking the weight ratio of CNT/AgNO ₃ /POE-imide to 1/20/20 as an example, when the temperature is increased from 160 ° C, 170 ° C, 300 ° C to 350 ° C, the sheet resistance can be 2.1 × 10 ⁵ Ω / sq, 2.0 × 10 ^-1 Ω/sq, 1.1×10 ^-1 Ω/sq is reduced to 1.0×10 ^-2 Ω/sq.

(3) The content of CNT also has an effect on the resistance. When the weight ratio of CNT/AgNO ₃ /POE-imide is 1/20/20, the sheet resistance is about 2 times lower than 1/10/10 and 1/40/40. An order of magnitude, but conductivity is still better than other films.

From the above examples and comparative examples, the following conclusions can be drawn:

1. The present invention can effectively disperse CNTs by an oily polyether amine compound.

2. By controlling the ratio of the dispersant to the carbon nanotubes, the carbon nanotubes can be uniformly dispersed in water or an organic solvent and can be kept stable for several months.

3. The polyamine (POE-imide or POE-amide-imide) used in the present invention has the functions of dispersing a carbon nanotube and stabilizing silver particles, and can control silver particles at a nanometer scale.

4. The silver/polyamine/nanocarbon tube composite dispersion can form a single nano-nano-carbon tube composite in addition to high concentration and high uniformity.

5. The silver/polyamine/nanocarbon tube composite can be made into a gel by concentration, heating or volatilization under reduced pressure. Body or powder.

6. The silver/polyamine/nanocarbon tube composite dispersion can be heated on any substrate to make the silver in a molten state and form a film to obtain a highly conductive film-forming material having a silver surface.

7. Polyamine/nanocarbon tube or silver/polyamine/nanocarbon tube composite can be blended with organic polymer to achieve nanometer scale dispersion to form a nanocomposite with better conductivity or antibacterial property; organic The polymer may be polyethylene (PE), polyethylene terephthalate (PET), polyimide (PI), epoxy resin, nylon (Nylon), polypropylene ( Polypropylene, PP), acrylonitrile-butadiene-styrene (ABS), polystyrene (PS), and polyaniline (PANI).

8. The silver/polyamine/nanocarbon tube composite can be redispersed back into water or organic solvent after processing or storage.

The products of the present invention can be used for tests such as antibacterial, antimicrobial, and composite properties, and other more tests are not limited to the description in the present invention.

Figure 1 is a reaction diagram for the preparation of a POE-imide (POE-ED-2003/ODPA) dispersant.

Figure 2 shows the UV absorbance of the carbon nanotube (CNT) solution at a wavelength of 550 nm over time with or without POE-imide.

Figure 3 shows the TEM image of the carbon nanotubes (CNT) and CNT/POE-imide that have been ultrasonically oscillated.

Figure 4 shows the characteristic absorption of nano silver particles (AgNPs) analyzed by Example 1 in a UV spectrometer.

Fig. 5 is a TEM image of nano silver particles (AgNPs) after completion of the reaction of Example 1.

Fig. 6 shows the particle size distribution of the nano silver particles (AgNPs) in Example 1.

Figure 7 is a reaction diagram for the preparation of a POE-amide-imide (POE-ED-2003/ODPA) dispersant.

Figure 8 is a reaction diagram for the preparation of a POE-amide (POE-ED-2003/ODPA) dispersant.

Figure 9 shows a TEM image of a single root type silver/polyamine/nanocarbon tube composite.

Figure 10 shows a TM-AFM image of a silver/polyamine/nanocarbon nanotube composite filmed at 170 °C.

Figure 11 shows a TM-AFM image of a silver/polyamine/nanocarbon nanotube composite filmed at 350 °C.

【annex】

Annex 1 is the structural formula and molecular weight of polyetheramine

Annex 2 is a dianhydride series connector

Attachment 3 is epoxy resin series connector

Annex 4 is the solubility of POE-ED-2003/ODPA.

Annex 5 is the resistance of different solutions to form a film on a PI substrate at a high temperature.

Claims (27)

A conductive film comprising silver and carbon nanotubes, comprising: a substrate, rigid or flexible, heat resistant to at least 100-600 ° C; carbon nanotube (CNT), diameter 20-80 nm, length 0.1-20 μm and attached to the substrate; and silver particles attached to the silver nanoparticle (AgNP) type having a diameter of 5 to 500 nm or a stacked layer having an average thickness of 0.05 to 5 μm The carbon nanotube and/or substrate surface has a weight ratio of the carbon nanotube to the silver of 1/1-1/40. The conductive film of claim 1, wherein the weight ratio of the carbon nanotube to the silver is 1/5-1/20. The electroconductive film of claim 1 has a sheet resistance of 1.0 × 10 ^{-3 to} 1.0 × 10 ^-1 Ω/sq. The conductive film of claim 1, wherein the carbon nanotube is a multi-walled carbon nanotube. The conductive film of claim 1, wherein the carbon nanotube has a diameter of 40 to 60 nm and a length of 0.5 to 10 μm. The conductive film of claim 1, wherein the silver particles are modified on the surface of the carbon nanotube and/or substrate by a silver nano (AgNP) type having a diameter of 20-30 nm. The electroconductive film of claim 1, wherein the silver particles are attached to the surface of the carbon nanotube and/or the substrate in a stacked layer having an average thickness of 0.3 to 5.0 μm. The conductive film of claim 1, wherein the substrate is heat resistant to 330-450 °C. The conductive film of claim 1, wherein the substrate is glass or polyimide (PI). A silver/nanocarbon tube composite comprising: a carbon nanotube (CNT) having a single root dispersion state; and a silver particle having a diameter of 20-30 nm of silver nanoparticles (AgNP) type Modification on the surface of a single carbon nanotube or attached to the surface of the carbon nanotube in a stacked layer And a polyamine having a molecular weight ranging from 2,000 to 200,000 g/mol, having a benzene ring functional group and a lone pair electrons functional group; wherein the benzene ring functional group can generate π-π adsorption with a carbon nanotube (π-π interaction), the lone pair electrons functional group can adsorb and disperse the nano silver particles on the surface of the carbon nanotubes. The silver/nanocarbon nanotube composite of claim 10, wherein the polyamine has an imide and a poly(oxyethylene) functional group. The silver/nanocarbon tube composite of claim 10, wherein the polyamine further has a poly(oxypropylene) functional group. The silver/nanocarbon tube composite of claim 11, wherein the structural formula of the polyamine is The POE is a poly(oxyethylene) segment. A method for dispersing a carbon nanotube comprises at least the following steps: (a) reacting a polyetheramine with an anhydride compound to synthesize a polyamine having an imide functional group at a reaction temperature of 50 to 320 ° C. The polyetheramine has a molecular weight of from 200 to 5,500, the polyamine has a molecular weight in the range of from 2,000 to 200,000 g/mol, the polyetheramine to anhydride compound has a molar ratio of from 1:10 to 10:1; and (b) the polyamine Mixing with a carbon nanotube in a solvent having a lone pair of electronic structures to form a CNT/polyamine dispersion having a weight ratio of the carbon nanotube to the polyamine of 0.01:1 to 0.25:1, and the solvent is N- N-methyl pyrrolidone (NMP), dimethylformamide (DMF), dimethyl pyrrolidone, tetrahydrofuran, THF), methyl ethyl ketone (MEK) or water. The method of claim 14, wherein the polyetheramine of step (a) is a polyvinyl ether diamine. The method of claim 14, wherein the anhydride compound of step (a) is TMA or ODPA. The method of claim 14, wherein the carbon nanotube of step (b) is a multi-walled carbon nanotube. The method of claim 14, wherein the carbon nanotubes of step (b) are present in the solvent in an amount of from 0.1 to 10% by weight. The method of claim 14, further comprising the steps of: (c) mixing metal ions with the CNT/polyamine dispersion, immobilizing the metal ions on the surface of the CNT by chelation of polyamine, and then using a polyamine. The reduction reduces the metal ions to nano metal particles and uniformly disperses them on the surface of the CNTs to obtain a metal/polyamine/nanocarbon tube composite. The method of claim 19, wherein the metal of step (c) is gold, silver, copper, platinum or iron. The method of claim 19, wherein the metal ion is a silver ion, provided by AgNO ₃ , and the weight ratio of polyamine to AgNO ₃ is from 0.1:1 to 10:1. The method of claim 19, wherein the metal ion is a silver ion, provided by AgNO ₃ , and the weight ratio of CNT to AgNO _{3 is 1/3} to 1/40. The method of claim 19, further comprising the steps of: (d) washing the metal/polyamine/carbon nanotube composite with a solvent, and removing the polyamine and the nano metal particles not on the carbon tube by centrifugation; The surface is bonded to a single root metal/polyamine/nanocarbon nanotube composite of the nano metal particles. The method of claim 23, wherein the solvent is a solvent having a lone pair of electronic structures. The method of claim 19, further comprising the steps of: (d) placing the metal/polyamine/carbon nanotube composite solution on a rigid or flexible, heat-resistant substrate of 100-600 ° C via heat treatment; The surface metal is melted to form a conductive film at a heat treatment temperature of 100 to 400 °C. The method of claim 25, wherein the heat treatment temperature of step (d) is from 170 to 200 °C. The method of claim 25, wherein the heat treatment temperature of the step (d) is gradually increased from 100 ° C Add to 400 ° C.