TWI341825B - Method of making carbon nanotube/polymer composite material - Google Patents

Description

1341825 _100 February 14th, nuclear replacement π VI, invention description: [Technical field of invention] [0001] The present invention relates to a preparation technology of a carbon nanotube composite material, in particular to a carbon nanotube / polymerization Method for preparing a composite material. [Prior Art] [0002] Since the discovery of carbon nanotubes (CNTs - Nanotubes, CNTs) by Ii Jima of NEC Corporation in 1991 (I i 1 i ma S., Nature, 1 991, 354, 56-58 ) 'Immediate attention to the scientific and industrial circles D carbon nanotubes have excellent mechanical and optical properties, ideal for composite materials. Nanocarbon tubes/polymer composites have become the hotspot of scientific research in the world since their first report (Ajjayan P.M., Stephan 0.,

Colliex C., Tranth D. Science. 1994, 265, 1212-1215: Calvert P., Nature, 1999, 399, 210-2Π). As a composite material formed by reinforcing Zhao and electrical conductors, the carbon nanotubes have antistatic properties, microwave absorption and electromagnetic shielding, and have wide application prospects. [0003] Nano carbon nanotube/polymer composite materials are usually prepared. In-situ polymerization, solution blending, and melt blending. In-situ polymerization involves the use of functional groups on the surface of carbon nanotubes to participate in polymerization or the use of initiators to open the 7-bonds of carbon nanotubes to participate in the polymerization. Achieve good compatibility with the organic phase. The solution blending method generally disperses a carbon nanotube into a good solvent of a polymer, dissolves the polymer therein, and then forms and removes the solvent, thereby preparing a composite material. The melt blending method melts and uniformly mixes the carbon nanotubes and the polymer matrix material in a temperature environment above the melting point of the matrix material to obtain a carbon nanotube/polymer composite material. 095129627 Form No. A0101 Page 3 of 28 1003046193-0 T341825 February 14, 2014 Nuclear Replacement Page [0004] The carbon nanotube/polymer composites obtained by these preparation methods generally have large electrical resistance. A good conductive network is not formed between the carbon nanotubes, and the spacing between the adjacent carbon nanotubes is large, and the mutual contact is poor. Therefore, the excellent electrical and thermal conductivity of the carbon nanotubes cannot be fully utilized. In view of the above, it is necessary to provide a method for preparing a carbon nanotube/polymer composite having good mutual contact between carbon nanotubes. SUMMARY OF THE INVENTION [0006] A method of preparing a carbon nanotube/polymer composite will be described below by way of examples.

[0007] - a carbon nanotube / polymer composite j step: providing a carbon nanotube base carbon nanotube base film placed in a volume of solution into the container containing the carbon nanotube base film; The prepolymerized polymer solution is polymerized and combined with the carbon nanotube-based impurities to form a carbon nanotube/polymer complex gi. The preparation method of the carbon nanotube base film includes the following luxury %, carbon tube and The dimercaptoamine solution is mixed and shaken by ultrasonic waves and waves f to further disperse the carbon nanotubes in the dimethylformamide solution to form a mixed solution; volatilization removes the second of the mixed liquids Mercaptoamine, thereby obtaining a carbon nanotube base film. [0008] A method for preparing a carbon nanotube/polymer composite, comprising the steps of: providing a carbon nanotube base film and a prepolymerized polymer solution; and second step, the nanometer The carbon tube base film is placed at the bottom of a container, and the prepolymerized polymer solution is poured into the container containing the carbon nanotube base film; the third step is to cause the prepolymerized polymer solution to be polymerized and form with 095129627 No. A0101 Page 4 of 28 1003046193-0 1341825 On February 14, 100, the nuclear replacement of the π-nano carbon nanotube base film was performed to form the first layer of carbon nanotube/polymer composite; Depositing another layer of carbon nanotube base film on the surface of the polymer layer of the first layer of carbon nanotube/polymer composite formed above, and then pouring a certain amount of prepolymerized polymer solution to make the prepolymerized polymer The solution is polymerized and combined with the surface of the polymer layer of the other layer of carbon nanotube film and the first layer of carbon nanotube/polymer composite to form a second layer of carbon nanotube/polymer composite The fifth step, the basis of the fourth step Repeat step 4 to obtain a plurality of layers of carbon nanotube/polymer composite. [0009] Compared with the prior art, the connection between the carbon nanotubes in the carbon nanotube base film of the technical solution is sufficient, so that the conductive properties and thermal conductivity of the prepared carbon nanotube/polymer composite conductive layer are good. The electrical conductivity reaches 120 Siemens/m, which is about two orders of magnitude higher than that of ordinary carbon nanotube/polymer composites. In addition, the carbon nanotube base film is tightly packed with high molecular polymer material, which makes Nye The connection between the carbon nanotubes is stable, and the carbon nanotube base film is firmly connected to the polymer material layer, which is superior to the products prepared by the prior art. The technical solution can also repeat the steps of preparing the carbon nanotube/polymer composite to prepare a plurality of layers of carbon nanotubes/polymer composite. [Embodiment] The present technical solution will be further described in detail below with reference to the accompanying drawings and specific embodiments. [0011] Please refer to FIG. 1, the embodiment provides a method for preparing a carbon nanotube/polymer composite material, which comprises the following steps: Step 1, providing a carbon nanotube base film and a prepolymerized polymer solution; Step 2, the carbon nanotube base 095129627 No. Α 0101 Page 5 / 28 pages 1003046193-0 1341825 On February 14, 100, the shuttle is replacing the π film at the bottom of a container, and the above prepolymerized polymer solution Pour into the container containing the carbon nanotube base film; in step 3, the prepolymerized polymer solution is polymerized and combined with the carbon nanotube base film to form a carbon nanotube/polymer composite material. The preparation method of the carbon nanotube/polymer composite will be explained step by step. [0012] Step 1. Providing a carbon nanotube base film and a prepolymerized polymer solution. [0015] [0015]

The carbon nanotube base film can be prepared by mixing a carbon nanotube with a dimercaptoamine solution and then volatilizing to remove the dimethyl decylamine, or by chemical vapor deposition (Chemical Vapor Deposition ' CVD) method. The carbon nanotubes and the dimercapto hydrazine are removed. The decyl decylamine forms a carbon nanotube production method & IP:. Next step: First, the carbon nanotubes and the dimethyl group a solution of the guanamine solution and further dispersing the carbon nanotubes in the bis-guanamine solution by ultrasonic vibration to form a mixed solution; secondly, the dodecyl guanamine in the doping solution Thus, a /'if* is obtained - the prepolymerized polymer solution used in the embodiment is a prepolymerized poly(mercapto acrylate) (PMMA) solution. The prepolymerized polymethyl methacrylate (PMMA) solution preparation step comprises: [0016] First, the polymer main body methyl methacrylate (MMA), the initiator azobisisobutyronitrile (AIBN) and the auxiliary agent a mixture of dibutyl phthalate (DBP) to form a mixed liquid, the weight percentage of methyl methacrylate in the mixture is 93 to 99. 98%, and the weight percentage of azobisisobutyronitrile 0.02~2%, the weight percentage of dibutyl phthalate is 095129627 Form No. A0101 Page 6 / Total 28 Page 1003046193-0 1341825 100 February 2004 Nuclear replacement page 0~50/〇 . [0017] In this embodiment, the main body is not limited to methyl methacrylate, and may be at least one of ethyl acrylate, butyl acrylate, styrene, butadiene, and acrylonitrile, and the initiator may be benzoquinone or At least one of azobisisobutyronitrile, the auxiliary agent may be dibutyl phthalate, cetyltridecyl bromide, polyvinyl acetate, polymethacrylate, C12-C18 higher fatty acid, At least one of a decane coupling agent, a titanate coupling agent, and an aluminate coupling agent. [0018] Next, the mixed liquid is placed in a temperature environment of about 80 to 95 ° C and stirred to carry out a prepolymerization reaction, and when the solution is prepolymerized to have a certain drilling property, the heating is stopped. [0019] In the present embodiment, the water is heated in a water bath of 80 to 95 degrees Celsius, and the stirring time is about 5 to 30 minutes, and the heating is stopped when the solution is prepolymerized to a glycerin state. [0020] Again, the above prepolymerized solution is cooled until the prepolymerization reaction is stopped. [0021] In the present embodiment, the glycerin-like prepolymerized solution is placed in the air to be naturally cooled. [0022] Step 2. The carbon nanotube base film is placed on the bottom of a container, and the prepolymerized solution is poured into the container containing the carbon nanotube base film. [0023] Preferably, after pouring the prepolymerization solution into the above-mentioned container filled with the carbon nanotube base film, the container is further placed for a certain period of time, so that the prepolymerization solution sufficiently fills the gap between the base film of the carbon nanotubes, Thereby, a mixed layer of a carbon nanotube base film and a prepolymerization solution is formed at the bottom of the container. Preferably, the upper 095129627 form number A0101 page 7 / 28 pages 1003046193-0 1341825 [0024] [0025] [0028] [0028] 095129627 100 February 2014 revised replacement page container 0. 5 to 2 hours. In step 3, the prepolymerized solution is polymerized and combined with a carbon nanotube base film to form a carbon nanotube/polymer composite. In the present embodiment, a carbon nanotube/polymer single-sided conductive composite film can be formed. In the present embodiment, the composite is carried out between the interface between the carbon nanotube base film at the bottom of the container and the prepolymerized solution. The polymer formed after the polymerization of the prepolymerized solution is sufficiently tightly bonded to the carbon nanotubes in the base film of the carbon nanotube, from the two-shaped Winel. Carbon tube/East composite. , '. The process of compounding the carbon nanotube base film of the above glycerin-like prepolymerization solution is as follows: the container of the carbon tube base ΜνΗΒΒΜΒΒΜΠΚί film and the prepolymerized polymer solution is placed at a temperature of 5 ° C • V*, in the environment, so that the above capacity is - electro-prepolymerization solution polymerization and compounding with the carbon nanotube base film, hourly; continue to heat the upper bucket container to a temperature of 90 ~ 100 degrees Celsius 'card, · ',; the polymerization solution continues. r': 〇per "V is polymerized and compounded with Naiqi Carbon Camper for about 2 hours to obtain a carbon nanotube/polymer single-sided conductive film carbon nanotube/polymer single side In practical applications, conductive films have different thicknesses depending on the application. In this embodiment, by adjusting the amount of the prepolymerization solution, different thicknesses of the carbon nanotube/polymer single-sided conductive film can be obtained, for example, various carbon nanotubes having a thickness range of 0.02 to 2 mm can be obtained/ Polymer single-sided conductive film. In addition, another layer of carbon nanotube base film is placed on the surface of the polymer layer of the carbon nanotube/polymer composite formed above, and then poured into a certain amount of prepolymerized form No. A0101, page 8 / 28 pages 1003046193 0 [0029] 1341825 On February 14, 100, according to the positive replacement page solution and placed for a certain period of time, the prepolymerized solution was polymerized and combined with the surface of the other layer of carbon nanotube base film and polymer layer to form a second layer of Nai a carbon nanotube/polymer composite; a step of repeatedly forming a second layer of carbon nanotube/polymer composite on the surface of the polymer layer of the formed second carbon nanotube/polymer composite to obtain a plurality of layers of naphthalene Carbon tube/polymer composite. [0030] Embodiment 1 [0031] Embodiment 1 provides a method for preparing a carbon nanotube/PMMA single-sided conductive composite film, which specifically includes the following steps: [0032] (1) providing a carbon nanotube base film and A prepolymerized PMMA. solution. [0033] The carbon nanotube base film is a carbon nanotube base film formed by volatilizing dimethylformamide from a mixture of a carbon nanotube and a dimethylformamide. The preparation process of the carbon nanotube base film in this embodiment is specifically: [0034] First, a 4 mg carbon nanotube is mixed with a 20 m.l dimethyl decylamine solution, preferably by ultrasonic vibration. The carbon nanotubes are further uniformly dispersed in the dimethyl decylamine solution. In the present embodiment, an ultrasonic wave having a frequency of 20 to 100 Hz is used, and the oscillating time is about 0.5 to 4 hours, preferably 2 hours, and the mixture of the carbon nanotubes is uniformly dispersed. [0035] wherein, the above carbon nanotubes may be single-walled carbon nanotubes or multi-walled carbon nanotubes. The dimercaptocarbamide is a solvent which can uniformly disperse the carbon nanotubes, and the saturated solubility of the carbon nanotubes therein is about 0.25 mg/ml. [0036] Next, the mixture is filled into a container. And the container with the mixed liquid is placed 095129627 Form No. A0101 Page 9 / Total 28 Page 1003046193-0 1341825 100 February, 2014 Press the replacement page [0037] [0038]

[0040] [0044] [0044] [0044] [0044] and wait in a dry box, ventilated and dried at a temperature of 100 degrees Celsius, drying time is about 2 hours, to be dimethyl After substantially completely volatilizing the carbamide, a carbon nanotube base film is obtained, and the carbon nanotube base film is located at the bottom of the container. The prepolymerized polymethyl methacrylate (PMMA) solution preparation step includes first, the polymer body Ethyl methacrylate (MMA), initiator azobisisobutyronitrile (AIBN) and auxiliaries dibutyl phthalate (DBP) are mixed to form a mixed solution in which methyl methacrylate is used. Weight 1 ... . . . The percentage of the content is 97%, the weight of the azo 〒龠 1 1. The 詈 contains 0.1%, the weight of the dibutyl phthalate | Next, the solution is heated To 92 degrees Celsius! , reopening 1 from; to make the solution pre-polymerization, when the solution is reacted until it has a certain iNt, the heating is stopped in this embodiment, and the water bath method is used to win the rroperty of the agricultural plus ^^9, and the reaction is to have a certain viscosity, Lang - 丨遂: When the glycerin is used, the heating is stopped wff'ce. Again, the glycerol-like prepolymerized solution is cooled until the prepolymerization is stopped. In this embodiment, the glycerin-like prepolymerized solution was placed in the air to be naturally cooled. (2) Placing a carbon nanotube base film on the bottom of a container, and pouring a glycerin-like prepolymerized solution into the container containing the carbon nanotube base film. In this embodiment, after pouring the glycerin-like prepolymerization solution into the container containing the carbon nanotube base film, the prepolymerization solution is filled for a certain period of time to fully fill the 095129627. Form No. A0101 Page 10 / Total 28 Page 1003046193-0 1341825 On February 14, 100, j was filled with the gap between the base film and the bottom layer of the container to form a mixed layer of nano-carbon base film and county solution. Preferably, the container is placed for 0.5 to 2 hours. [0045] (2) The prepolymerized solution is polymerized and combined with a carbon nanotube base film to form a carbon nanotube/polymer composite. In this embodiment, a nano-destructive/polymer single-sided conductive composite film can be formed. [0046] In the present embodiment, the polymerization process of the glycerin-like prepolymerization solution and the compounding with the nano carbon base film is as follows: First, the above container containing the nano carbon base film and the prepolymerization solution is used. Placed in a temperature environment of 6 ° C, the polymerization reaction of the prepolymerized solution in the above container is carried out and compounded with the carbon nanotube base film for 4 to 10 hours; the container is further heated to 90 to 1 ° C. In the temperature environment, the prepolymerized polymer solution is further subjected to polymerization reaction and compounded with the carbon nanotube base film for about 2 hours to obtain a carbon nanotube/pMMA single-sided conductive film. [0047] Referring to FIG. 2 and FIG. 3 in June, FIG. 2 is a front SEM photograph of a carbon nanotube/PMMA single-sided conductive film formed according to the present embodiment, and it can be seen that a plurality of carbon nanotubes are exposed; FIG. 3 is According to the side SEM photograph of the carbon nanotube/PMMA single-sided conductive film formed in this example, it can be seen that the layer thickness of the carbon nanotube is about 10 μm. [0048] Please refer to FIG. 4, FIG. 5 and FIG. 6, which are currents of a carbon nanotube/PMMA single-sided conductive composite film formed according to the present embodiment in a low temperature environment of 77K, a room temperature environment of 297K, and a high temperature environment of 420K. The voltage curve, whose abscissa represents voltage, is in the form of V, in volts (V); the ordinate represents current, the sign is I, and the unit is ampere (A). It can be seen that in various temperature environments 095129627 Form No. A0101 Page/Total 28 pages 1003046193-0 1341825 The correction page of February 14, 2014 has a small resistance and stable performance. Embodiment 2 [0050] Embodiment 2 provides another method for preparing a carbon nanotube array/PMMA single-sided conductive film, which specifically includes the following steps: [0051] (1) providing a carbon nanotube array and A prepolymerized PMMA solution. [0052] The carbon nanotube array uses an array of carbon nanotubes prepared by chemical vapor deposition. The preparation process of the carbon nanotube array in this embodiment is specifically: [0055] [0056] First, a substrate is provided, and an alloy of iron is selected.

Next, a (Fe), cobalt (Co), and nickel are deposited on the substrate (N again, the substrate on which the catalyst-agent layer is deposited is placed in a scale_gas, and heat treated at 3Q0 ° C to 500 ° C (3⁄4. 2~ After lg hours, the catalyst layer is annealed, ^ wiellectua 丨 • to form oxidized particles; 〜 , :.3 ΘΓΤΥ again, the substrate is placed in the reaction device to pass the shielding gas, and heated to a predetermined temperature under the protection of the shielding gas, generally 400 to 750 degrees Celsius, in addition, the shielding gas used for preheating is an inert gas or nitrogen gas, preferably, the shielding gas is argon gas; and [0057] again, a mixed gas of carbon source gas and shielding gas is introduced, and heated to 400 to 750 degrees Celsius reaction 0. 1~2 hours to grow a carbon nanotube array, the carbon source gas in the mixed gas of the carbon source gas and the shielding gas is a hydrocarbon, which may be acetylene, ethylene, etc., preferably, a carbon source The gas is acetylene; the shielding gas is an inert gas or nitrogen gas, preferably, the shielding gas is argon. 095129627 Form No. A0101 Page 12 of 28 1003046193-0 1341825 100 February 2011 [0058] The prepolymerized polymethyl methacrylate (PMM A ) solution, the preparation steps include: [0059] First, the polymer body methacrylate methacrylate (MMA), the initiator azobisisobutyronitrile ( AIBN) and the auxiliary dibutyl phthalate (DBP) are mixed to form a mixed liquid in which the weight percentage of methyl methacrylate is 95%, and the weight of azobisisobutyronitrile is 100%. The content of the component is 1%, and the weight percentage of dibutyl phthalate is 4%; [0060] Next, the solution is heated to 95 degrees Celsius, stirred for 10 minutes, the solution is prepolymerized, and the solution is reacted until Heating is stopped when certain viscosity is applied [0061] In this embodiment, the solution is heated to 95 degrees Celsius by a water bath method, and heating is stopped when it reacts until it has a certain viscosity and glycerin shape. [0062] Again, the prepolymerized solution is cooled until the pre-polymerization The polymerization reaction is stopped. [0063] In the present embodiment, the glycerin-like prepolymerized solution is placed in the air to be naturally cooled. [0064] (2) The carbon nanotube array is placed at the bottom of a container and glycerin is formed. The prepolymerized solution is poured into the bottom Preferably, after the glycerin-like prepolymerized solution is poured into the bottom of the container in which the carbon nanotube array is placed, the container is further placed for a certain period of time to allow the prepolymerization to be carried out. 5〜2小时。 [0066] The present invention is filled with a mixture of a carbon nanotube base film and a prepolymerized solution. In the embodiment, the standing time is 1 hour. 095129627 Form No. A0101 Page 13 of 28 1003046193-0 1341825 Correction replacement page [0267] on February 14, 100 (3) Polymerization of glycerol prepolymerization solution And combined with the carbon nanotube base film to form a carbon nanotube. [0068] In the present embodiment, the polymerization process of the glycerin-like prepolymerization solution and the compounding with the carbon nanotube base film is as follows: First, the above-mentioned container containing the carbon nanotube base film and the prepolymerization solution is placed. The temperature of the temperature is between 50 and 60 degrees Celsius, the prepolymerized solution in the above container is polymerized and combined with the carbon nanotube base film for 2.5 hours; the above container is further heated to a temperature of 90 to 100 degrees Celsius Next, the prepolymerized polymer solution is continuously subjected to polymerization reaction and compounded with the carbon nanotube base film for about 2 hours, thereby allowing the #nano carbon camp to be aligned with the single-sided conductive film.

〇[0069] Please refer to FIG. 7 , which is based on the side SEM photograph of the single-sided conductive composite film, and the carbon nanotube array height is about 100 μm, and the 7MMA layer is layered. [0070] Example 3 inteilectual [ 0071] Embodiment 3 provides a method for preparing a plurality of layers of nano tube composite film, which comprises the following steps: [0072] In the first step, the sample obtained in Example 1 or Example 2 is obtained. The carbon nanotube base film is placed on the bottom of a container; [0073] In the second step, the prepolymerized polymer solution prepared in Example 1 or Example 2 is poured into the above-mentioned container filled with the carbon nanotube base film, and placed. For a certain period of time, the prepolymerized polymer solution is sufficiently filled into the gap between the base film of the carbon nanotubes to form a mixed layer of the carbon nanotube base film and the prepolymerized polymer solution at the bottom of the container; 095129627 Form No. A0101 Page 14 5〜2小时。 The above container is placed for 0.5 to 2 hours. In this embodiment, the placement time is 1 hour. [0075] In the third step, the prepolymerized polymer solution is polymerized and combined with the carbon nanotube base film to form a first layer of carbon nanotube/polymer composite; [0076] In this embodiment, The process of polymerizing the prepolymerized polymer solution and recombining with the carbon nanotube base film is as follows: first, the container containing the carbon nanotube base film and the prepolymerized polymer solution is placed at 50 to 60 degrees Celsius. In the temperature environment, the prepolymerized polymer solution in the above container is subjected to polymerization reaction and compounded with the carbon nanotube base film for about 2 hours; the container is further heated to a temperature of 90 to 100 degrees Celsius to make the above pretreatment The polymerized polymer solution is subjected to polymerization reaction and compounded with a carbon nanotube base film for about 2 hours, whereby a first layer of carbon nanotube/polymer composite film can be obtained. [0077] In the fourth step, another layer of the carbon nanotube base film is placed on the surface of the polymer layer of the formed carbon nanotube/polymer composite, and a certain amount of the prepolymerized polymer solution is poured into the surface for a certain period of time. Polymerizing the prepolymerized polymer solution and compounding with the surface of the polymer layer of the other layer of the carbon nanotube base film and the first layer composite film to form a second layer of carbon nanotube/polymer composite film; [0078 In the fifth step, the fourth step is repeated on the basis of the fourth step to obtain a plurality of layers of carbon nanotube/polymer composite film. [0079] Please refer to FIG. 8 , which is a multi-layer carbon nanotube array/polymer composite thin film 095129627 prepared by using the carbon nanotube array prepared in Example 2 and a prepolymerized polymer solution. Form No. A0101 Page 15 / Total 28 pages 1003046193-0 1341825 On February 14, 100, the page film 10 was replaced. The first layer of carbon nanotube array/polymer composite film 11 comprises a carbon nanotube/polymer composite layer 110 and a polymer layer 120, and the carbon nanotube array/polymer composite layer 110 is prepolymerized in the second step. The polymer solution is formed by infiltrating into the gap between the packed carbon nanotube arrays. The carbon nanotube base film of the second embodiment adopts a carbon nanotube array prepared by a vapor deposition method, and the carbon nanotubes 100 are arranged in an orderly manner, so that the carbon nanotube array/polymer composite layer 110 is prepared. The medium carbon nanotubes 100 are arranged in an orderly manner. The second layer of carbon nanotube array/polymer composite film 12 is also the same as the first layer of carbon nanotube array/polymer composite film 11, including carbon nanotube array/polymer composite layer 130 and polymer layer 140. Re-copying the second nano-carbon to abandon the JI/polymer composite film, || I I I - |1|||||'|__ _illillill I Ί II I π

Liiuouj, please refer to Fig. 9; the tantalum base film prepared in Example 1 and the prepolymerized high molecular electrolyte solution prepared by the molecular solution. The first layer of carbon nanotubes / polymer I complex greet membrane 21 package 1 carbon nanotube / polymer composite layer 210 and polymer / polymer composite layer rroDorlv 21 0 series due to the pre-polymerization of the second step The solution is formed by infiltrating the interstitial space between the packed carbon nanotubes Γ/Γ} I Λ Ρ. The carbon nanotube base film used in Example 1 is formed by volatilization of dimethyl decylamine by a mixture of a carbon nanotube and a dimethyl decylamine, and the carbon nanotubes 200 are disorderly distributed, so the carbon nanotubes are arranged. The carbon nanotubes 200 are randomly arranged in the polymer composite layer 210. The second layer of carbon nanotube/polymer composite film 22 also includes a carbon nanotube/polymer composite layer 230 and a polymer layer 240. The steps of preparing the second layer of carbon nanotube/polymer composite film are repeated to form a plurality of layers of carbon nanotube/polymer composite film 20. [0081] The carbon nanotube/polymer composite material prepared in this embodiment has a good guide 095129627 Form No. Α0101 Page 16/28 page 1003046193-0 1341825 After the 14th of February, the page is replaced with electricity and thermal conductivity, conductance The rate reaches 120 Siemens/m, which is about two orders of magnitude higher than that of ordinary carbon nanotube/polymer composites. In addition, the carbon nanotube base film is tightly packed with polymer material to make the carbon nanotubes The stable connection between the carbon nanotube base film and the polymer material layer is stronger, and the mechanical properties of the product obtained by the prior art are more excellent. [0082] In the carbon nanotube/PMMA single-sided conductive composite film prepared in Example 1 and Example 2, the conductivity and thermal conductivity of the carbon nanotube layer are good, and the connection between the carbon nanotube layer and the PMMA layer is stable. Nano carbon tube / PMMA single-sided conductive composite film can be applied as antistatic material, thermal interface material. [0083] The plurality of layers of carbon nanotubes/polymer composite film produced in Example 3 is insulated between layers, and a plurality of layers can be formed on a thinner thickness, the process is simple, and the performance is superior to that of the composite material and the direct A product prepared by a thermoplastic lamination method. The plurality of layers of carbon nanotube/polymer composite film can be used as a capacitor, an electromagnetic mask material, or the like. [0084] In summary, the present invention complies with the requirements of the invention patent, and submits a patent application according to law. However, the above description is only the preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described embodiments, and those skilled in the art will be able to make equivalent modifications or changes in accordance with the spirit of the present invention. It should be covered by the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS [0085] FIG. 1 is a schematic flow chart of a method for preparing a carbon nanotube/polymer composite material of the present technical solution. 2 is a front side scanning electron microscope of a carbon nanotube/PMMA single-sided conductive composite film prepared according to a first embodiment of the present technology (Scanning 095129627 Form No. A0101, page 17 / 28 pages 1003046193-0 TT41825) Correction of the replacement page Electron Microscope, SEM) on February 14, 100. 3 is a side scanning electron microscope (SEM) photograph of a carbon nanotube/Ρ Μ A single-sided conductive composite film prepared according to the first embodiment of the present technical solution. 4 is a current-voltage curve of a carbon nanotube/Ρ Μ A single-sided conductive composite film prepared according to the first embodiment of the present technology in a low-temperature environment of 77K. 5 is a current-voltage curve of a carbon nanotube/Ρ Μ A single-sided conductive composite film prepared according to the first embodiment of the present technical solution at room temperature of 297 K. [0089] FIG.

6 is a carbon nanotube/PMMA single-sided conductive composite film prepared according to the first embodiment of the present technical solution at 42: 鹌 鹌 辕 辕 T T T T T T 电压 电压 电压 009 009 009 009 009 009 009 009 009 009 009 009 According to the technical solution, the second PMMA single-sided conductive composite film sheet 0 tube array / (SEM) photo [0092] FIG. 8 is a third embodiment of the present technical solution to produce a plurality of layers of carbon nanotubes -» ► Array /铨 ^ ^ 聚合物 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 009 Schematic diagram of the cross-sectional structure of the composite film. [Main component symbol description] [0094] Multiple layer carbon nanotube array/polymer composite film: 10 [0095] First layer of carbon nanotube array/polymer composite film: 11 [ 0096] Second layer of carbon nanotube array/polymer composite film: 12 [0097] carbon nanotube: 1 00, 200 [0098] carbon nanotube array / polymer composite layer: 110, 130 095129627 Form No. A0101 Page 18 of 28 Page 303046193-0 1341825 February 14th, 100th Nuclear Replacement Page [0099] Polymer Layer: 1 20, 1 40, 220, 240 [〇1〇 Multiple layers of carbon nanotubes/polymer composite film: 20 [0101] First layer of carbon nanotube/polymer composite film: 21 [0102] Second layer of carbon nanotube/polymer composite film: 22 [0103 ] Carbon nanotube / polymer composite layer: 210, 230 095129627 Form No. A0101 Page 19 / Total 28 Page 1003046193-0

Claims (1)

-1341825 February 14, 100 nuclear replacement page VII, the scope of application for patents: 1. A method for preparing a carbon nanotube/polymer composite material, comprising the following steps: providing a carbon nanotube base film and a pre- Polymerizing the polymer solution; placing the carbon nanotube base film on the bottom of a container, and pouring the prepolymerized polymer solution into the container; causing polymerization of the prepolymerized polymer solution and performing with the carbon nanotube base film Compounding to form a carbon nanotube/polymer composite, wherein the method for preparing the carbon nanotube base film comprises the following steps: The carbon nanotubes and the bismuth-based medicinal materials are melt-forged and mixed, and the nano-carbon tubes are further separated into liquids by ultrasonic oscillating method to form a mixed liquid; The dimethylformamidine was also approved, and a film of the carbon tube was obtained. _... The method for preparing a carbon tube/party composite according to the invention described in claim 1, wherein the carbon nanotube or multi-walled nRr^^r:r ?-, ,. VS * '*' m carbon tube. I;·· ' I *v<u,V } ^ tv·^ % .. The method for preparing a carbon nanotube/polymer composite according to claim 1, wherein the nanocarbon The solubility of the tube in the dimethyl guanamine solution is less than or equal to the saturated solubility of the carbon nanotubes in the dimethyl guanamine solution. 5〜4小时。 The ultrasonic wave oscillating time is 0. 5~4 hours. 5. The method for preparing a carbon nanotube/polymer composite according to claim 1, wherein the method for preparing the prepolymerized polymer solution comprises 095129627 Form No. A0101 Page 20/28 Page 1003046193 -0 1341825 On February 14, 100, the replacement page is as follows: The polymer body, the initiator and the auxiliary agent are mixed to form a mixed solution, wherein the weight percentage of the polymer body is 93~ 99. 98%, the weight percentage of the initiator is 0. 02~2%, the weight percentage of the auxiliary agent is 0 - 5 %; the above mixed solution is placed in a temperature environment of 80~95 degrees Celsius and stirred 5~ After 30 minutes, the solution was prepolymerized until the solution was in the form of glycerol, and the stirring was stopped; the solution was cooled until the prepolymerization was stopped. 6. The method for producing a carbon nanotube/polymer composite according to claim 5, wherein the glycerin-like prepolymerized high molecular solution is naturally cooled by being placed in air. 7. The method for preparing a carbon nanotube/polymer composite according to claim 5, wherein the polymer main system is butyl methacrylate, ethyl acrylate, butyl acrylate, styrene, At least one of butadiene and acrylonitrile, the initiator is at least one of albino or azobisisobutyronitrile, and the auxiliary is dibutyl phthalate or cetyl trifeptyl bromide. At least one of an amine, a polyvinyl acid salt, a polymethacrylate, a C12-C18 higher fatty acid, a decane coupling agent, a titanate coupling agent, and an aluminate coupling agent. The method for producing a carbon nanotube/polymer composite according to any one of the preceding claims, wherein after the prepolymerized polymer solution is poured into the bottom of the container containing the carbon nanotube base film, the container is further placed at 0.5. ~2 hours, the prepolymerized polymer solution is filled into the gap between the base film of the carbon nanotubes to form a mixed layer of the carbon nanotube base film and the prepolymerized polymer solution at the bottom of the container. 095129627 Form No. A0101 Page 21 of 28 1003046193-0 1341825 February 14, 2014 Shuttle replacement page 9. The preparation method of the carbon nanotube/polymer composite according to claim 1 of the patent application, Wherein the process of polymerizing the prepolymerized polymer solution and recombining with the carbon nanotube base film comprises the steps of: placing the above-mentioned container containing the carbon nanotube base film and the prepolymerized polymer solution in the container In a temperature of 50 to 60 degrees Celsius for 4 hours, the prepolymerized polymer solution in the above container is subjected to polymerization reaction and compounded with a carbon nanotube base film to heat the container to 90 to 100 degrees Celsius for 2 hours. The prepolymerized polymer solution is continuously subjected to polymerization and complexed with a carbon nanotube base film. Ίο. The preparation method of the composite material according to claim 1, wherein the composite solution and the carbon nanotube base film contact each other interface • · / 11 . A carbon nanotube / polymer The preparation of the composite material comprises the following steps: First, providing a carbon nanotube-based i-film preparation molecular solution; the second step, the carbon nanotube base film; the Syrian portion, and the pre-polymerization is high The molecular solution is poured into the third step of the container, so that the prepolymerized polymer solution is polymerized and combined with the carbon nanotube base film to form a first layer of carbon nanotube/polymer composite, the fourth step, Depositing another layer of carbon nanotube base film on the surface of the polymer layer of the first layer of carbon nanotube/polymer composite formed above, and then pouring the prepolymerized polymer solution to polymerize the prepolymerized polymer solution Reacting and compounding with the surface of the polymer layer of the other layer of the carbon nanotube base film and the first layer of composite material to form a second layer of carbon nanotube/polymer composite; 095129627 Form No. A0101 Page 22 of 28 pages 1003046193-0 1341 825, the second step of the correction replacement page on February 14, 1985, the fourth step is repeated on the basis of the fourth step to obtain a plurality of layers of carbon nanotubes/polymer composites, wherein the carbon nanotube base film The preparation method comprises the following steps: mixing a carbon nanotube with a dimethylformamide solution, and further dispersing the carbon nanotube in the dimercaptoamine solution by ultrasonic vibration to form a mixed solution; The dimethylformamide in the above mixture was removed to obtain a carbon nanotube base film. 095129627 Form No. A0101 Page 23 of 28 1003046193-0