CN107108954B - High strength polymers containing carbon nanotubes - Google Patents
High strength polymers containing carbon nanotubes Download PDFInfo
- Publication number
- CN107108954B CN107108954B CN201680004245.9A CN201680004245A CN107108954B CN 107108954 B CN107108954 B CN 107108954B CN 201680004245 A CN201680004245 A CN 201680004245A CN 107108954 B CN107108954 B CN 107108954B
- Authority
- CN
- China
- Prior art keywords
- polymer composite
- carbon nanotubes
- carbon
- high strength
- strength polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Abstract
The present invention provides a high strength polymer composite comprising: thermoplastic polymers and carbon nanotubes; wherein the BET specific surface area is 40m2/g～120m2(iv) g, bulk density of 10 to 60kg/m3The content of the carbon nano tube relative to the total weight of the polymer composite material is 5-15 wt%. By adjusting and optimizing the specific surface area and the volume density at the same time, the content of the carbon nanotubes contained in the polymer composite material can be increased without reducing the dispersibility of the carbon nanotubes, and a high-strength polymer composite material with improved mechanical strength can be provided.
Description
Technical Field
The present application claims priority based on korean patent application No. 10-2015-0135974, filed on 25/09/2015, the entire contents of which are incorporated by reference.
The present invention provides a polymer composite material having improved mechanical strength by improving dispersibility in the composite material, by providing a polymer composite material containing carbon nanotubes having a high specific surface area and a high bulk density.
Background
Generally, a carbon nanotube (hereinafter referred to as "CNT") is a cylindrical carbon tube having a diameter of about 3 to 150 , specifically about 3 to 100 , and a length of several times, for example, 100 times or more, the diameter. Such CNTs consist of layers of aligned carbon atoms, having cores of different morphologies. Such CNTs are also referred to as carbon fibers or hollow carbon fibers, for example.
Such CNTs are used as additives for various composite materials because of their high electrical conductivity, thermal stability, tensile strength, and recovery. The uniformity of dispersion of the CNT bundles is a particularly important factor when CNTs are used as additives to composite materials. In the case of polycarbonate/carbon nanotube composites, the physical properties of the composite are also changed depending on the degree of uniformity of the dispersion of the carbon nanotubes in the polymer matrix (matrix). However, since the length of the CNT is relatively longer than the diameter thereof and the attraction force of the carbon nanotubes to each other is strong, the dispersion degree of the CNT is very low compared to the polymer.
In order to solve these problems, one of the prior art techniques used in the industry is a technique of immersing CNTs in a solution of nitric acid, sulfuric acid, or a mixture thereof to oxidize the surface thereof, thereby increasing the degree of dispersion of the carbon nanotubes. However, in such a technique, since an acid solution is used in the production process, various problems such as safety problems and environmental problems occur, and it is difficult to secure process stability in mass production.
On the other hand, polycarbonate (polycarbonate) is an engineering plastic, has excellent transparency, mechanical strength and impact strength, and high heat resistance, and is widely used in many fields, and particularly, has attracted attention as a housing material for electronic products. Electromagnetic wave shielding performance is sometimes required for a case material of an electronic product, and particularly when the case material is used as a case material of an electronic device such as a mobile phone case, which generates a large amount of electromagnetic waves, the electromagnetic wave shielding performance and mechanical strength are essential physical properties. A technique for increasing electromagnetic wave shielding performance in a polymer material is a technique of adding an inorganic substance or a carbon-based substance capable of exhibiting an electromagnetic wave shielding function to a polymer resin, but in this case, there is a problem that moldability of the material is lowered. Therefore, studies have been recently conducted to add a small amount of carbon nanotubes to a polymer resin while satisfying excellent electromagnetic wave shielding performance and moldability.
Patent document 1 discloses a method for producing a polymer/carbon nanotube composite by dissolving polycarbonate and carbon nanotubes in a solvent to form a preliminary composite, and then mixing the preliminary composite with a polycarbonate resin in an extruder.
Patent document 2 relates to a method for producing a CNT powder composition with improved dispersibility in a polymer matrix. The CNT powder composition is obtained by a method of spraying an excess amount of acrylic acid over the CNT in a solution state, mixing the solution with the CNT, heating the mixture, dropping acrylic acid together with an initiator into the CNT, heating the mixture to form polyacrylic acid, or adsorbing acrylic acid vapor and then performing heat treatment, and the like, and is mixed with various polymers to prepare a polymer composite with improved conductivity.
Patent document 3 relates to a method for producing polymer-carbon nanotube composite particles. Dispersing CNT and polymer in a solvent by using an ultrasonic oscillator to obtain a suspension, forming the suspension into a liquid crystal state by using a spraying device, and drying to prepare the composite particle, wherein the weight ratio of the CNT to the polymer is 0.01: 1-0.1: 1.
Patent document 4 discloses a method for producing a polymer composite. A polymer composite is prepared by dissolving a thermoplastic resin in a water-insoluble solvent to obtain a resin binder solution, mixing and stirring a suspension of 100 to 1500 parts by weight of carbon nanotubes and water per 100 parts by weight of the thermoplastic resin to obtain a highly mixed carbon nanotube resin composition, and mixing the highly mixed carbon nanotube resin composition with a matrix (base) resin. The binder resin used was polyethylene or polyvinyl chloride, and the matrix resin used was ABS.
Prior art documents
Patent document
(patent document 0001) Korean patent application laid-open No. 10-2011-
(patent document 0002) Korean patent application laid-open No. 10-2008-0065688
(patent document 0003) Korean patent application laid-open No. 10-2012 and 0124611
(patent document 0004) Korean patent application laid-open No. 10-2012-0027263
Disclosure of Invention
Technical subject
The present invention addresses the problem of providing a high-strength polymer composite material containing carbon nanotubes with improved dispersibility by adjusting the specific surface area and the bulk density.
Means for solving the problems
In order to solve the problems of the present invention, the present invention provides a polymer composite material containing a thermoplastic polymer and carbon nanotubes. Wherein the BET specific surface area is 40m2G to 120m2G, bulk density 10kg/m3To 60kg/m3The content of the carbon nano tube relative to the total weight of the composite material is 5-15 wt%.
In addition, the polymer composite material in one embodiment may have a strength improvement rate of 10% or more, as compared to before the addition of the carbon nanotubes.
In addition, the length-width ratio range of the carbon nano tube can be 1-100, and the diameter can be 20-100 nm.
In addition, the volume density of the carbon nano tube can be 30-60 kg/m3。
The average size of the carbon nanotube aggregates contained in the polymer composite material may be 5 μm or less.
The carbon nanotubes used as the raw material may have an average particle diameter of 100 to 800 μm.
In addition, the carbon nanotube may have a potato-shaped or spherical twisted (angled) two-dimensional structure.
The method for producing the carbon nanotube comprises a step of loading a catalytic component and an active component on a spherical α -alumina carrier, introducing a supported catalyst calcined at 600 ℃ or lower into a reactor, and injecting a carbon supply source or a mixture of the carbon supply source and hydrogen, nitrogen, or a mixture thereof into the reactor at a temperature of 650 ℃ or higher and less than 800 ℃, and a step of injecting the carbon supply source or the mixture into the reactor
And decomposing the carbon supply source on the surface of the catalyst by the injection, thereby growing the carbon nanotube.
In addition, the calcination temperature may be 400 to 600 ℃.
The catalytic component and the active component may be supported by about 10 to 25 parts by weight based on 100 parts by weight of the spherical α -alumina.
The weight ratio of the catalytic component to the active component may be 10 to 30:1 to 14.
The catalyst component may contain one or more selected from Fe, Co, and Ni.
In addition, the active ingredient may contain one or more of Mo and V.
The method for producing the supported catalyst comprises a step of mixing a spherical α -alumina carrier with an aqueous metal solution containing a catalyst component precursor and an active component precursor to form an aqueous solution containing a supported catalyst precursor, a step of aging and impregnating the aqueous solution containing the supported catalyst precursor to obtain a mixture, a step of vacuum-drying the mixture to coat the catalyst component and the active component on the surface of the carrier, and a step of calcining the product obtained by vacuum-drying at a temperature of 600 ℃ or less to form the supported catalyst.
In addition, the concentration of the metal aqueous solution can be 0.1-0.4 g/ml.
According to one embodiment, the curing, impregnation process may be performed at a temperature of 20 to 100 ℃ for 30 minutes to 15 hours.
In order to solve another problem, the present invention provides a method for producing a composite material, comprising:
a step of mixing a thermoplastic polymer with carbon nanotubes; and the number of the first and second groups,
and melting, mixing and extruding the mixture by using an extruder.
Advantageous effects
The polymer composite material of the present invention has a high specific surface area of the carbon nanotubes, so that the polymer composite material contains a high content of carbon nanotubes, and has a high volume density and a large diameter, so that the dispersibility of the carbon nanotubes in the composite material can be improved, and the mechanical strength and physical properties of the polymer composite material can be effectively improved.
Drawings
FIGS. 1a and 1b show SEM images of polymer composite extrudates/injection moldings of comparative example 5.
Fig. 2a and 2b show SEM images of the polymer composite extrudate/injection molded article in example 1.
Fig. 3 shows an SEM image of the strength-improving carbon nanotube used in example 1.
Detailed Description
The terms and words used in the specification and claims of the present invention should not be interpreted as being limited to the meanings in the common or dictionary, and the inventors should only interpret the meanings and concepts conforming to the technical idea of the present invention on the basis of the principle that the concept of the terms can be appropriately defined in order to best explain their own invention.
The present invention will be described in detail below.
According to a preferred embodiment of the present invention, there is provided a polymer composite,
which is a polymer composite containing a thermoplastic polymer and carbon nanotubes. Wherein the BET specific surface area is 40m2/g～120m2G, bulk density 10kg/m3～60kg/m3The carbon nanotubes being contained in a proportion relative to the total weight of the composite materialThe amount is 5 to 15 wt%.
The polymer composite may have a tensile strength improvement rate of 10% or more, as compared to that before the addition of the carbon nanotubes.
That is, the present invention can increase the content of carbon nanotubes that can be contained in the polymer by increasing the specific surface area of the carbon nanotubes, thereby improving the physical properties exhibited by the increase in the content of carbon nanotubes in the polymer composite. In addition, in order to solve the problem of the decrease in dispersibility due to the increase in the content of the carbon nanotubes, the volume density is adjusted, and the decrease in dispersibility in the polymer composite material can be suppressed. By virtue of the above characteristics, a high-strength polymer composite material having excellent mechanical strength, in which the tensile strength is improved by about 10% or more by adding the carbon nanotubes, can be provided.
In addition, the polymer composite of the present invention can be prepared by the following method: a step of mixing a thermoplastic polymer with carbon nanotubes; and melting, kneading and extruding the mixture by an extruder. At this time, the aggregates of the carbon nanotubes remaining in the composite material obtained by extrusion injection molding of the aggregates by the extruder may be present in a size of 5 μm or less, and this may indicate that the carbon nanotubes are excellent in dispersibility in the polymer.
Carbon nanotube
According to an embodiment of the present invention, the specific surface area of the carbon nanotube is preferably 40 to 100m2G, bulk density of 60kg/m3Below, for example, 10 to 60kg/m3Preferably 30 to 60kg/m3More preferably 30 to 50kg/m3. Although the lower the specific surface area of the carbon nanotubes, the more the loading content in the composite material can be increased, the dispersibility and density thereof will be reduced. In addition, the smaller the bulk density, the lower the dispersibility in the polymer resin and the possibility of forming aggregates of carbon nanotubes, which may become a factor of degrading mechanical and electrical properties.
The content of the carbon nanotubes in the polymer composite material is 5 to 15 wt%, more preferably 5 to 10 wt%, based on the total weight of the composite material. When the content is less than 5% by weight, the mechanical strength cannot be sufficiently improved.
Therefore, the present invention can optimize the loading content and dispersibility of the carbon nanotubes by simultaneously adjusting the specific surface area and the bulk density of the carbon nanotubes, and can prepare a polymer composite material having excellent physical properties, particularly, significantly improved mechanical strength.
The average size of the carbon nanotube aggregates contained in the polymer composite injection-molded article may be 5 μm or less, which is an index showing that the dispersibility of the composite material is improved, and the effect of improving the physical properties of the composite material can be exhibited.
In addition, the carbon nanotubes contained in the polymer composite may have an average aspect ratio of 1 to 100, preferably 10 to 60, and more preferably 10 to 30.
In addition, the diameter of the carbon nanotubes contained in the polymer composite may be 20 to 100nm, preferably 30 to 100 nm.
The average length and aspect ratio of the carbon nanotubes can be measured by SEM (Scanning Electron Microscope) or TEM (transmission Electron Microscope) photographs. That is, after a photograph of the powdery carbon nanotube as a raw material is obtained by these measuring devices, it can be analyzed by an image analyzer (image analyzer), for example, Scandium 5.1(Olympus soft Imaging Solutions GmbH, germany), and an average length is obtained.
According to one embodiment, the carbon nanotubes used as the raw material have an average particle diameter of about 5 μm to 1000 μm or 100 to 800 μm, preferably 200 μm to 600 μm, more preferably 300 μm to 4000 μm, and a thickness ranging from 10nm to 1000 μm. The bundled carbon nanotubes having the average length and thickness in the above ranges are more advantageous in improving the electrical conductivity of the thermoplastic polymer-containing composite material. The carbon nanotubes have a network structure in the matrix of the polymer composite containing the thermoplastic polymer, and the carbon nanotubes having a longer length are more advantageous for forming the network, resulting in improvement of physical properties of the polymer composite.
The CNT of the present invention can satisfy a potato-shaped or spherical twisted type having a bundle diameter of 10 to 50nm, a flattening ratio of 0.9 to 1.0, and a particle size distribution value (Dcnt) of 0.5 to 1.0.
The term "bulk density" used in the present invention is defined by the following formula 1, and the density distribution or specific range of grown CNTs can be obtained by increasing the reaction temperature at the time of CNT synthesis by adjusting the calcination temperature of the supported catalyst.
[ formula 1 ]
Bulk density (kg) weight of CNT/volume of CNT (m)3)
In addition, the flattening ratio and the shape of the bundle can be obtained by the above-described unique process of preparation using the supported catalyst of the present invention. In this case, the flattening ratio is defined by the following formula 2.
[ formula 2 ]
Aspect ratio (shortest diameter through CNT center/longest diameter through CNT center)
Further, the particle size distribution value (Dcnt) can be defined by the following formula 3.
[ formula 3 ]
Dcnt＝[Dn90-Dn10]/Dn50
In the calculation formula, Dn90 indicates a number average particle size measured in an absorption (adsorption) mode at 90% standard, Dn10 indicates a number average particle size measured in a 10% standard, and Dn50 indicates a number average particle size measured in a 50% standard, after placing CNTs in distilled water for 3 hours.
The carbon nanotube of the present invention can be prepared using a supported catalyst in which a spherical α -alumina carrier is calcined at 600 ℃ or less, and more preferably, can be prepared using the following preparation method.
The method for producing the carbon nanotube comprises a step of loading a catalytic component and an active component on a spherical α -alumina support, feeding a supported catalyst calcined at 600 ℃ or lower into a reactor, and injecting a carbon supply source or the carbon supply source and hydrogen, nitrogen or a mixed gas thereof into the reactor at a temperature of 650 ℃ or higher and less than 800 ℃, and a step of growing the carbon nanotube by decomposing the injected carbon supply source on the surface of the catalyst.
That is, the present invention uses α -alumina carrier and adjusts the catalyst calcination temperature and reaction temperature to prepare the catalyst with BET specific surface area of 40m2G to 120m2G, bulk density of 60kg/m3The following CNTs.
The supported catalyst for CNT synthesis according to one specific example is characterized in that a catalytic component and an active component are supported on a spherical α -alumina support and calcined at 600 ℃.
Usually, the chemical formula is Al2O3In α -alumina (corundum), the oxide ions form a hexahedral closed structure, the alumina ions are distributed symmetrically in the octahedral voids.
It is also known that gamma-alumina is frequently used as a catalyst support due to its high porosity, but α -alumina is rarely used as a catalyst support due to its very low porosity, and it is unexpected that, in the case of preparing a supported catalyst using spherical α -alumina as a support, it is possible to suppress the generation of amorphous carbon while reducing the specific surface area to control the diameter at the time of synthesizing CNTs by adjusting the calcination temperature for forming the supported catalyst.
As described above, the supported catalyst for CNT synthesis according to the present invention is technically characterized in that a catalytic component and an active component are supported on a spherical α -alumina carrier and calcined at a temperature of 600 ℃ or lower, and the calcination temperature may be, for example, in the range of 400 ℃ to 600 ℃ inclusive.
In the case of the spherical α -alumina used in the present invention, the term "spherical" includes not only a perfect spherical shape but also a true spherical shape, and also a case where the cross section is elliptical, such as a potato shape.
According to one embodiment, the spherical α -alumina can be prepared using methods well known in the art, such as the Bayer (Bayer) process, which is widely used in the industry for preparing alumina from bauxite (bauxite). similarly, the spherical α -alumina can be prepared as gamma-Al2O3Or any aqueous (hydro) oxide, to a temperature in excess of 1000 c.
For example, the spherical α -alumina used in the present invention can have a particle size of about 1m when measured by the BET method2G to about 50m2In the present invention, the spherical α -alumina used as the carrier has a smooth surface and very low porosity, unlike the existing carriers, and may have a surface area of 0.001 to 0.1cm, for example3Pore volume in g.
The spherical α -alumina as the carrier may carry a relatively low amount of metal, and the carried metal may be, for example, about 10 to 25 parts by weight or about 15 to 20 parts by weight of the catalytic component and the active component based on 100 parts by weight of the spherical α -alumina.
The catalytic component and the active component supported in the spherical α -alumina may be used in a content of 10 to 30:1 to 14 by weight, and in the above content range, a more excellent CNT preparation activity can be exhibited.
The catalytic component used in the present invention may be one or more selected from Fe, Co and Ni. For example, it may be one or more selected from the group consisting of Fe salt, Fe oxide, Fe compound, Co salt, Co oxide, Co compound, Ni salt, Ni oxide and Ni compound, and may be, for example, Fe (NO)3)2·6H2O、Fe(NO3)2·9H2O、Ni(NO3)2·6H2O、Co(NO3)2·6H2And nitrides such as O.
The active ingredient used in the present invention may be, for example, one or more of Mo and V, a Mo salt, a Mo oxide, a Mo compound, a V salt, a V oxide, a V compound, or the like, and further, for example, (NH)4)6Mo7O24·4H2The nitride of O and the like are dissolved in distilled water and used.
As described above, the supported catalyst for CNT synthesis according to the present invention can be prepared by an impregnation method.
According to one embodiment, the method for preparing a supported catalyst for CNT synthesis according to the present invention comprises:
(1) a step of mixing a spherical α -alumina carrier with an aqueous metal solution containing a catalytic component precursor and an active component precursor to form an aqueous solution containing a supported catalyst precursor;
(2) a step of aging and impregnating the aqueous solution containing the supported catalyst precursor to thereby obtain a mixture;
(3) a step of drying the mixture in vacuum and coating the catalytic component and the active component on the surface of the carrier; and
(4) a step of subjecting a product obtained by the vacuum drying to calcination at a temperature of 600 ℃ or less, thereby forming a supported catalyst.
In the production method, an aqueous solution containing a supported catalyst precursor is formed in step (1), which is formed by mixing an Al-based carrier with an aqueous metal solution containing a catalyst component precursor and an active component precursor, wherein the catalyst component, the active component and a spherical α -alumina carrier are contained, and the above-mentioned components are explained above.
The concentration of the aqueous metal solution is more effective when taking the impregnation efficiency into consideration, for example, in the range of 0.1 to 0.4g/ml, or 0.1 to 0.3g/ml, and as described above, the spherical α -alumina carrier mixed in the aqueous metal solution is used in an amount of, for example, about 10 to 25 parts by weight, or about 15 to 20 parts by weight, of the catalytic component and the active component, based on 100 parts by weight of the spherical α -alumina.
In step (2) of the production method, the supported catalyst precursor solution is aged and impregnated to obtain a mixture. In this case, the curing and impregnation are not limited to these, and may be carried out at a temperature ranging from 20 ℃ to 100 ℃, or from 60 ℃ to 100 ℃ for 30 minutes to 15 hours, or from 1 hour to 15 hours. The above range can provide higher load efficiency.
In step (3) of the production method, the aging and impregnation product obtained in step (2), i.e., the mixture, is vacuum-dried, and the surface of the support is coated with the catalytic component and the active component. The vacuum drying refers to a process of drying by rotary evaporation under vacuum, and may be performed, for example, at 45 to 80 ℃ for less than one hour, or in the range of one minute to one hour. The residual metal salt that is not impregnated in the carrier can form a uniform impregnation film on the surface of the alumina by a drying process.
In the vacuum drying described in the present specification, the meaning of "vacuum" is not particularly limited in the case of conforming to the vacuum range applicable to usual vacuum drying.
In step (4) of the production method, the product obtained by the vacuum drying of step (3) is calcined, thereby forming a final product, i.e., the supported catalyst of the present invention. The above calcination may be carried out at a temperature ranging from about 400 to 600 c, and may be carried out in air or under inert gas conditions. It may be carried out within about 30 minutes to 5 hours, but the calcination time is not limited thereto.
According to one embodiment, after the vacuum drying in the step (3), pre-calcination may be performed at about 250 to 400 ℃ at least 1 time before the calcination in the step (4), in which case, it is preferable in terms of reaction efficiency that at most 50% of the total supported catalyst precursor aqueous solution is impregnated in the amorphous α -alumina support before the pre-calcination and that the supported catalyst precursor aqueous solution residue is impregnated in the spherical α -alumina support immediately after or before the pre-calcination is performed.
The volume shape of the supported catalyst prepared in the above-described method depends on the volume morphology of the spherical α -alumina carrier used, but is not limited thereto, that is, the supported catalyst for CNT synthesis has a spherical volume shape and a structure in which a single layer or multiple layers (2 or 3 or more layers) of catalytic components are coated on the surface of the carrier.
The supported catalyst for CNT production provided in the present invention has, for example, a particle size or an average particle size of about 30 to 150 μm, and when observed by SEM, the surface particle size may be in the range of about 10 to 50 , and it is preferable that the CNT diameter is adjusted within this range and the catalyst activity is optimized within this range.
On the other hand, in the supported catalyst in which the catalytic component and the active component are coated on the surface of the spherical α -alumina carrier, when the particle size of the alumina carrier or the average particle size range is considered, the number average particle size can be measured within 5%, specifically within 3%, by defining the particle size of 32 μm or less as the amount of the ultrasonic (ultrasonic) fine powder based on the mesh size measurement.
For reference, in the ultrasonic process, the fine powder is not screened out as an aggregate of the catalytic material and the active material attached to the catalyst by a screen, but the particle size and the catalytic activity are different from those of the catalyst-active material coated on the carrier in a good state, and the CNT yield is remarkably decreased by island (island) like aggregates attached to the catalyst in the above state. Further, since the substance is slightly weakly adhered to the catalyst, the substance is separated during the ultrasonic treatment, and a fine powder is formed.
In the present invention, the amount of the ultrasonic fine powder means the amount of the number average particle diameter fine powder measured by a particle size analyzer after the ultrasonic treatment, in which case the carrier includes a plurality of layers of carriers.
Particularly, the supported catalyst for CNT synthesis obtained according to the present invention is preferably spherical when considering the specific surface area. It has been also found that the supported catalyst for CNT synthesis actually prepared in the present invention is also close to a spherical shape, an approximately spherical shape, or an actually spherical shape.
The process for preparing CNTs from the supported catalyst obtained by the above method includes, but is not limited to, the following steps:
a step of charging the supported catalyst of the present invention into a reactor and introducing a carbon supply source or a mixture of the carbon supply source and hydrogen, nitrogen, or a mixture thereof into the reactor at a temperature of about 650 to about 800 ℃; and
and decomposing the carbon supply source injected onto the surface of the catalyst to grow the carbon nanotubes.
According to one embodiment, a fixed bed reactor or a fluidized bed reactor may be used as the reactor without limitation.
According to the CNT manufacturing method of the present invention, as defined in the following examples, CNTs having a non-bundle-like two-dimensional structure and a spherical volume shape can be manufactured.
Thermoplastic polymers
When the moldability is taken into consideration, the thermoplastic polymer preferably has a relative viscosity of 1.5 to 5, more preferably 2 to 4.5, as measured at 25 ℃ at a concentration of 1 g/dl. When the relative viscosity is less than 1.5, the viscosity is too low, and therefore, processing after melt kneading becomes difficult, and it may be difficult to obtain preferable physical properties. On the other hand, if it exceeds 5, the viscosity becomes too high, so that the fluidity at the time of molding becomes poor, and a sufficient injection pressure cannot be applied, so that it may be difficult to prepare a molded product.
In addition, the thermoplastic polymer according to the invention preferably has a melt index of from 0.5 to 100g/min, more preferably from 1.0 to 80 g/min. However, when the melt index is less than 0.5g/min, melt kneading is difficult because a high shear force is required, the carbon nanotubes are poorly dispersed in the thermoplastic polymer, and when the melt index exceeds 100g/min, the impact strength of the molded product may be seriously lowered.
The thermoplastic polymer that can be used for the conductive composite material is not limited as long as it is a material used for the thermoplastic polymer in the related industry. For example, a polycarbonate resin, a polypropylene resin, an aromatic polyamide resin, an aromatic polyester resin, a polyolefin resin, a polycarbonate resin, a polyphenylene ether resin, a polysulfone resin, a polyethersulfone resin, a polyarylene resin, a cycloolefin resin, a polyetherimide resin, a polyacetal resin, a polyvinylacetal resin, a polyketone resin, a polyetherketone resin, a polyetheretherketone resin, a polyarylketone resin, a polyethernitrile resin, a liquid crystal resin, a polybenzimidazole resin, a polyoxamide resin, a polyamide resin, or
A vinyl polymer or copolymer resin obtained by polymerizing or copolymerizing at least one vinyl monomer selected from the group consisting of an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound, or
One or more selected from the group consisting of diene-aromatic alkenyl compound copolymer resin, vinyl cyanide-diene-aromatic alkenyl compound copolymer resin, aromatic alkenyl compound-diene-vinyl cyanide-N-phenyl maleimide copolymer resin, vinyl cyanide- (ethylene-diene-propylene (EPDM)) -aromatic alkenyl compound copolymer resin, polyolefin, vinyl chloride resin, chlorinated vinyl chloride resin. Specific kinds of these resins are common knowledge, and those skilled in the art can appropriately select examples that can be used for the composition of the present invention.
Examples of the polyolefin resin include, but are not limited to, polypropylene, polyethylene, polybutylene, and poly (4-methyl-1-pentene), and combinations thereof. In one embodiment, the polyolefin is selected from the group consisting of polypropylene homopolymers (e.g., atactic (atactic) polypropylene, isotactic (isotactic) polypropylene, and syndiotactic (syndiotic) polypropylene), polypropylene copolymers (e.g., polypropylene random copolymers), and mixtures thereof. Suitable polypropylene copolymers include, but are not limited to, random copolymers prepared by polymerization of propylene in the presence of comonomers selected from ethylene, but-1-ene (i.e., 1-butene), and hex-1-ene (i.e., 1-hexene). While any specified amount of comonomer may be included in these polypropylene random copolymers, it is generally included in an amount of less than about 10 wt% (e.g., about 1 to about 7 wt%, or about 1 to about 4.5 wt%).
The polyester resin is a polycondensate of a dicarboxylic acid component skeleton and a diol component skeleton, i.e., a homopolyester or a copolyester, wherein the homopolyester is represented by Polyethylene terephthalate (Polyethylene terephthalate), Polypropylene terephthalate (Polypropylene terephthalate), polybutylene terephthalate (polybutylene terephthalate), Polyethylene naphthalate (Polyethylene-2, 6-naphthalene), 1, 4-cyclohexanedimethylester terephthalate (Poly-1, 4-cyclohexanedimethylene terephthalate), Polyethylene diphenyl terephthalate (Polyethylene terephthalate), and Polyethylene terephthalate (Polyethylene terephthalate), and the like, and particularly, the copolyester is preferably Polyethylene terephthalate because of its low cost and can be used in various applications, and the copolyester is defined as a polycondensate of 3 or more kinds of components having a dicarboxylic acid skeleton and a diol component having a diol skeleton, i.e., 3 or more kinds of components having a diol skeleton, 1 '-cyclohexane dicarboxylic acid, 4' -diol terephthalate, 1 '-cyclohexane dicarboxylic acid, 4-cyclohexane dicarboxylic acid, 1' -diol, 4-cyclohexane-1, 4-cyclohexane-4-diol, 5-1 '-diol, 5-cyclohexane-1' -diol, 4-naphthalene-5-1 '-diol, 5-cyclohexane-4-diol, 5-1' -diol, 5-bis-1 '-naphthalene-1' -diol, 5-bis-5-cyclohexane diol, and the like.
The polycarbonate resin may be prepared by reacting a biphenyl with phosgene (phosgene), a haloformate (haloform), a carbonate, or a combination thereof. Specific examples of the biphenyl include hydroquinone, resorcinol, 4 '-dihydroxybiphenyl, 2-bis (4-hydroxyphenyl) propane (also referred to as "bisphenol-A"), 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, resorcinol, 4' -dihydroxybiphenyl, 2-bis (4-hydroxyphenyl) propane, bisphenol A, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, and the like. Among them, 2-bis (4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane or 1, 1-bis (4-hydroxyphenyl) cyclohexane is preferably used, and 2, 2-bis (4-hydroxyphenyl) propane is more preferably used.
The polycarbonate resin may be a mixture of copolymers prepared from 2 or more biphenyls. Further, as the polycarbonate resin, a linear polycarbonate resin, a branched (branched) polycarbonate resin, a polycarbonate copolymer resin, or the like can be used.
The linear polycarbonate resin may be a bisphenol-A polycarbonate resin. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride or trimellitic acid with biphenyl and a carbonate. The polyfunctional aromatic compound is 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polycarbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with biphenyls and a carbonate. In this case, as the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, and the like can be used.
Examples of the cyclic olefin polymer include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof. Specific examples thereof include APEL (ethylene-cycloolefin copolymer manufactured by Mitsui chemical Co., Ltd., Japan), ATON (norbornene polymer manufactured by JSR Co., Ltd., Japan), ZEONOR (norbornene polymer manufactured by Rapulus japonicus Co., Ltd., Japan), and the like.
The polyphenylene ether resin is also called polyphenylene ether, and has a structure in which-O-is bonded to a phenylene group as a repeating unit. The phenylene group may have various substituents, for example, methyl, ethyl, halogen, hydroxy, and the like.
As the polyamide resin, a nylon copolymer resin, and a mixture thereof can be used. As the nylon resin, polyamide-6 (nylon 6) obtained by ring-opening polymerization of a lactam such as epsilon-caprolactam and omega-laurolactam, which are well known, can be used; nylon polymers obtainable from amino acids such as aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.; aliphatic, alicyclic or aromatic diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2, 4-trimethylhexamethylenediamine, 2,4, 4-trimethylhexamethylenediamine, 5-methylnonahexamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1, 3-bisaminomethylcyclohexane, 1, 4-bisaminomethylcyclohexane, 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane, bis (4-aminocyclohexane) methane, bis (4-methyl-4-aminocyclohexyl) methane, 2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperidine and the like, nylon polymers obtained by polymerization with aliphatic, alicyclic or aromatic dicarboxylic acids such as adipic acid, sebacic acid (sebasic), azelaic acid (azelaical), terephthalic acid, 2-chloroterephthalic acid and 2-methylterephthalic acid; copolymers or mixtures thereof. Nylon copolymers include polycaprolactam (nylon 6) and polyhexamethylene sebacamide (nylon 6, 10), polycaprolactam (nylon 6) and polyhexamethylene adipamide (nylon 66), polycaprolactam (nylon 6) and polydodecalactam (nylon 12), and the like.
Other additives
The conductive composite material may further contain one or more additives selected from the group consisting of flame retardants, flame retardant aids, lubricants, plasticizers, heat stabilizers, drip retardants, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives and anti-dripping agents in an amount of 5 parts by weight or less based on 100 parts by weight of the carbon nanotubes, within a range that does not affect the conductivity and physical properties. The specific kinds of these additives are common general knowledge, and those skilled in the art can appropriately select examples that can be used in the composition of the present invention.
The conductive composite material according to the present invention may be prepared by an extrusion injection molding process. In general, the extrusion process is a molding method in which a raw material is supplied to an extruder, pushed out of a structure in the form of a heating cylinder, and converted into a continuous body having a constant cross section. The raw material of the conductive composite material supplied to the extruder is heated, softened, and melted in a hot cylinder, and is kneaded and compressed by the rotation of a screw and conveyed. The raw material flow forming a uniform molten mass is continuously extruded outward from the opening portion of the die made into the target shape, and then subjected to a cooling process to obtain an extruded product.
In the above extrusion process, when the raw material is subjected to a kneading process under mechanical pressure in a heated state, the physical properties of the raw material may be changed. For example, since mechanical breakage occurs in the carbon nanotubes having a fine structure, the carbon nanotubes remaining in the extruded product may have a shape different from that of the carbon nanotubes supplied as the raw material. Therefore, it is preferable to perform the extrusion process while maintaining the physical properties of the raw material, and for this purpose, it is necessary to appropriately control the extrusion conditions of the extruder. In the present invention, damage to the raw material can be suppressed by controlling the rotation speed of the rotary screw attached to the extruder.
In the present invention, the extruder can be divided into a single-screw extruder having 1 screw and a multi-screw extruder having a plurality of screws. The multi-screw extruder may be a twin-screw extruder having 2 screws for uniformly kneading the additive.
When a twin-screw extruder is used as the extruder, the screw of the twin-screw extruder is not particularly limited, and screws of a complete-intermeshing type, an incomplete-intermeshing type, a non-intermeshing type, and the like can be used. From the viewpoint of kneading and reactivity, a fully intermeshing propeller is preferred.
The rotation direction of the propellers may be either the same direction or the opposite direction, but the same direction rotation is preferable from the viewpoint of kneading property and reactivity. The propellers are most preferably of the co-rotating fully intermeshing type.
According to one embodiment, in the extrusion process, in order to suppress thermal deterioration of the resin, an inert gas may be introduced into the raw material input portion to melt and knead the resin, and the inert gas may be, for example, nitrogen gas.
Examples of the kneading method using the extruder include a method of kneading a thermoplastic resin and carbon nanotubes together, a method of producing a resin composition (Masterpellet) containing carbon nanotubes at a high concentration in a thermoplastic resin, adding the resin composition and carbon nanotubes to a predetermined concentration, and melt-kneading the mixture (masterbatch method), and the like, and any kneading method can be used. As a method different from this, in order to suppress breakage of the carbon nanotubes, a method of feeding a thermoplastic resin from the extruder side, supplying the carbon nanotubes to the extruder using a side feeder (side feeder), and melt-kneading the carbon nanotubes can be used.
Examples
The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited thereto.
Preparation example 1 preparation of catalyst
As the catalyst metal precursor, Fe (NO) having a content as reported in Table 1 below was used3)29H2O、Co(NO3)2·6H2O、(NH4)6Mo7O24And NH4VO3This was completely dissolved in 15.0ml of distilled water to complete the preparation in flask A.
As a carrier, spherical α -Al is contained2O3(pore volume: 0.01cm3(g), BET specific surface area: 4.9m2Per g, product of Saint Gobain Co.) 12.5mg, or α -Al2O3(pore volume: 0.55cm3(ii)/g, BET specific surface area: 185m2G, product of Saint Gobain Co.) 12.5mg (comparative example 1) of flask B, the material in flask A was added to support the catalyst metal precursor on spherical α -Al2O3Then, the mixture was stirred and aged in a constant temperature reactor including a 100 ℃ reflux tank for 15 hours.
After drying in a 60 ℃ thermostat at 100rpm for 30 minutes in a rotary vacuum at 150mbar, 15ml of ethanol were added, and after dispersion by mixing at 100rpm, drying was carried out, which process was repeated 2 times in total. After the intermediate calcination of the dried catalyst was completed at 350 ℃, the catalyst was calcined in a nitrogen (or air) atmosphere at a calcination temperature (400 ℃ to 600 ℃) for 3 hours to prepare a uniform (homogeneous) supported catalyst. The catalyst prepared was completed to form spherical particles upon drying.
Preparation example 2 CNT preparation
A synthesis test of carbon nanotubes was performed in a fixed bed reaction apparatus on a laboratory scale using the catalyst for CNT synthesis prepared in preparation example 1. Specifically, the catalyst for CNT synthesis prepared in the above process was attached to the hollow part of a quartz tube having an inner diameter of 55mm, and then heated to 650 ℃ in a nitrogen atmosphere while maintaining the temperature, and hydrogen gas was flowed at a flow rate of 60sccm to synthesize a carbon nanotube aggregate in a predetermined amount for 2 hours. The physical properties (bulk density, average particle diameter, specific surface area) of the prepared carbon nanotubes are reported in table 1 below.
Example 1
A polymer composite material was prepared by melt-kneading 5 wt% of the carbon nanotubes (see fig. 3) prepared in preparation example 2, which had the physical property conditions shown in table 1 below, and polycarbonate at 280 ℃.
Example 2
A polymer composite was prepared by melt-kneading, using a twin-screw extruder, 10 wt% of the carbon nanotubes prepared in preparation example 2, which had the physical property conditions shown in table 1 below, with polycarbonate at 280 ℃.
Comparative example 1
The preparation was completed under the same conditions as in example 1 except that no carbon nanotube was added.
Comparative example 2
The preparation was completed in a method equivalent to example 1 except that 2 wt% of the carbon nanotube having the physical property conditions in comparative example 2 as reported in the following table 1 was added.
Comparative example 3
The preparation was completed in a method equivalent to example 1, except that 2 wt% of the carbon nanotubes having the physical property conditions in comparative example 3 as reported in the following table 1 were added.
Comparative example 4
The preparation was completed in a manner identical to example 1, except that 5 wt% of the carbon nanotubes having the physical property conditions in comparative example 4, as reported in table 1 below, were added.
Comparative example 5
The preparation was completed in a manner identical to example 1, except that 5 wt% of the carbon nanotubes having the physical property conditions in comparative example 4 as reported in the following table 1 were added.
[ TABLE 1 ]
Tensile Strength evaluation
The measurement was carried out according to ASTM D638 using UTM from INSTRON corporation at a speed of 5mm/sec at room temperature.
[ TABLE 2 ]
As can be seen from the results in table 2, the polymer composites of examples 1 and 2 showed an increase in tensile strength of at least 10% as compared with the control of comparative example 1, i.e., the polymer composite not mixed with carbon nanotubes. This means that high mixing of carbon nanotubes can be achieved by increasing the specific surface area and the bulk density is increased, so that the polymer composite as in comparative example 5 in fig. 1, that is, the decrease in dispersibility and the amount and size of aggregates generated, etc., which may occur in the case where the specific surface area of carbon nanotubes has a large value and the bulk density has a small value, can be reduced, and thus a high-strength carbon composite, as shown in fig. 2, in which few or few aggregates are generated, can be prepared.
Industrial applicability
The polymer composite material according to the present invention can be used in various fields such as energy materials, functional composite materials, medicines, batteries, semiconductors, display elements, and manufacturing methods thereof, because the polymer composite material contains carbon nanotubes at a higher content by increasing the specific surface area of the carbon nanotubes, and the polymer composite material has a higher volume density and a larger diameter, so that the dispersibility of the carbon nanotubes in the composite material can be improved, and the mechanical strength and physical properties of the polymer composite material can be more effectively improved.
Claims (11)
1. A high strength polymer composite comprising a thermoplastic polymer and carbon nanotubes, wherein,
the carbon nano tube has a BET specific surface area of 40m2/g～100m2(iv) g, bulk density of 30 to 60kg/m3The content of the carbon nano tube relative to the total weight of the composite material is 5-15 wt%,
the diameter of the carbon nanotube is 30 to 100nm, and
the average particle diameter of the carbon nanotubes used as a raw material in the polymer composite material is 100 to 800 μm.
2. The high strength polymer composite of claim 1,
the tensile strength improvement rate of the high-strength polymer composite material added with the carbon nanotubes is improved by more than 10% compared with that before the carbon nanotubes are added.
3. The high strength polymer composite of claim 1,
the length-width ratio range of the carbon nano tube is 1-100.
4. The high strength polymer composite of claim 1,
carbon nanotube aggregates are contained in the polymer composite material, and the average size thereof is 5 μm or less.
5. The high strength polymer composite of claim 1,
the carbon nano tube has a potato-shaped or spherical winding-shaped two-dimensional structure.
6. A method for preparing the high-strength polymer composite material according to claim 1, comprising a step of mixing carbon nanotubes with a thermoplastic resin, and the method for preparing the carbon nanotubes comprises:
a step of loading a catalyst component and an active component on a spherical α -alumina carrier, introducing a supported catalyst calcined at 600 ℃ or lower into the reactor, and injecting a carbon supply source or a mixture of the carbon supply source and hydrogen, nitrogen or a mixture thereof into the reactor at a temperature of 650 ℃ or higher and less than 800 ℃, and a step of mixing the carbon supply source with hydrogen, nitrogen or a mixture thereof
And decomposing the carbon supply source on the surface of the catalyst by the injection, thereby growing the carbon nanotube.
7. The method for preparing a high strength polymer composite according to claim 6,
the calcining temperature is 400-600 ℃.
8. The method for preparing a high strength polymer composite according to claim 6,
the catalytic component and the active component are supported in an amount of 10 to 25 parts by weight based on 100 parts by weight of the spherical α -alumina.
9. The method for preparing a high strength polymer composite according to claim 6,
the catalytic component and the active component are mixed in a weight ratio of 10 to 30:1 to 14.
10. The method for preparing a high strength polymer composite according to claim 6,
the catalytic component contains one or more selected from Fe, Co and Ni.
11. The method of preparing a high strength polymer composite according to claim 6, further comprising:
the method comprises the steps of mixing a spherical α -alumina carrier with a metal aqueous solution containing a catalyst component precursor and an active component precursor to form a supported catalyst precursor-containing aqueous solution, aging and impregnating the supported catalyst precursor-containing aqueous solution to obtain a mixture, vacuum-drying the mixture to coat the catalyst component and the active component on the surface of the carrier, and calcining the product obtained by vacuum-drying at a temperature of 600 ℃ or lower to form a supported catalyst.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2015-0135974 | 2015-09-25 | ||
| KR1020150135974A KR101923465B1 (en) | 2015-09-25 | 2015-09-25 | High strength polymer composite comprising carbon nanotubes |
| PCT/KR2016/007986 WO2017052057A1 (en) | 2015-09-25 | 2016-07-22 | High strength polymer comprising carbon nanotube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107108954A CN107108954A (en) | 2017-08-29 |
| CN107108954B true CN107108954B (en) | 2020-03-10 |
Family
ID=58386177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680004245.9A Active CN107108954B (en) | 2015-09-25 | 2016-07-22 | High strength polymers containing carbon nanotubes |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101923465B1 (en) |
| CN (1) | CN107108954B (en) |
| WO (1) | WO2017052057A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115667138B (en) * | 2020-08-12 | 2024-01-26 | 株式会社Lg化学 | Carbon nanotubes with low density and composite materials containing the same |
| CN116490719A (en) * | 2020-11-12 | 2023-07-25 | 深圳烯湾科技有限公司 | Gas storage tank and method for manufacturing same |
| WO2022126227A1 (en) * | 2020-12-18 | 2022-06-23 | Socpra Sciences Et Génie S.E.C. | Carbon nanotubes based composites with high shielding efficiency and method of production thereof |
| CN114316238B (en) * | 2021-12-10 | 2023-06-09 | 卓尔博（宁波）精密机电股份有限公司 | Bisphenol A type polycarbonate composite material for motor housing and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410475A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Polymer/carbon nano pipe composite powder and its solid phase shear break up preparation method |
| CN101541675A (en) * | 2006-11-30 | 2009-09-23 | 阿克马法国公司 | Process for synthesizing nanotubes, especially carbon nanotubes, and their uses |
| CN104774359A (en) * | 2014-01-15 | 2015-07-15 | 宁波大学 | Preparation method of polymer/carbon nanotube composite material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003291133A1 (en) * | 2002-11-26 | 2004-06-18 | Carbon Nanotechnologies, Inc. | Carbon nanotube particulates, compositions and use thereof |
| FR2893947A1 (en) | 2005-11-30 | 2007-06-01 | Arkema Sa | Obtaining pulverulent compositions, useful as polymeric materials, reinforcement and/or modifying agent, comprises contact of carbon nanotubes e.g. with a monomer (mixture), optional heat treatment, purification and/or separation |
| KR101183016B1 (en) * | 2008-02-22 | 2012-09-18 | 주식회사 엘지화학 | Carbon Nanotube-polymer Nanocomposite Improved In Electrical Conductivity And Preparation Method Thereof |
| KR101226522B1 (en) * | 2008-12-22 | 2013-01-25 | 제일모직주식회사 | Supported Catalyst with Solid Sphere Structure, Method for Preparing Thereof and Carbon Nanotube Using the Same |
| JP4787892B2 (en) | 2009-06-16 | 2011-10-05 | 株式会社ナノストラクチャー研究所 | Carbon nanotube high compounding resin granular material and manufacturing method thereof |
| KR101135055B1 (en) | 2009-06-26 | 2012-04-13 | 고려대학교 산학협력단 | Fabrication method of polymer/carbon nanotube composite with good electromagnetic interference shielding efficiency and polymer/carbon nanotube composite using the same |
| KR101576658B1 (en) * | 2009-12-30 | 2015-12-14 | 주식회사 효성 | - Carbonnanotube-polymer nanocomplex with fluidizing bed multi-walled carbon nanotube and preparation method thereof |
| KR101303899B1 (en) | 2011-05-04 | 2013-09-05 | (주)마크스톤 | Method for preparing of polymer-carbon nanotube composite particles |
| KR101620194B1 (en) * | 2013-09-30 | 2016-05-12 | 주식회사 엘지화학 | Process for preparing carbon nanotube agglomerates having a controlled bulk density |
-
2015
- 2015-09-25 KR KR1020150135974A patent/KR101923465B1/en active IP Right Grant
-
2016
- 2016-07-22 WO PCT/KR2016/007986 patent/WO2017052057A1/en active Application Filing
- 2016-07-22 CN CN201680004245.9A patent/CN107108954B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410475A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Polymer/carbon nano pipe composite powder and its solid phase shear break up preparation method |
| CN101541675A (en) * | 2006-11-30 | 2009-09-23 | 阿克马法国公司 | Process for synthesizing nanotubes, especially carbon nanotubes, and their uses |
| CN104774359A (en) * | 2014-01-15 | 2015-07-15 | 宁波大学 | Preparation method of polymer/carbon nanotube composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170036984A (en) | 2017-04-04 |
| WO2017052057A1 (en) | 2017-03-30 |
| CN107108954A (en) | 2017-08-29 |
| KR101923465B1 (en) | 2018-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101741327B1 (en) | Composite having improved mechanical property and molded articles comprising same | |
| KR101654405B1 (en) | Composite having improved mechanical propery and plastics comprising same | |
| CN107108954B (en) | High strength polymers containing carbon nanotubes | |
| KR101800486B1 (en) | Composite having improved conductivity and plastics comprising same | |
| JP5357047B2 (en) | Conductive thermoplastic resin composition and plastic molded article | |
| CN1724247A (en) | Carbon fiber composite material and method of producing the same | |
| KR20170090040A (en) | Thermoplastic resin composition and molded article manufactured using same | |
| WO2013122323A1 (en) | Carbon nano-material pellets and a method for preparing the pellets from powder of carbon nano-material | |
| WO2013111862A1 (en) | Method for producing master batch for conductive resin, and master batch | |
| KR102172152B1 (en) | High heat resistant carbon nanotubes and polymer composite comprising same | |
| KR20150041400A (en) | Polymer nanocomposites containing nano carbon materials having multiple hydrogen bonding motifs and their fabrication method | |
| KR20180045746A (en) | A method for manufacturing high heat-radiating filament for three dimensional printing | |
| KR20170060059A (en) | Thin wall moldable conductive compositions with improved physical properties and uses thereof | |
| JP2013166849A (en) | Method of producing polysulfone composition and method of producing molded product | |
| WO2021041493A1 (en) | Graphene-polymer matrix composite materials with controlled intrinsic viscosity and preparation method thereof | |
| KR101672089B1 (en) | Processing method for resin composite and plastic goods obtained from same | |
| US20160090522A1 (en) | Flexible heat-dissipating composite sheet including filler and low-viscosity polymerizable thermoplastic resin and cost effective mass producible method for preparing the same | |
| CN107075262B (en) | Composite materials with enhanced electrical conductivity and methods of making the same | |
| CN117597382A (en) | Extrudable composition comprising carbon nanotube coated polymer particles | |
| KR101741301B1 (en) | Composite having improved mechanical propery and plastics comprising same | |
| KR101773646B1 (en) | Thermoplastic resin composition for outer pannel of automobile | |
| KR101733222B1 (en) | Method for manufacturing a conductive polymer composite and a conductive polymer composite manufactured by the same | |
| KR20140073866A (en) | Carbon nano-material solids and a method for solidifying the powder of carbon nano-material | |
| KR20160079195A (en) | Composite having improved conductivity and Preparation Method Thereof | |
| EP4197969A1 (en) | Low-density carbon nanotubes and composite comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |