KR20150041400A - Polymer nanocomposites containing nano carbon materials having multiple hydrogen bonding motifs and their fabrication method - Google Patents
Polymer nanocomposites containing nano carbon materials having multiple hydrogen bonding motifs and their fabrication method Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08J2300/00—Characterised by the use of unspecified polymers
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- C08L2310/00—Masterbatches
Abstract
The present invention relates to a polymer nanocomposite using a carbon nanomaterial having a high-order structure by multiple hydrogen bonds and a method for producing the same, and a method for manufacturing a polymer nanocomposite using a polymer resin and a carbon nanomaterial, A first step of forming a carbon nanomaterial having a higher-order structure by multiple hydrogen bonding between carbon nanomaterials by introducing a functional group capable of multiple hydrogen bonding at the terminal; A second step of preparing a master batch by mixing a conductive paste and a polymer resin formed by dispersing a carbon nanomaterial having a higher order structure by the multiple hydrogen bonding in a solvent; And a third step of mixing and melting the master batch and the polymer resin to produce a nanocomposite. The polymer nanocomposite using a carbon nanomaterial having a higher order structure by multiple hydrogen bonds and a method of manufacturing the same do. Accordingly, by introducing a functional group capable of forming three or more multi-hydrogen bonds into a conductive carbon nanomaterial such as carbon nanotubes or graphene, a composition having a supramolecular structure between materials is formed without using a dispersing agent, and the composition is mixed with a polymer resin A masterbatch of a polymer-carbon nanomaterial is formed and mixed with the polymer resin to form a nanocomposite. The nanocomposite is advantageous in that a high content and a high degree of dispersion of the carbon nanomaterial are maintained without using a dispersant.
Description
The present invention relates to a polymer nanocomposite using a carbon nanomaterial having a higher-order structure by multiple hydrogen bonding and a method for producing the same. More particularly, the present invention relates to a nanocomposite comprising a conductive carbon nanomaterial such as carbon nanotubes and graphene, By introducing a functional group capable of forming a hydrogen bond, a composition in which supramolecular structures are formed between materials is formed without using a dispersant and mixed with a polymer resin to form a polymer-carbon nanomaterial masterbatch, which is mixed and melted with a polymer resin to form a nanocomposite Polymer nanocomposite using a carbon nanomaterial having a high-order structure by multiple hydrogen bonding and a method for producing the nanocomposite.
Generally, conductive carbon nanomaterials such as carbon nanotubes, graphene, carbon fibers, and carbon black are used as transparent electrodes, antistatic, electromagnetic shielding, electrode materials for energy generation and storage devices, heat radiation materials, conductive fibers, sensors, emitters, It can be applied to various fields such as X-ray source.
And, in the application field of conductive polymer, a technique of forming a master batch by mixing a carbon nanomaterial and a polymer resin is a very important technology, and studies have been made on this.
In particular, carbon nanotubes are expected to be widely used not only in the next generation electronic information industry but also in various industrial fields owing to excellent physical properties and various application possibilities. Japan, Germany, France, In order to secure competitiveness in the industrial field and to secure the competitiveness of high performance composite materials, we are pursuing research on the synthesis and application of carbon nanotubes under national support. In particular, we are promoting research on synthesis and application of carbon nanotubes, Systems, mechatronics, and high-performance complexes are expected to become more active in the future.
Techniques using carbon nanotubes have been developed to replace conventional carbon fibers with carbon nanotubes and to develop materials suitable for the required characteristics by making full use of the properties of carbon nanotubes. Composite materials based on the mechanical properties of carbon nanotubes are mainly composed of composite materials based on polymers. In addition, attempts have been made for carbon - carbon composite materials and carbon - ceramic composite materials. In addition, attempts have been made to develop functional materials such as conductive thin films utilizing characteristics other than the mechanical properties of carbon nanotubes. For example, a patent has been disclosed in which carbon nanotubes are used as electromagnetic interference (EMI) blocking materials.
Toray, Japan, discloses a thermoplastic resin containing carbon fibers and carbon nanotubes (JP2002-097375, JP2003- < 238816), a process for producing a polymer composite material containing carbon nanotubes (JP2003-286350) (JP2004-067952), which is a composition containing carbon nanotubes based on polyamide, and Rice University has disclosed a technique for adding carbon nanotubes during polymerization (US20050074390). After the basic technologies for polymer composite materials containing such carbon nanotubes have been disclosed, many techniques for composites containing carbon nanotubes by polymer types have been disclosed.
Nanotech Co., Ltd. has disclosed a technology (KR2002-007233) for a composite material containing carbon nanotubes based on a heat-resistant resin such as polyimide and polysulfone, and has been developed by Kanekafuchi Chemical of Japan -246927, JP2004-123867) and Aerospace Laboratory (JP2004-250646) based on polyimide, and Toyobo of Japan on carbon nanotubes-containing nanocomposite based on polybenzazole .
(KR2003-005710) containing carbon nanotubes in Korea University, composite material (US685410) containing carbon nanotubes based on acrylonitrile in Geogia Tech Research, (KR2005-0027415, JP2004-123770, etc.) based on rubber, and the application range of the technology is gradually increasing.
Also, as carbon black or carbon fiber is used as a conductive medium for polymer scaffolds, research on nanocomposites that can be applied to optoelectronics using the high electrical conductivity of carbon nanotubes is under way.
Hyperion of the United States has disclosed a technology (US678702, US6746627, US20040217336) on nanocomposite materials containing carbon nanotubes based on polyvinylidene fluoride (PVDF), the main content of which is the electrical conductivity of the carbon nanotubes and the surface lubrication The present invention relates to a technique for applying a characteristic to a raw material of a sliding part.
Other patents include technologies related to an electrically conductive composite (disclosed by Siemens, General Electric Company, etc.) utilizing an electric conduction characteristic of a carbon nanotube, an EMI shielding material, an antenna, and a medical device part.
In order to improve the electrical properties of the conventional polymer resin, many studies have been conducted by adding fillers such as carbon black, carbon fiber, steel fiber, and silver flake. However, Too much expensive filler is required for improvement, and there are many problems in processing with resin.
Therefore, carbon nanotube-polymer nanocomposite which can improve the electrical properties by adding a small amount of carbon nanotubes instead of conventional fillers or reducing the amount of existing filler and adding carbon nanotubes together is under study. An in-situ polymerization method (KR2006-0077993) in which a nanotube is mixed with a polymer monomer and then polymerized, a solution mixing method (KR2007-0077560) in which a polymer is dissolved in a solvent to be mixed with carbon nanotubes And a melt mixing method (KR2006-0007723) in which a polymer is melted and mixed with carbon nanotubes under a high shear force.
The in-situ polymerization method and the solution mixing method require a process of dispersing carbon nanotubes in a solvent by ultrasonic waves. However, it takes a long time to disperse the carbon nanotubes, and since the size of the reaction tank used for dispersion can not be increased, There is a problem of falling and a cost being increased.
As described above, the nanocomposite formed by mixing the carbon nanomaterial and the polymer resin can be used for various industrial fields such as parts materials for electric / electronic products, parts materials and materials for fax machines and copy machines, .
Therefore, there is an urgent need to develop a polymer-carbon nanotube nanocomposite which has excellent rheological properties such as mechanical properties, facilitates process control in its production, and exhibits sufficient electric conductivity when necessary.
However, in order to prepare a master batch by dispersing conductive carbon nanomaterials such as carbon nanotubes, graphenes, carbon fibers and carbon black at a high concentration in a polymer resin, it is necessary to add a large amount of dispersant or ultrasonic treatment for dispersion It is very difficult to uniformly disperse the carbon nanomaterial in the polymer matrix.
DISCLOSURE Technical Problem Accordingly, the present invention has been made in order to solve the problems of the prior art described above, and it is an object of the present invention to provide a method of manufacturing a conductive carbon nanomaterial by introducing a functional group capable of forming three or more multiple hydrogen bonds in a carbon nanotube, Carbon nanomaterial masterbatch is formed by mixing a polymeric resin with a polymeric resin to form a composition in which a supramolecular structure between materials is formed, and then mixing and melting the polymeric resin with a polymer resin to form a nanocomposite. A polymer nanocomposite using the material, and a method for producing the same.
In order to accomplish the above object, the present invention provides a method for producing a polymer nanocomposite using a polymer resin and a carbon nanomaterial, which comprises: introducing a functional group capable of forming multiple hydrogen bonds on the surface and end of a conductive carbon nanomaterial, A first step of forming a carbon nanomaterial having a higher-order structure by hydrogen bonding; A second step of preparing a master batch by mixing a conductive paste and a polymer resin formed by dispersing a carbon nanomaterial having a higher order structure by the multiple hydrogen bonding in a solvent; And a third step of mixing and melting the master batch and the polymer resin to produce a nanocomposite. The polymer nanocomposite using a carbon nanomaterial having a higher order structure by multiple hydrogen bonds and a method of manufacturing the same do.
It is preferable that the carbon nanomaterial is at least one of carbon nanotubes, carbon fibers, graphenes, and carbon black.
The polymer resin may be at least one selected from the group consisting of polycarbonate, polyester resin, polystyrene resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, nylon resin, polyimide resin, polyamide resin, Based resin, a urethane resin, a polyacrylate resin, a polysulfone resin, a polyphenylene sulfide resin, a polyphenylene ether resin, polystyrene, polyvinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, polyetheretherketone And all random, gradient, or block copolymers thereof.
The functional groups capable of multiple hydrogen bonding in the first step are 2-ureido-4 [1H] pyrimidinone derivatives, 2-ureido-4 [H] pyrimidinol 4-ureido-4 [1H] pyrimidinol) derivatives, 2-uriedo-4-pyrimidone derivatives, diacylpyrimidine derivatives, ureidoacylpyrimidine derivatives , Acetylaminotriazine derivatives, ureidotriazine derivatives, 2,6-di (acetylamino) -4-pyridyl derivatives, thymine derivatives, thymine derivative, a 2-aminobenzimidazole derivative, a 2,7-diamino-1,8-naphthyridine derivative, a di (hexanoyl) (Hexanoylamino) pyrimidine derivatives, and 2-butylureido-4-acetylaminopyridine derivatives are preferable.
In the second step, the content ratio of the carbon nanomaterial in the conductive paste is preferably 0.01 to 50 parts by weight based on 100 parts by weight of the solvent.
In the second step, it is preferable that 40 to 95 parts by weight of the polymer resin and 5 to 60 parts by weight of the conductive paste are melted and kneaded under a high shear force to prepare a master batch.
In the second step, it is preferable that the carbon nanomaterial paste having a higher order structure by the multiple hydrogen bonding is mixed with the polymer resin solution to produce a master batch.
In the third step, the carbon nanomaterial content of the nanocomposite is preferably 0.01 to 30.0 parts by weight based on 100 parts by weight of the nanocomposite.
The conductive paste and the nanocomposite prepared in the second and third steps may be prepared by solution spinning or melt spinning to produce a conductive fiber.
Accordingly, by introducing a functional group capable of forming three or more multi-hydrogen bonds into a conductive carbon nanomaterial such as carbon nanotubes or graphene, a composition having a supramolecular structure between materials is formed without using a dispersing agent, and the composition is mixed with a polymer resin A masterbatch of a polymer-carbon nanomaterial is formed and mixed with the polymer resin to form a nanocomposite. The nanocomposite is advantageous in that a high content and a high degree of dispersion of the carbon nanomaterial are maintained without using a dispersant.
According to the present invention, by introducing a functional group capable of forming three or more multi-hydrogen bonds in a conductive carbon nanomaterial such as carbon nanotubes or graphenes, a composition having supramolecular structures between the materials is formed without using a dispersant or the like The polymer-carbon nanomaterial masterbatch is formed by mixing with a polymer resin, and the nanocomposite is formed by mixing and melting the polymer-carbon nanomaterial masterbatch with the polymer resin, thereby maintaining a high content and high dispersibility of the carbon nanomaterial without using a dispersant.
Hereinafter, preferred embodiments of the present invention will be described.
The present invention relates to a method for producing a polymer / carbon nanomaterial nanocomposite by mixing and melting a master batch formed by mixing a carbon nanomaterial and a polymer resin having a higher-order structure by multiple hydrogen bonds with a polymer resin, and a polymer / The present invention relates to a carbon nanomaterial nanocomposite, which comprises introducing a functional group capable of forming multiple hydrogen bonds on the surface and ends of a conductive carbon nanomaterial; Preparing a master batch by mixing the multi-hydrogen bond introduced carbon nanomaterial with a polymer resin; And then mixing and melting the masterbatch and the polymer resin to prepare a polymer / carbon nanomaterial nanocomposite.
Accordingly, by introducing a functional group capable of forming three or more multiple hydrogen bonds in a conductive carbon nanomaterial such as carbon nanotube, graphene, carbon fiber, carbon black, and graphite without using a dispersant, formation of supramolecular structure between the materials is induced It is possible to prepare masterbatches of polymers / carbon nanomaterials having a high content of high-degree of acidity in masterbatch production, and thus, a high content and a high degree of dispersion of carbon nanomaterials are maintained The nanocomposite of the present invention can be produced. Therefore, the polymer / carbon nanomaterial composite prepared according to the production method of the present invention has excellent electrical and rheological properties.
The nanocomposite prepared by mixing the nanocomposite with the intermediate material of the polyimide or polyimide modified body can be melted in a solvent to be made into a film or melted to form a sheet or a three-dimensional structure It is possible to produce polyimide or modified polyimide excellent in conductivity and excellent in heat resistance.
Hereinafter, the present invention will be described in detail with reference to specific examples
≪ Embodiment 1 >
As a first embodiment of the present invention, a functional group capable of quadruple hydrogen bonding is introduced into a multi-walled carbon nanotube, dispersed in a solvent without a dispersant, and polycarbonate (manufactured by SAMYANG Corp.) , Korea) to prepare a master batch, and mixing and melting the master batch with a polycarbonate resin to produce a polymer / carbon nanotube nanocomposite.
First, 10 g multi-walled carbon nanotubes were mixed in a 200 ml sulfuric acid: nitric acid mixture (7: 3 volume ratio), heated to 80 ° C, stirred for 24 hours and cooled to room temperature.
It is then diluted with 800 ml of distilled water. The acid solution remaining in the carbon nanotubes is removed through filtration using filter paper four times or more and then dried to prepare a multi-walled carbon nanotube having a carboxyl group (-COOH) introduced therein.
The carbon nanotubes into which the carboxyl group (-COOH) has been introduced are dispersed in a dimethylformamide solvent at a concentration of 100 mg / L, and thiols (-SH) or diisocyanates into which an amine group is introduced, And the mixture is stirred at 100 ° C for 12 hours to introduce an isocyanate group.
Subsequently, amino-4-hydroxy-6-methyl-pyrimidine was mixed with the isocyanate-introduced carbon nanotubes and stirred at 100 ° C for 20 hours to carry out a bonding reaction 2-ureido-4 [1 H] pyrimidinone, which has a quadruple hydrogen bond, was introduced in such a manner as to carry out the reaction.
The prepared multi-hydrogen bonded supramolecular carbon nanotubes were prepared by using dimethylformamide as a solvent and by simple stirring without using any other additive to prepare a conductive paste having a carbon nanotube solid content of 20% by weight.
The carbon nanotube paste prepared above was fed into a side feeder of a twin-screw extruder, and a polycarbonate and an antioxidant were put into a main hopper, and melted at a kneading speed of 300 rpm and a processing temperature of 250 ° C And kneaded to prepare a polycarbonate-carbon nanotube master batch containing 50% by weight of carbon nanotubes.
The polycarbonate-carbon nanotube masterbatch prepared above and the polycarbonate were fed into a twin-screw extruder and melt-kneaded at a kneading speed of 250 rpm and a processing temperature of 260 ° C to prepare a polycarbonate-carbon nano- Tube nanocomposite was fabricated and nanocomposite with high concentration of carbon nanotube was formed.
≪ Embodiment 2 >
As a second embodiment of the present invention, graphene having multiple hydrogen bonds is used as a conductive carbon nanomaterial, and a master batch is prepared by mixing with a polymer resin, and the resultant is mixed with polycarbonate (SAMYANG Corp., Korea) and And to a method for producing a polymer / graphene nanocomposite by mixing and melting.
First, graphene (oxidized graphene) into which a carboxyl group was introduced was prepared by treating pure graphite with sulfuric acid and KMnO 4 for 3 days and purifying it with hydrogen peroxide and hydrochloric acid using an ultrasonic disperser.
After the prepared graphene oxide was dispersed in dimethyl formamide at a concentration of 500 mg / L, isocyanate and amino-4-hydroxy-6-methylpyrimidine were reacted in the same manner as in Example 1, Was introduced.
The graphene thus prepared was simply stirred to prepare a paste having a solid content of 10%. Hydrazine (N 2 H 4 ) was added and the mixture was stirred at 100 ° C for 12 hours for reduction.
The graphene paste prepared above was fed into a side feeder of a twin-screw extruder. Polycarbonate and an antioxidant were put into a main hopper, and melt-kneaded at a kneading speed of 300 rpm and a processing temperature of 250 ° C To prepare a polycarbonate-graphene master batch containing 30 wt% graphene.
The polycarbonate-graphene masterbatch prepared above and the polycarbonate were fed into a twin screw extruder and melt-kneaded at a kneading speed of 250 rpm and a processing temperature of 260 ° C to obtain a polycarbonate-graphene nano composite The graphene nanocomposite was found to be dispersed at a high concentration.
≪ Third Embodiment >
As a third embodiment of the present invention, the present invention relates to the production of nanocomposites prepared by mixing polycarbonate (SAMYANG Corp., Korea) with carbon nanotubes and graphene.
Carbon nanotubes / graphenes having multiple hydrogen bonds in the same manner as in the first and second embodiments were prepared by mixing carbon nanotubes functionalized with a carboxyl group in the first embodiment and the graphene oxide prepared in the second embodiment The carbon nanotube / graphene composite paste, which is used as a conductive carbon nano material, is put into a side feeder of a twin screw extruder, polycarbonate and an antioxidant are put into a main hopper, Melted and kneaded at a speed of 250 rpm and a processing temperature of 250 占 폚 to prepare a polycarbonate-carbon nanotube / graphen master batch containing 20% by weight of carbon nanotubes / graphene.
The prepared polycarbonate-carbon nanotube / graphene master batch and polycarbonate were fed into a twin-screw extruder and melt-kneaded at a kneading speed of 280 rpm and a processing temperature of 270 ° C to obtain a poly Carbon nanotube / graphene nanocomposite, carbon nanotube / graphene nanocomposite was formed at high concentration.
<Fourth Embodiment>
As a fourth embodiment of the present invention, a master batch was prepared by the same method as in the first embodiment using polyethylene terephthalate (PET) (K177Y, KOLON Ind. Inc.) as a polymer resin, And a nanocomposite having a high concentration of carbon nanotubes was formed.
<Fifth Embodiment>
As a fifth embodiment of the present invention, a master batch was prepared in the same manner as in Example 2 using polypropylene (PP) (PPJ700, HYOSUNG Corp., Korea) and mixed and melted with a polystyrene resin to prepare a nanocomposite. It was found that a nanocomposite having a high concentration of graphene was formed.
<Sixth Embodiment>
As a sixth embodiment of the present invention, a master batch was prepared in the same manner as in Example 3 using nylon 66 (Nylon 66, Kolon Corporation) and mixed and melted with a nylon resin to prepare a nanocomposite. It was found that the nanocomposite dispersed at a high concentration was formed.
<Seventh Embodiment>
As a seventh embodiment of the present invention, in order to introduce a carbon nanomaterial into polyimide having excellent heat resistance and mechanical strength, a functional group capable of multiple hydrogen bonding is introduced into a carbon nanomaterial in the same manner as in the first embodiment to prepare a conductive paste And mixed with polyamic acid, which is a precursor of polyimide, to prepare a polyimide precursor nanocomposite containing carbon nanomaterial. The carbon nanomaterial-containing polyimide nanocomposite can be prepared by dissolving it in a solvent or fiberizing it in a molten state, forming a city form or a three-dimensional structure, and then performing heat treatment at 100 ° C, 250 ° C and 350 ° C for 2 hours, respectively.
≪ Eighth Embodiment >
As a eighth embodiment of the present invention, there is provided a method for producing a synthetic fiber based on a carbon nanomaterial having a high-order structure by thermoplastic polymer and multiple hydrogen bonding, comprising the steps of: Or more of the carbon nanomaterial is prepared and mixed and melted with a polyamide resin to prepare a nanocomposite pellet.
And extruding it to produce conductive fibers. The prepared fibers are improved in conductivity through heat treatment and stretching during or after spinning. It was confirmed that when 30 wt% of the carbon nanomaterial was contained before the heat treatment and stretching, the electric conductivity was 10 3 S / m or less, while the electric conductivity was 10 3 S / m or more after the heat treatment and stretching.
The conductive fibers according to the present invention can be easily mixed with low-dimensional metal materials such as metal nanowires and metal nanoparticles, metal oxides and conductive polymers as well as carbon nanomaterials, thereby increasing the electric conductivity to 10 4 S / m or more have.
<Comparative Example>
As a comparative example of the present invention, a nanocomposite was prepared in the same manner as in Example 1 except that only a functional group such as a carboxyl group was introduced into a carbon nanotube without introducing a functional group into the carbon nanotube. As a result of the experiment, it was confirmed that it was impossible to mix 5 wt% or more of the carbon nanotubes into the polycarbonate resin.
As described above, by introducing a functional group capable of forming three or more multi-hydrogen bonds in a conductive carbon nanomaterial such as carbon nanotubes or graphene without using a dispersant, it is possible to induce the formation of a supramolecular structure between materials, It is possible to prepare a masterbatch of polymer / carbon nanomaterial having a high content of high-degree of acidity in the production of a masterbatch, thereby making it possible to produce a nanocomposite having a high content and a high dispersibility.
Claims (10)
A first step of forming a carbon nanomaterial having a high-order structure by multiple hydrogen bonding between carbon nanomaterials by introducing a functional group capable of multiple hydrogen bonding at the surface and end of the conductive carbon nanomaterial;
A second step of preparing a master batch by mixing a conductive paste and a polymer resin formed by dispersing a carbon nanomaterial having a higher order structure by the multiple hydrogen bonding in a solvent; And
And a third step of mixing and melting the master batch and the polymer resin to produce a nanocomposite. The method for producing a polymer nanocomposite using a carbon nanomaterial having a higher order structure by multiple hydrogen bonding.
Wherein the amount of the carbon nanomaterial is in the range of 0.01 to 50 parts by weight based on 100 parts by weight of the solvent. The method for producing a polymer nanocomposite using a carbon nanomaterial having a higher order structure by multiple hydrogen bonding.
Wherein 40 to 95 parts by weight of the polymer resin and 5 to 60 parts by weight of the conductive paste are melted and kneaded under a high shear force to prepare a masterbatch.
Wherein the masterbatch is formed by mixing the carbon nanomaterial paste having a higher order structure by the multiple hydrogen bonding with the polymer resin solution. The method for producing a polymer nanocomposite using the carbon nanomaterial having a higher order structure by multiple hydrogen bonding.
Wherein the ratio of the carbon nanomaterial to the nanocomposite is 0.01 to 30.0 parts by weight based on 100 parts by weight of the nanocomposite. The method for producing a polymer nanocomposite using the carbon nanomaterial having a higher order structure by multiple hydrogen bonding.
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| KR102174536B1 (en) * | 2019-05-21 | 2020-11-05 | 연세대학교 산학협력단 | Polyamide-carbon nanotube nanocomposite and method for manufacturing the same |
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| US10549996B2 (en) | 2015-12-29 | 2020-02-04 | Georgia Tech Research Corporation | Polymer coated multiwall carbon nanotubes |
| KR101974046B1 (en) * | 2017-11-15 | 2019-08-23 | 울산과학기술원 | Method of manufacturing nylon prepreg having carbon nano material |
| KR20200046235A (en) * | 2018-10-23 | 2020-05-07 | 현대자동차주식회사 | A composite material composition having electromagnetic wave shielding function and a shaped product comprising the same |
| JP7426375B2 (en) | 2019-03-06 | 2024-02-01 | 富士フイルム株式会社 | Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and thermal base generator |
| KR102174536B1 (en) * | 2019-05-21 | 2020-11-05 | 연세대학교 산학협력단 | Polyamide-carbon nanotube nanocomposite and method for manufacturing the same |
| KR102183789B1 (en) * | 2019-08-05 | 2020-11-27 | 부산대학교 산학협력단 | Hybrid nano composites with controlled absorption or luminescence properties and methods for their preparation |
| KR20220030766A (en) * | 2020-09-03 | 2022-03-11 | (주)투디엠 | Filler for polymer composites and the process for producing the same |
| WO2023008813A1 (en) * | 2021-07-29 | 2023-02-02 | 주식회사 네오엔프라 | Led mask polycarbonate resin composition comprising graphene, and led mask manufacturing method using composition |
| KR20230018101A (en) * | 2021-07-29 | 2023-02-07 | 주식회사 네오엔프라 | Polycarbonate resin composition for led mask containing graphene and manufacturing method of led mask using the composition |
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