WO2008106572A1 - Process and performance aid for carbon nanotubes - Google Patents
Process and performance aid for carbon nanotubes Download PDFInfo
- Publication number
- WO2008106572A1 WO2008106572A1 PCT/US2008/055212 US2008055212W WO2008106572A1 WO 2008106572 A1 WO2008106572 A1 WO 2008106572A1 US 2008055212 W US2008055212 W US 2008055212W WO 2008106572 A1 WO2008106572 A1 WO 2008106572A1
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- WIPO (PCT)
- Prior art keywords
- carbon nanotubes
- polymer composition
- polymer
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- resin
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- 0 CC(*)(*)CCCCOC(C(CC1)CCC1C(OOC(C(CC1)CCC1C(OC)=O)=O)=O)=O Chemical compound CC(*)(*)CCCCOC(C(CC1)CCC1C(OOC(C(CC1)CCC1C(OC)=O)=O)=O)=O 0.000 description 1
- SFNCDJVWOAZMFE-UHFFFAOYSA-N O=C(c(cc1)ccc1C(OCCCCOC(c1ccc2cc1)=O)=O)OCCCCOC2=O Chemical compound O=C(c(cc1)ccc1C(OCCCCOC(c1ccc2cc1)=O)=O)OCCCCOC2=O SFNCDJVWOAZMFE-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the present invention relates to a process and performance aid for carbon nanotubes which enhances the handling and processing of carbon nanotubes in preparing a variety of carbon nanotube containing polymer matrixes which exhibit improved performance, including but not limited to electrical conductivity and mechanical properties.
- Nanotubes are known to be composed either of a single sheet, in which case they are called single-walled nanotubes (SWNTs), or made up from several concentric sheets, when they are called multi-walled nanotubes (MWNTs).
- SWNTs single-walled nanotubes
- MWNTs multi-walled nanotubes
- Carbon nanotubes can be formed from petroleum-based sources or form biological-based sources.
- Multi-walled carbon nanotubes are marketed as nanotubes compounded in a resin matrix.
- the resin matrix is formed depending upon customer needs. For example, if the customer is interested in compounding MWCNT's into polyamide-6, a resin matrix of carbon nanotubes in polyamide-6 is prepared.
- the MWCNT's concentration in such matrixes typically ranges from approximately 2% to approximately 20%.
- These matrices are called master batches. This process requires a distinct master batch for each end use. Such a process is costly and inefficient.
- the present invention is directed toward carbon nanotubes encapsulated into a resin matrix and a polymer composition which incorporates carbon nanotubes encapsulated into a resin matrix.
- the resin matrix comprises chains containing aromatic groups, oxygen and/or nitrogen atoms, has a low melting temperature, and a molecular weight such that melt viscosity is low.
- a preferred resin matrix is cyclic butylene terephthalate.
- the carbon nanotube resin matrix is compatible in a wide variety of polymer compositions which have a variety of end uses.
- the resin matrix of the present invention enables easier handling, provides good compatibility with many thermoplastic and thermoset polymer systems, e.g., polyamides, polyesters, polycarbonates, acrylics, chloropolymers, fluoropolymers, epoxies, etc. and is easy to use exhibiting a low melting point and low viscosity in melt and is low in cost.
- the incorporation of the resin matrix into the polymer composition also provides higher electrical conductivity and/or improved mechanical properties. It has now been discovered that a variety of polymer composites containing a resin matrix of cyclic butylene terephthalate and carbon nanotubes display higher electrical conductivity than the analogous composites absent cyclic butylene terephthalate.
- the mechanical properties of a variety of polymer composites can be modified by incorporating therein a resin matrix encapsulating carbon nanotubes, such as cyclic butylene terephthalate and carbon nanotubes.
- a resin matrix encapsulating carbon nanotubes such as cyclic butylene terephthalate and carbon nanotubes.
- the present invention provides a single resin matrix encapsulating carbon nanotubes which can be used in a variety of polymer compositions to modify mechanical properties and/or electric conductivity.
- Figure 1 is a graph of surface electrical conductivity as a function of carbon nanotube concentration in a carbon nanotubes / cyclic butylene terephthalate composite in cyclic butylene terephthalate.
- Figure 2 is a graph of bulk electrical conductivity as a function of carbon nanotubes concentration in a carbon nanotubes / cyclic butylene terephthalate / PA-11 composite.
- Figure 3 is a graph of bulk and surface electrical conductivity as a function of carbon nanotubes concentration in a carbon nanotubes / cyclic butylene terephthalate / PA-11 composite.
- Figure 4 is a graph of mechanical properties as a function of carbon nanotubes concentration in a carbon nanotubes / cyclic butylene terephthalate / PA-11 composite.
- Figure 5 is a graph of bulk electrical conductivity as a function of carbon nanotubes concentration in a carbon nanotubes / cyclic butylene terephthalate / polycarbonate matrix, and electrical conductivity as a function of carbon nanotubes concentration in a carbon nanotubes / polycarbonate matrix.
- Figure 6 is a graph of bulk electrical conductivity in several polymer compositions that comprise 2% carbon nanotubes - introduced as 25% carbon nanotubes / cyclic butylene terephthalate resin matrix or as plain carbon nanotubes.
- Figure 7 is a graph of the effect of process conditions in preparation of carbon nanotubes / cyclic butylene terephthalate resin matrix on electrical conductivity of resultant polymer matrix in which said resin matrix is introduced.
- Figure 8 is a graph of the effect of carbon nanotubes /cyclic butylene terephthalate resin matrix on mechanical properties of epoxy polymer matrix.
- Figure 9a is a transmission optical photograph of the epoxy matrix listed as "Composite" in Figure 8.
- Figure 9b is a transmission optical photograph of the epoxy matrix listed as
- the present inventors discovered that incorporation of carbon nanotubes into a resin matrix simplifies melt processing in polymer matrixes and/or addition into polymer matrixes and provides a polymer matrix having higher electrical conductivity and/or improved mechanical properties.
- the resin matrix comprises chains containing aromatic groups, oxygen and/or nitrogen atoms, has a low melting temperature (less than about 200° C), and a molecular weight such that melt viscosity is low (less than about 5000 centipoise).
- a preferred resin matrix is cyclic butylene terephthalate (CBT).
- the concentration of carbon nanotubes in the resin matrix is preferably between about 0.1 and 50% by weight, more preferably between about 5 and 33% by weight and most preferably about 25% by weight. Unless otherwise specified, all percentages herein are percentages by weight and all temperatures are in degrees Centigrade (degrees Celsius).
- carbon nanotubes can increase the electrical conductivity of a polymer matrix at relatively low concentration, hi many cases, less than 5% by weight, and often less than 2% by weight. This makes the polymer matrix suitable for numerous applications, such as electrostatic painting, static charge dissipation, and electromagnetic interference shielding. Metals can be used in these applications, but conductive polymers offer a lower-cost, lighter-weight, alternative. Carbon black can provide a conductivity effect in polymers. However, with carbon black, much higher concentrations are required, typically 10-20% by weight. Such a level of additives, while providing good electrical conductivity, reduces other properties of the polymer, such as mechanical strength, impact resistance, gas/liquid permeability, etc.
- Carbon nanotubes provide good electrical conductivity while also maintaining other desirable polymer properties.
- Some examples of applications where a polymer/nanotube composition could be advantageous are: conductive polymer fuel handling components of automobiles, electrostatically paintable thermoplastic automotive body/interior components, coatings to shield electronic equipment, etc.
- carbon nanotubes Another property of importance in the use of carbon nanotubes is an increase in mechanical properties of a polymer matrix at a relatively low concentration of carbon nanotubes. This makes the polymer matrix suitable for applications where otherwise, heavier, more expensive materials are needed, such as metals.
- Some examples of carbon nanotube - containing composites are tennis rackets, baseball bats, golf clubs, bicycle components and possibly automotive and aeronautical components.
- Still more applications for carbon nanotube containing composites, with carbon nanotubes properly dispersed in a polymer matrix include, but are not limited to: membranes employed for selective separation of gases, composites displaying enhanced flame retardancy, coatings or composites showing enhanced resistance to UV degradation, coatings showing enhanced absorption of visible light, coatings and composites showing enhanced wear resistance, coatings showing enhanced scratch resistance, coatings and composites having enhanced chemical resistance to dissolving/swelling agents, composites in which stress/ strain/defects can be detected easily, composite acoustic sensors and actuators, electrode materials in capacitors, fuel cells, rechargeable batteries, electrically conductive and injury-resistant fabric, composites in a variety of electronic devices, such as glucose sensors, LED displays, solar cells, pH sensors
- Cyclic butylene terephthalate is a monomer of polybutylene terephthalate. The monomer and polymer are depicted below. Cyclic butylene terephthalate is non- hazardous and is compatible with a wide variety of thermoplastic and thermoset polymers where incorporation of carbon nanotubes may be desirable such as polyamides, polyesters, polycarbonates, polyacrylics, polyolefms, chloropolymers, fluoropolymers, and epoxies etc. Cyclic butylene terephthalate is easy to use, having a low melting point (15O 0 C) and viscosity in melt which is low, like water.
- the carbon nanotube in cyclic butylene terephthalate resin matrix can be prepared by an evaporation process where the carbon nanotubes are dispersed in a liquid medium such as a solvent, such as by stirring and/or sonication, followed by dissolution of cyclic butylene terephthalate in the medium, followed by evaporation of the liquid medium.
- This process or any other suitable process forms a resin matrix of carbon nanotubes in a matrix of cyclic butylene terephthalate.
- This resin matrix can be mixed with a polymer matrix via conventional processes such as mixing in an extruder or any other suitable process. Heating can be provided with microwave heating equipment.
- the carbon nanotube in cyclic butylene terephthalate resin matrix can be prepared by direct melt mixing of carbon nanotubes on melt mixing equipment.
- the work applied during mixing can impact the physical properties of the final polymer composition.
- the amount of working applied during melt mixing is a function of the equipment being used and its operating conditions such as: the temperature, screw speed and mixing time.
- the inventors found that an upper limit on mixing was provided in a DSM Research B. V MIDI 2000 twin screw extruder having a 15 cm 3 capacity when the temperature was about 150 0 C or greater, at a screw speed of 100 rpm or less and a mixing time of 10 minutes or less. Providing working about or less than these parameters is preferred.
- Preferred operation parameters were temperature about 200°C at a screw speed of 25 rpm and a mixing time of about 2 to 3 minutes. Based upon these parameters, a person skilled in the art could determine the desired conditions for other extruding equipment to avoid over working and degrading the desirable properties provided the present invention.
- Polymer matrixes incorporating a resin matrix of carbon nanotubes in cyclic butylene terephthalate have been found to exhibit enhanced electrical conductivity, a low percolation threshold and enhanced mechanical properties.
- concentration of carbon nanotubes in the polymer composition can range from about 0.01 to 25% by weight, preferably from about 0.1 to 10%, more preferably from about 0.5 to 5% and most preferably from about 1 to 3%.
- Figure 3 shows bulk and surface electrical conductivity as a function of carbon nanotubes concentration for a matrix of carbon nanotubes / cyclic butylene terephthalate / PA-I l composite in accordance with the present invention.
- PA-I l is RilsanTM BMNO PCG available form Arkema Inc. Measurement of conductivity was by simple 2-probe measurement. Note there is three parts cyclic butylene terephthalate for every one part carbon nanotubes. Silver paint was employed to ensure good contact.
- Figure 4 shows mechanical properties as a function of carbon nanotube concentration for a matrix of carbon nanotubes / cyclic butylene terephthalate / PA-11 composite in accordance with the present invention.
- PA-11 is RilsanTM BMNO PCG.
- the matrixes were prepared via melt mixing at 21O 0 C and injection molding was at 200 0 C. Note there is three parts cyclic butylene terephthalate for every one part carbon nanotubes.
- Figure 5 shows bulk electrical conductivity as a function of carbon nanotubes concentration for a matrix of carbon nanotubes / cyclic butylene terephthalate / polycarbonate composite in accordance with the present invention. Preparation is according to Example 11. Also shown are same results for a polymer matrix of carbon nanotubes / polycarbonate. Polycarbonate is from Dow Chemical Co. - Water White. Measurement of conductivity was by simple 2-probe measurement. For composites containing cyclic butylene terephthalate, there were three parts cyclic butylene terephthalate for every one part carbon nanotubes. Silver paint was employed to ensure good contact.
- Figure 6 shows bulk electrical conductivity in several polymer matrices that comprise 2% carbon nanotubes - introduced as 25% carbon nanotubes / cyclic butylene terephthalate resin matrix, or as plain carbon nanotubes.
- Conditions are according to Example 9. Measurement of conductivity was by simple 2-probe measurement. For composites containing cyclic butylene terephthalate, there were three parts cyclic butylene terephthalate for every one part carbon nanotubes. Silver paint was employed to ensure good contact.
- Figure 7 shows the effect of process conditions in the preparation of carbon nanotubes / cyclic butylene terephthalate resin matrix on the electrical conductivity of resultant polymer matrix in which said resin matrix is introduced.
- the polymer matrix was Polyamide-12 (Arkema Inc. Rilsan AMNO TLD).
- the conditions of preparation were as in Examples 7 and 8, and conditions of polymer matrix preparation were as in Example 10.
- Each comprised 2% carbon nanotubes - introduced as 25% carbon nanotubes / cyclic butylene terephthalate resin matrix. Measurement of conductivity was by simple 2-probe measurement. Silver paint was employed to ensure good contact.
- Figure 8 is a graph of the effect of carbon nanotubes /cyclic butylene terephthalate resin matrix on the mechanical properties of an epoxy polymer matrix, and of said polymer matrices. Conditions were according to Example 11.
- Figures 9a and 9b are transmission optical microscope images of the epoxy polymer matrix with carbon nanotubes/cyclic butylene terephthalate of Figure 8.
- Example 1 4.5 g of carbon nanotubes (Graphistrength ® ClOO available from Arkema France was used in all examples) were added to about 165 g of solution of cyclic butylene terephthalate in methylene chloride (9% by weight). This mixture was sonicated with a Sonics & Materials VC-505 unit set at 50% amplitude for about 2 hours. The resultant mixture was cast on aluminum foil and solvent allowed to evaporate. The resultant powder was about 20% by weight carbon nanotubes.
- Example 2 21 g of carbon nanotubes were added to 800 g of methylene chloride. Sonication was performed with a Sonics & Materials VC-505 unit set at 50% amplitude for about 4 hours. Stirring was continuous with a magnetic stir bar. To this was added 64 grams of cyclic butylene terephthalate. Stirring on a roll mill was performed for about 3 days. The resultant mixture was cast on aluminum foil and solvent allowed to evaporate. The resultant powder is about 25% by weight carbon nanotubes.
- Example 1 Materials from Examples 1 and 2 were blended with fresh cyclic butylene terephthalate, and melt mixed on a DSM midi extruder. Parameters were: 15O 0 C, 75 rpm for 10 minutes. In Figure 1 is shown electrical conductivity as a function of carbon nanotubes concentration. Method 1 comprises use of material from Example
- Method 2 comprises use of material from Example 2.
- Figure 1 shows the higher conductivity and lower percolation threshold for material made via Example 2 both advantageous properties. Measurement was by simple 2-probe measurement.
- the process of Example 2 is a preferred preparation method of carbon nanotubes / cyclic butylene terephthalate composites. Sonication prior to resin introduction is preferred.
- Figure 2 shows the conductivity of carbon nanotubes / cyclic butylene terephthalate / PA-I l composite (line A), and carbon nanotubes / PA-I l composite
- PA-I l is RilsanTM BMNO PCG available for Arkema Inc. Carbon nanotubes / cyclic butylene terephthalate composite was made according to Example
- Example 3 Cyclic butylene terephthalate was added to a round bottom flask and melted with a surrounding heating mantle. Carbon nanotubes already present were mixed in with a combination of stirring and sonication. Allowing cyclic butylene terephthalate to solidify resulted in a solid carbon nanotubes / cyclic butylene terephthalate composite.
- Example 5 Cyclic butylene terephthalate and carbon nanotubes were mixed in dry form, then melt mixed in a DSM midi extruder (15 cm 3 capacity) at 15O 0 C. The resultant product was a solid carbon nanotubes / cyclic butylene terephthalate composite comprising approximately 10% carbon nanotubes.
- Example 6 The use of a carbon nanotubes / cyclic butylene terephthalate resin matrix to introduce carbon nanotubes into a polymer matrix was studied.
- the polymer chosen was polyamide-11. Specifically used were Rilsan ® BMNO PCG available form Arkema Inc. Polyamides such as Polyamide -11 may be an important end use application for carbon nanotubes.
- a carbon nanotubes / cyclic butylene terephthalate composite prepared in accordance with Example 2 was melt mixed with polyamide PA-I l in a DSM midi extruder for 10 minutes at 75 rpm at 285 0 C. The extrudate was captured. There were three parts cyclic butylene terephthalate for every one part carbon nanotubes. Therefore, the sample at 2% carbon nanotubes was 6% cyclic butylene terephthalate and 92% polyamide PA-11.
- raw carbon nanotubes were considered as well.
- Raw carbon nanotubes were melt mixed with PA-I l in the DSM midi extruder for 10 minutes at 75 rpm at 285 0 C. Extrudate was captured. Since there is no cyclic butylene terephthalate, the sample at 2% carbon nanotubes, was 98% PA-11.
- One obvious benefit of cyclic butylene terephthalate is that it makes melt compounding of carbon nanotubes much easier. Experiments with raw carbon nanotubes were difficult. Those with cyclic butylene terephthalate were not. Mixtures of PA-I l and raw carbon nanotubes, as dilute as 0.5% carbon nanotubes, caused jamming of the extruder barrel.
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Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009551837A JP5466952B2 (en) | 2007-03-01 | 2008-02-28 | Processing and performance aids for carbon nanotubes |
EP08730904A EP2115041A4 (en) | 2007-03-01 | 2008-02-28 | Process and performance aid for carbon nanotubes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US89230207P | 2007-03-01 | 2007-03-01 | |
US60/892,302 | 2007-03-01 |
Publications (1)
Publication Number | Publication Date |
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WO2008106572A1 true WO2008106572A1 (en) | 2008-09-04 |
Family
ID=39721607
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2008/055212 WO2008106572A1 (en) | 2007-03-01 | 2008-02-28 | Process and performance aid for carbon nanotubes |
Country Status (7)
Country | Link |
---|---|
US (1) | US9029458B2 (en) |
EP (1) | EP2115041A4 (en) |
JP (1) | JP5466952B2 (en) |
KR (1) | KR101471824B1 (en) |
CN (2) | CN101627072A (en) |
TW (1) | TWI448415B (en) |
WO (1) | WO2008106572A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009197056A (en) * | 2008-02-19 | 2009-09-03 | Teijin Chem Ltd | Conductive resin molding material |
EP2426163A1 (en) | 2010-09-07 | 2012-03-07 | Bayer MaterialScience AG | Method for manufacturing polymer-CNT composites |
JP2012526885A (en) * | 2009-05-12 | 2012-11-01 | アルケマ フランス | Fiber substrate, method for producing the fiber substrate, and use thereof |
EP2810977A1 (en) | 2013-06-07 | 2014-12-10 | Bayer MaterialScience AG | Composition and process for the preparation of polymer-CNT composites |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2918081B1 (en) * | 2007-06-27 | 2009-09-18 | Cabinet Hecke Sa | METHOD FOR IMPREGNATING FIBERS CONTINUOUS BY A COMPOSITE POLYMERIC MATRIX COMPRISING A THERMOPLASTIC POLYMER |
JP5619547B2 (en) * | 2010-09-17 | 2014-11-05 | 日信工業株式会社 | Method for producing carbon fiber composite material and carbon fiber composite material |
KR20120058347A (en) * | 2010-11-29 | 2012-06-07 | 현대자동차주식회사 | Thermo plastic complex for stiffener and Preparing method thereof |
CN102654672B (en) * | 2011-11-18 | 2015-07-22 | 京东方科技集团股份有限公司 | Display device and array substrate as well as color filter substrate and manufacturing method thereof |
WO2014039509A2 (en) | 2012-09-04 | 2014-03-13 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
US9381449B2 (en) * | 2013-06-06 | 2016-07-05 | Idex Health & Science Llc | Carbon nanotube composite membrane |
US9115266B2 (en) | 2013-07-31 | 2015-08-25 | E I Du Pont De Nemours And Company | Carbon nanotube-polymer composite and process for making same |
US20150073088A1 (en) * | 2013-09-06 | 2015-03-12 | Korea Institute Of Science And Technology | Composite of filler and polymer resin and method for preparing the same |
KR101612454B1 (en) * | 2014-09-30 | 2016-04-15 | 한국과학기술연구원 | Heat-dissipating sheet including composite layer of filler and polymer resin and method for preparing the same |
WO2023070439A1 (en) * | 2021-10-28 | 2023-05-04 | Cabot Corporation | Dispersion of carbon nanostructures |
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US20050186378A1 (en) * | 2004-02-23 | 2005-08-25 | Bhatt Sanjiv M. | Compositions comprising carbon nanotubes and articles formed therefrom |
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US20060210466A1 (en) * | 2005-03-11 | 2006-09-21 | Somenath Mitra | Microwave induced functionalization of single wall carbon nanotubes and composites prepared therefrom |
US20060274049A1 (en) * | 2005-06-02 | 2006-12-07 | Eastman Kodak Company | Multi-layer conductor with carbon nanotubes |
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JP2001348215A (en) * | 2000-05-31 | 2001-12-18 | Fuji Xerox Co Ltd | Manufacturing method of carbon nanotube and/or fullerene and manufacturing device therefor |
US8999200B2 (en) | 2002-07-23 | 2015-04-07 | Sabic Global Technologies B.V. | Conductive thermoplastic composites and methods of making |
KR20050096099A (en) * | 2002-12-23 | 2005-10-05 | 다우 글로벌 테크놀로지스 인크. | Electrically conductive polymerized macrocyclic oligomer carbon nanofiber compositions |
JP2006063307A (en) * | 2004-07-27 | 2006-03-09 | Ezaki Glico Co Ltd | Carbon nanotube-containing solution, film, and fiber |
EP1728822A1 (en) * | 2005-05-30 | 2006-12-06 | Nanocyl S.A. | Nanocomposite and process for producing the same |
KR20080032186A (en) * | 2005-07-15 | 2008-04-14 | 시클릭스 코포레이션 | Macrocyclic polyester oligomers as carriers and/or flow modifier additives for thermoplastics |
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2008
- 2008-02-28 CN CN200880006693A patent/CN101627072A/en active Pending
- 2008-02-28 JP JP2009551837A patent/JP5466952B2/en active Active
- 2008-02-28 KR KR1020097018181A patent/KR101471824B1/en active IP Right Grant
- 2008-02-28 CN CN201510329769.2A patent/CN104893265A/en active Pending
- 2008-02-28 WO PCT/US2008/055212 patent/WO2008106572A1/en active Application Filing
- 2008-02-28 EP EP08730904A patent/EP2115041A4/en not_active Withdrawn
- 2008-02-28 US US12/524,932 patent/US9029458B2/en active Active
- 2008-02-29 TW TW097107400A patent/TWI448415B/en active
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US20030125478A1 (en) * | 2000-05-17 | 2003-07-03 | Mari Beek Franciscus Johannes | High performance thermoplastic compositions with improved melt flow properties |
US20050186378A1 (en) * | 2004-02-23 | 2005-08-25 | Bhatt Sanjiv M. | Compositions comprising carbon nanotubes and articles formed therefrom |
US20060067055A1 (en) * | 2004-09-30 | 2006-03-30 | Heffner Kenneth H | Thermally conductive composite and uses for microelectronic packaging |
US20060210466A1 (en) * | 2005-03-11 | 2006-09-21 | Somenath Mitra | Microwave induced functionalization of single wall carbon nanotubes and composites prepared therefrom |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2009197056A (en) * | 2008-02-19 | 2009-09-03 | Teijin Chem Ltd | Conductive resin molding material |
JP2012526885A (en) * | 2009-05-12 | 2012-11-01 | アルケマ フランス | Fiber substrate, method for producing the fiber substrate, and use thereof |
EP2426163A1 (en) | 2010-09-07 | 2012-03-07 | Bayer MaterialScience AG | Method for manufacturing polymer-CNT composites |
WO2012031989A1 (en) | 2010-09-07 | 2012-03-15 | Bayer Materialscience Ag | Process for producing polymer-cnt composites |
EP2810977A1 (en) | 2013-06-07 | 2014-12-10 | Bayer MaterialScience AG | Composition and process for the preparation of polymer-CNT composites |
Also Published As
Publication number | Publication date |
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JP2010520331A (en) | 2010-06-10 |
TW200904744A (en) | 2009-02-01 |
KR101471824B1 (en) | 2014-12-15 |
JP5466952B2 (en) | 2014-04-09 |
TWI448415B (en) | 2014-08-11 |
CN101627072A (en) | 2010-01-13 |
KR20090127127A (en) | 2009-12-09 |
US9029458B2 (en) | 2015-05-12 |
US20100210781A1 (en) | 2010-08-19 |
EP2115041A4 (en) | 2012-09-05 |
EP2115041A1 (en) | 2009-11-11 |
CN104893265A (en) | 2015-09-09 |
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