EP1893689A1 - Kohlenstoffnanoröhren enthaltende polymermaterialien und verfahren zu ihrer herstellung aus einer vormischung mit einem dispergiermittel - Google Patents

Kohlenstoffnanoröhren enthaltende polymermaterialien und verfahren zu ihrer herstellung aus einer vormischung mit einem dispergiermittel

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Publication number
EP1893689A1
EP1893689A1 EP06764818A EP06764818A EP1893689A1 EP 1893689 A1 EP1893689 A1 EP 1893689A1 EP 06764818 A EP06764818 A EP 06764818A EP 06764818 A EP06764818 A EP 06764818A EP 1893689 A1 EP1893689 A1 EP 1893689A1
Authority
EP
European Patent Office
Prior art keywords
polymer matrix
cnts
premix
dispersing
polymers
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.)
Withdrawn
Application number
EP06764818A
Other languages
English (en)
French (fr)
Inventor
Nour-Eddine El Bounia
Ludwik Leibler
Sylvie Tence-Girault
Corinne Soulie-Ziakovic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Original Assignee
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from FR0506439A external-priority patent/FR2887554B1/fr
Application filed by Centre National de la Recherche Scientifique CNRS, Arkema France SA filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP1893689A1 publication Critical patent/EP1893689A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • 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
    • 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
    • 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
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the present invention relates to a process for dispersing carbon nanotubes in polymer materials containing carbon nanotubes and the polymer materials obtained.
  • CNTs carbon nanotubes
  • Nanotubes composed of a single sheet are known and are then referred to as SWNTs (for Single Wall Nanotubes) or nanotubes composed of several concentric sheets then called MWNT (for Multi Wall
  • SWNTs being generally more difficult to manufacture than MWNTs.
  • CNTs are in powder form, making them difficult to handle with HSE risks for operators.
  • EP 692,136 describes polymer compositions containing up to 20% by weight of CNTs; these thermoplastic or thermosetting compositions are prepared by melt blending the polymers with the CNTs.
  • the dispersion of the CNTs within the polymer matrix is not homogeneous and the expected mechanical and / or electrical properties are insufficient.
  • EP 1,359,121 and EP 1,359,169 propose to improve the dispersion of CNTs in polymer matrices by functionalization of CNTs.
  • the polyamide may be a copolymer with polyamide blocks and polyether blocks.
  • this document does not deal with the problem of dispersion of carbon nanotubes within polymer matrices.
  • the present invention relates to a method for easily dispersing carbon nanotubes within polymer matrices.
  • the process for dispersing the CNTs developed by the Applicant consists in dispersing and coating the CNTs by premixing the CNTs with a dispersing and coating agent chosen from polyamide block and polyether block copolymers (PEBA) and / or polyester block copolymers and polyether blocks.
  • a dispersing and coating agent chosen from polyamide block and polyether block copolymers (PEBA) and / or polyester block copolymers and polyether blocks.
  • NTC + dispersing agent NTC + dispersing agent
  • the CNTs can represent up to 70 parts by weight of the total mass of the premix.
  • the carbon nanotubes used can be of any type:
  • MWNT MWNT
  • DWNT double wall
  • SWNT functionalized or not.
  • the carbon nanotubes have a shape ratio (L / D) greater than or equal to 5 and preferably greater than or equal to 50 and advantageously greater than or equal to 100.
  • the carbon nanotubes have a diameter of between 0 , 4 and 50 nm and a length of 100 and 100,000 times their diameter.
  • the carbon nanotubes are in multiwall form (MWT), their diameter being between 5 and 30 nm and their length being greater than or equal to 0.3 ⁇ m.
  • the amount of carbon nanotubes advantageously represents from 0.1 to 70 parts by weight, and advantageously from 0.1 to 30 parts by weight, and still more preferably from 0.5 to 20 parts by weight of the total mass of the premix.
  • PEBAs resulting from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends such as, inter alia:
  • Polyamide sequences with dicarboxylic chain ends with polyoxyalkylene sequences with diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxy aliphatic polyoxyalkylene aliphatic sequences called polyether diols.
  • the polyamide sequences with dicarboxylic chain ends come for example from the condensation of polyamide precursors in the presence of a dicarboxylic acid chain limiter.
  • the polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine.
  • Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks. For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. A polymer having essentially polyether blocks, polyamide blocks of very long length is obtained. variable, but also the various reagents reacted randomly that are distributed randomly (statistically) along the polymer chain.
  • polyetherdiamine polyamide precursors and a chain-limiting diacid.
  • the amount of polyether blocks in these polyamide block copolymers and polyether blocks generally represents 10 to 70% by weight of the copolymer.
  • polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or aminated to be converted into polyether diamines and condensed with polyamide blocks having carboxylic ends. They can also be mixed with polyamide precursors and a diacid chain limiter to make the polyamide block and polyether block polymers having statistically distributed patterns.
  • PEBAX® which are PEBAs may for example be mentioned.
  • VESTAMID® which are PEBAs may for example be mentioned.
  • polyether block copolymers and polyether blocks are block polyetheresters. They consist of flexible polyether blocks which are the residues of polyetherdiols and rigid segments (polyester blocks) which result from the reaction of at least one dicarboxylic acid with at least one short chain-extending diol unit. The polyester blocks and the polyether blocks are linked by ester bonds resulting from the reaction of the acid functions of the acid with the OH functions of the polyetherdiol.
  • the short chain extending diol may be chosen from the group consisting of neopentyl glycol, cyclohexanedimethanol and aliphatic glycols of formula HO (C 1) n OH in which n is an integer ranging from 2 to 10.
  • the diacids are dicarboxylic acids aromatic compounds having 8 to 14 carbon atoms. Up to 50 mol% the aromatic dicarboxylic acid may be replaced by at least one other aromatic dicarboxylic acid having 8 to 14 carbon atoms, and / or up to 20 mol% may be replaced by an aliphatic dicarboxylic acid having 2 to 12 carbon atoms. carbon.
  • aromatic dicarboxylic acids examples include terephthalic acid, isophthalic acid, bibenzoic acid, naphthalene dicarboxylic acid, 4,4'-diphenylenedicarboxylic acid, bis (p-carboxyphenyl) methane, and ethylene bis benzoic acid, 1-4 tetramethylene bis (p-oxybenzoic) acid, bis (para-oxybenzoic) ethylene acid, 1,3-trimethylene bis (p-oxybenzoic acid).
  • polyester block and polyether block copolymers are, for example, copolymers having polyether units derived from polyetherdiols such as PEG, PPG or PTMG, dicarboxylic acid units such as terephthalic acid and glycol (ethane diol) units or butane diol, 1-4.
  • polyethers and diacids forms the flexible segments whereas the linking of the glycol or butanediol with the diacids forms the rigid segments of the copolyetherester.
  • copolyetheresters are for example described in patents EP 402 883 and EP 405227. These polyetheresters are thermoplastic elastomers; they may contain plasticizers.
  • the premix can be made by solvent or melt.
  • the solvent route consists of solubilizing the dispersing agent in a solvent and incorporating the CNTs into this solution. From this solution containing dispersion CNTs, it is possible to prepare any type of object of selected shape and size, in particular of films, for example by filling a mold of selected dimensions and evaporation of the solvent.
  • PEBA solvents By way of examples of PEBA solvents, mention may be made, for example, of mixtures of at least one solvent of the polyether blocks, such as benzene, chloroform, dichloromethane, ethanol and tetrahydrofuran, and at least one solvent of the polyamide blocks, such as dimethylformamide, dimethylsulfoxide, hexafluoroisopropanol (HFIP), cresol.
  • solvent of the polyether blocks such as benzene, chloroform, dichloromethane, ethanol and tetrahydrofuran
  • solvent of the polyamide blocks such as dimethylformamide, dimethylsulfoxide, hexafluoroisopropanol (HFIP), cresol.
  • the solution of dispersing agent, solvent and CNT is prepared at temperatures generally ranging from 0 to 100 ° C., preferably close to ambient temperature (for economic reasons) and below the boiling temperatures of the solvents. or solvent mixtures used.
  • the amount of solvent used depends on the solubility of the dispersing agent and can represent up to 90 parts by weight of the total mass of the solution. It is preferred, however, not to "dilute" the dispersion agent solutions as much as the next step will be to remove the solvent.
  • the dispersions of CNTs in the dispersing agent solutions are stable in duration and temperature (several months at ambient temperature), which is an advantage in the case of storage prior to incorporation of these dispersions into polymeric materials.
  • the second way of preparing the premix according to the invention is to operate by melting: the dispersion agent is heated until complete melting and the CNTs are introduced simultaneously and / or after its melting.
  • any mixing apparatus that can be used for the dispersing agents according to the invention, such as kneader, internal mixer, single or twin screw extruder, bus, ultraturax type mixer, blender. ultrasound or any type of mixing tool known to those skilled in the art.
  • the present invention also relates to polymeric materials comprising at least one premix as defined above and a polymer matrix.
  • the proportion of CNTs in the mixed polymer material is from 1 to 20 parts by weight.
  • polymer matrix is meant any composition based on polymer (s) of any kind: thermoplastic or thermosetting, rigid or elastomeric, amorphous, crystalline and / or semi-crystalline, homopolymer, copolymer, ... which are compatible with at least l one of the blocks of the dispersing agent; these compositions may be mixtures of one or more different polymers with various additives, additives and / or fillers conventionally added to the polymers, such as stabilizers, plasticizers, polymerization catalysts, dyes, pigments, lubricants, flame retardants, reinforcements and / or fillers , polymerization solvents, ...
  • the present invention also relates to the process for preparing polymeric materials comprising the premix according to the invention described above with a polymer matrix compatible with said premix. It can be carried out for example by melting or by solvent.
  • the preparation process can use different technologies such as those used for rubbers, polymers, liquids, depending on the nature of the polymers present in the final polymer material.
  • technologies such as those used for rubbers, polymers, liquids, depending on the nature of the polymers present in the final polymer material.
  • polymeric materials can be obtained directly by melt blending the polymer matrix (s) and the premix, the latter serving as a master batch or master batch as described in WO 91/03057 or US 5.646.990, EP 692,136 or US 5,591,382 US 5,643,502 or US 5,651,922, US 6,221,283.
  • polymers previously described can also be obtained by solvent, by solubilizing the premix and the polymer matrix in one or more solvents followed by a step of removing the solvent or solvents, for example by evaporation.
  • polymers which are compatible with dispersing agents mention may be made of amide-functional polymers, mention may be made of polymers resulting from the condensation of: one or more amino acids, such as aminocaproic acids, amino-7 heptanoic, amino-11-undecanoic (PA-11) and amino-12-dodecanoic (PA-12) of one or more lactams such as caprolactam (PA-6), oenantholactam and lauryllactam;
  • one or more salts or mixtures of diamines such as hexamethylenediamine, dodecamethylenediamine, metaxylylenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylenediamine with diacids such as isophthalic, terephthalic, adipic, azelaic, suberic, sebacic acids; and dodecanedicarboxylic;
  • copolyamides for example PA-6/12 by condensation of caprolactam and lauryllactam.
  • aliphatic polyamides resulting from the condensation of an aliphatic diamine having from 6 to 12 carbon atoms and an aliphatic diacid having from 9 to 12 carbon atoms mention may be made of: the resulting PA 6-12 condensation of hexamethylenediamine and 1,12-dodecanedioic acid,
  • aliphatic polyamides resulting from the condensation of an aliphatic diamine having from 6 to 12 carbon atoms and an aliphatic diacid having from 9 to 12 carbon atoms and amino acids mention may be made of:
  • the amide functional polymer can be plasticized.
  • plasticizer they are generally chosen from benzene sulphonamide derivatives, such as n-butyl benzene sulphonamide (BBSA), ethyl toluene sulphonamide or N-cyclohexyl toluene sulphonamide; hydroxybenzoic acid esters, such as 2-ethylhexyl parahydroxybenzoate and 2-decyl hexyl parahydroxybenzoate; esters or ethers of tetrahydrofurfuryl alcohol, such as oligoethyleneoxytetrahydrofurfurylalcohol; and esters of citric acid or hydroxy-malonic acid, such as oligoethyleneoxy malonate.
  • BBSA n-butyl benzene sulphonamide
  • ethyl toluene sulphonamide or N-cyclohexyl toluene sulphonamide hydroxybenz
  • a particularly preferred plasticizer is n-butyl benzene sulfonamide (BBSA).
  • BBSA n-butyl benzene sulfonamide
  • the plasticizer (s) may be introduced into the polyamide during the polycondensation or subsequently.
  • the proportion of plasticizer can generally be up to 30% by weight of the amide functional polymer.
  • the amide-functional polymer may also be a copolymer with polyamide blocks and polyether blocks (PEBA) as defined above.
  • PEBA polyether blocks
  • polyurethanes consisting of flexible polyether blocks which are residues of polyetherdiols and rigid blocks (polyurethanes) which result from the reaction of at least one diisocyanate with at least one short diol.
  • the short chain extending diol may be chosen from the glycols mentioned above in the description of the polyetheresters.
  • the polyurethane blocks and the polyether blocks are connected by bonds resulting from the reaction of the isocyanate functional groups with the OH functions of the polyetherdiol.
  • polyesterurethanes for example those comprising diisocyanate units, units derived from amorphous polyester diols and units derived from a short chain-extending diol. They may contain plasticizers.
  • thermoplastic polyurethanes As an example of commercial thermoplastic polyurethanes, ELASTOLLAN® from Elastogran Bayer can for example be mentioned.
  • ether-functional polymers mention may be made of polyoxyalkylenes and in particular polyoxymethylene (POM), poly (propylene oxide-ethylene oxide) block copolymers and polyphenylene oxide (PPO).
  • POM polyoxymethylene
  • PPO polyphenylene oxide
  • polyalkylene glycols which are polyethers terminated by hydroxyl functions, such as polyethylene glycol (PEG), polypropylene glycol, polytetramethylene glycol (PTMG) as well as the block copolymers polyesters and polyether blocks defined above.
  • PEG polyethylene glycol
  • PTMG polytetramethylene glycol
  • ester function-derived polymers and in particular (alkyl) acrylate polymers or acrylic polymers, homo-and copolymers of one or more alkyl (alkyl) acrylates, which are described in particular in US Pat. Kirk Othmer, Encyclopedia of Chemical Technology, 4th edition, vol 1, pages 292-293 and Volume 16, pages 475-478 and in particular (co) methyl methacrylate polymer (PMMA).
  • polymers containing units derived from one or more vinyl esters of saturated carboxylic acids such as, for example, acetate or vinyl propionate.
  • copolymers of ethylene and vinyl acetate marketed in particular under the names EVATANE®, ELVAX®, ULTRATHENE®, may be mentioned.
  • o polycarbonates o EPR elastomers (ethylene - propylene - rubber) and EPDM elastomers (ethylene - propylene - diene) possibly maleised, o copolymers of butadiene and acrylonitrile, or nitrile rubber (NBR) optionally comprising carboxylic functions polymers containing vinyl functions, homo- and copolymers, which derive in particular from vinyl monomer (s), such as vinyl chloride.
  • vinyl polymers mention may be made of polyvinyl chloride (PVC), superchlorinated PVC, possibly plasticized, etc.
  • the polymeric materials according to the invention may advantageously replace the polymer materials containing CNTs of the state of the art and be used in many fields, in particular in electronics (depending on the temperature and their structure, they may be conductive, semiconductors or insulators), in mechanics, for example for reinforcing materials composites (the CNTs are a hundred times stronger and six times lighter than steel) and electromechanical (they can lengthen or contract by charge injection).
  • materials intended for example for the packaging of electronic components, with electromagnetic shielding and anti-static dissipation such as mobile phone housings, computers, on-board electronic devices on motor vehicles, rail and air vehicles, medical instruments, fuel lines, antistatic coatings or coatings, thermistors, electrodes, especially for supercapacitors, etc.
  • PEBA1 comprising PTMG polyether blocks (2000 g / mol) and PA-12 blocks (600 g / mol) in the form of millimeter-sized granules
  • PEBA2 comprising polyether PTMG blocks (1000 g / mol) and PA-11 blocks (2000 g / mol) in the form of granules of millimeter size
  • Carbon particles Carbon nanotubes obtained according to the method described in WO 03/002456 A2 are used. These nanotubes have a diameter of between 10 and 30 nm and a length of> 0.4 ⁇ m. They are multipurpose (MWT) unpurified and non-functionalized and are totally or more than 98% in distinct form that is to say not aggregated.
  • Polymer Material :
  • Tg, Tf glass transition temperature and melting temperature measured by differential scanning calorimetry analysis
  • the molar ratio of the mixture of solvents CH 2 CI 2 / HFIP is 9/1, it is equal to 3/1 for the PEBA 2 /.
  • the CNTs are then dispersed in the dispersion agent solution previously prepared.
  • the mass concentration of CNT is always expressed relative to the amount of dispersing agent which represents 10 parts by weight of the total mass of the solution.
  • the dispersions which have been prepared are at 0, 5, 10 and respectively 20% by weight of CNT.
  • Each dispersion thus obtained is introduced into a closed bottle and left to rest for several weeks at room temperature so as to follow its long-term stability.
  • Conductivity the conductivity of PEBA1 and PEBA2 premixes is measured; samples of 5 mm width and scatterer ranging from 100 to 400 ⁇ m are made. At each end, the samples are clamped between 2 copper plates, so as to leave a gap of length 12.2 mm.
  • the copper plates are connected 2 to 2 to a current generator which delivers a direct current of voltage 9 V; the intensity of the current flowing through the circuit is measured using an ammeter.
  • the dispersing agent granules are first introduced into a 3g mini-extruder of DACA followed by the nanotubes using a piston, and the whole is mixed for about 2 minutes.
  • the speed is adjusted to 100 rpm and the temperature to 150 0 C for premixes based on PEBA1 and 180 0 C for premixes based on PEBA2.
  • Visual appearance of the rushes and films made from the rushes To the touch, all the rushes are brilliant, supple and seem homogeneous. The films are black, shiny, opaque and flexible; from 10% by weight of CNT, they become duller.
  • rods are extruded from 10 parts by weight of film of one of the previously described PEBA2-based pre-mixes previously cut into pieces and 90 parts by weight of PA-11; the rushes are also perfectly homogeneous, smooth and shiny and have good mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
EP06764818A 2005-06-24 2006-06-22 Kohlenstoffnanoröhren enthaltende polymermaterialien und verfahren zu ihrer herstellung aus einer vormischung mit einem dispergiermittel Withdrawn EP1893689A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0506439A FR2887554B1 (fr) 2005-06-24 2005-06-24 Materiaux polymeres contenant des nanotubes de carbone, leur procede de preparation a partir de pre-melange avec un agent de dispersion
US72952405P 2005-10-24 2005-10-24
PCT/FR2006/001426 WO2006136715A1 (fr) 2005-06-24 2006-06-22 Matériaux polymeres contenant des nanotubes de carbone, leur procede de preparation a partir de pre-melange avec un agent de dispersion

Publications (1)

Publication Number Publication Date
EP1893689A1 true EP1893689A1 (de) 2008-03-05

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EP06764818A Withdrawn EP1893689A1 (de) 2005-06-24 2006-06-22 Kohlenstoffnanoröhren enthaltende polymermaterialien und verfahren zu ihrer herstellung aus einer vormischung mit einem dispergiermittel

Country Status (3)

Country Link
EP (1) EP1893689A1 (de)
MX (1) MX2008000330A (de)
WO (1) WO2006136715A1 (de)

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FR2995815B1 (fr) 2012-09-26 2016-11-11 Peugeot Citroen Automobiles Sa Procede d'elaboration d'un materiau composite thermoplastique renforce par des nanotubes de carbone
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