EP1893689A1 - Polymer materials containing carbon nanotubes, method for preparing same from a premix with a dispersant - Google Patents

Polymer materials containing carbon nanotubes, method for preparing same from a premix with a dispersant

Info

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Withdrawn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
German (de)
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/en
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/en
Withdrawn legal-status Critical Current

Links

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.

Abstract

The invention concerns a polymer material containing carbon nanotubes prepared from a premix of carbon nanotubes and at least one copolymer with polyamide blocks and polyester blocks and/or a copolymer with polyester blocks and polyether blocks, facilitating in particular dispersion of the carbon nanotubes in the polymer matrix. The polymer materials can be used as reinforcing agents and/or for their excellent electrical and thermal properties.

Description

MATÉRIAUX POLYMERES CONTENANT DES NANOTUBES DE CARBONE, LEUR PROCEDE DE PREPARATION A PARTIR DE PRE-MELANGE AVECPOLYMER MATERIALS CONTAINING CARBON NANOTUBES, PROCESS FOR PREPARING THEM FROM PRE-MIXING WITH
UN AGENT DE DISPERSIONA DISPERSION AGENT
DOMAINE TECHNIQUE La présente invention concerne un procédé de dispersion de nanotubes de carbone au sein de matériaux polymères contenant des nanotubes de carbone ainsi que les matériaux polymères obtenus.TECHNICAL FIELD The present invention relates to a process for dispersing carbon nanotubes in polymer materials containing carbon nanotubes and the polymer materials obtained.
Du fait de leurs propriétés mécaniques et du ratio longueur/diamètre très élevés, les nanotubes de carbone (NTC) sont des matériaux présentant de grands avantages, tels qu'agents de renfort. De plus leurs propriétés électriques et thermiques permettent également de les utiliser pour modifier les propriétés conductrices des matériaux dans lesquels ils sont incorporés.Because of their very high mechanical properties and length / diameter ratio, carbon nanotubes (CNTs) are materials with great advantages, such as reinforcing agents. In addition, their electrical and thermal properties also make it possible to use them to modify the conductive properties of the materials in which they are incorporated.
Ils sont composés de feuillets graphitiques enroulés terminés par des hémisphères constitués de pentagones et d'hexagones de structure proche des fullerènes.They are composed of coiled graphitic sheets terminated by hemispheres consisting of pentagons and hexagons of structure close to fullerenes.
On connaît des nanotubes composés d'un seul feuillet et l'on parle alors de SWNT (pour Single Wall Nanotubes) ou de nanotubes composés de plusieurs feuillets concentriques appelés alors MWNT (pour Multi WallNanotubes 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
Nanotubes), les SWNT étant en général plus difficiles à fabriquer que les MWNT.Nanotubes), SWNTs being generally more difficult to manufacture than MWNTs.
Une fois synthétisés, les NTC se présentent sous forme pulvérulente, ce qui les rend de manipulation difficile avec des risques HSE pour les opérateurs.Once synthesized, CNTs are in powder form, making them difficult to handle with HSE risks for operators.
TECHNIQUE ANTÉRIEUREPRIOR ART
Dans EP 692.136 sont décrits des compositions polymères contenant jusqu'à 20 % en poids de NTC ; ces compositions, thermoplastiques ou thermodurcissables, sont préparées par mélange à l'état fondu des polymères avec les NTC. Or, on constate que la dispersion des NTC au sein de la matrice polymère n'est pas homogène et les propriétés mécaniques et/ou électriques attendues sont insuffisantes. II existe une demande non satisfaite pour améliorer la façon de disperser des NTC au sein des matériaux polymères dans lesquels ils sont incorporés afin d'obtenir des matériaux plus homogènes.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. However, it is found that the dispersion of the CNTs within the polymer matrix is not homogeneous and the expected mechanical and / or electrical properties are insufficient. There is an unmet demand for improving the manner of dispersing CNTs within the polymeric materials in which they are incorporated in order to obtain more homogeneous materials.
EP 1.359.121 et EP 1.359.169 proposent d'améliorer la dispersion des NTC dans des matrices polymères par fonctionnalisation des NTC.EP 1,359,121 and EP 1,359,169 propose to improve the dispersion of CNTs in polymer matrices by functionalization of CNTs.
La demanderesse décrit dans EP 1.449.885 des mélanges de polyamide et de polyoléfine contenant des NTC, le polyamide pouvant être un copolymère à blocs polyamides et à blocs polyéther. Toutefois, ce document ne traite pas du problème de dispersion des nanotubes de carbone au sein de matrices polymères.The Applicant describes in EP 1.449.885 mixtures of polyamide and polyolefin containing CNTs, the polyamide may be a copolymer with polyamide blocks and polyether blocks. However, this document does not deal with the problem of dispersion of carbon nanotubes within polymer matrices.
EXPOSÉ DE L'INVENTIONSTATEMENT OF THE INVENTION
La présente invention concerne un procédé permettant de disperser facilement des nanotubes de carbone au sein de matrices polymères.The present invention relates to a method for easily dispersing carbon nanotubes within polymer matrices.
Le procédé pour disperser les NTC mis au point par la demanderesse consiste à disperser et enrober les NTC par pré-mélange des NTC avec un agent de dispersion et d'enrobage choisi parmi les copolymères à blocs polyamides et blocs polyéthers (PEBA) et/ou les copolymères à blocs polyesters et blocs polyéthers.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.
Il est ensuite aisé d'introduire ce pré-mélange (NTC+agent de dispersion) dans des matrices polymères, par exemple par voie fondue ou par voie solvant.It is then easy to introduce this premix (NTC + dispersing agent) in polymer matrices, for example by melting or by solvent.
Dans les pré-mélanges selon l'invention, les NTC peuvent représenter jusqu'à 70 parties en poids de la masse totale du pré-mélange. Les nanotubes de carbone mis en œuvre peuvent être de tout type :In the premixes according to the invention, 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, DWNT (double paroi), SWNT, fonctionnalisés ou non.MWNT, DWNT (double wall), SWNT, functionalized or not.
De préférence, les nanotubes de carbone ont un rapport de forme (L/D) supérieur ou égal à 5 et de préférence supérieur ou égale à 50 et avantageusement supérieur ou égal à 100. Avantageusement, les nanotubes de carbone ont un diamètre compris entre 0,4 et 50 nm et une longueur comprise 100 et 100.000 fois leur diamètre. Suivant un mode de réalisation de l'invention préférée, les nanotubes de carbone sont sous forme multi-parois (MWT), leur diamètre étant compris entre 5 et 30 nm et leur longueur étant supérieure ou égale à 0,3 μm.Preferably, 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. Advantageously, the carbon nanotubes have a diameter of between 0 , 4 and 50 nm and a length of 100 and 100,000 times their diameter. According to one embodiment of the preferred invention, 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 μm.
La quantité de nanotubes de carbone représente de manière avantageuse de 0,1 à 70 parties en poids, et avantageusement de 0,1 à 30 parties en poids , et encore plus avantageusement de 0,5 à 20 parties en poids de la masse totale du pré-mélange.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.
A titre d'agent de dispersion, on peut citer les PEBA résultent de la copolycondensation de séquences polyamides à extrémités réactives avec des séquences polyéthers à extrémités réactives, telles que, entre autres :As dispersing agent, mention may be made of PEBAs resulting from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, inter alia:
1) séquences polyamides à bouts de chaîne diamines avec des séquences polyoxyalkylènes à bouts de chaînes dicarboxyliques.1) polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends.
2) séquences polyamides à bouts de chaînes dicarboxyliques avec des séquences polyoxyalkylènes à bouts de chaînes diamines obtenues par cyanoéthylation et hydrogénation de séquences polyoxyalkylène alpha-oméga dihydroxylées aliphatiques appelées polyétherdiols.2) 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.
3) séquences polyamides à bouts de chaînes dicarboxyliques avec des polyétherdiols, les produits obtenus étant, dans ce cas particulier, des polyétheresteramides.3) Polyamide sequences with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides.
Les séquences polyamides à bouts de chaînes dicarboxyliques proviennent par exemple de la condensation de précurseurs de polyamides en présence d'un diacide carboxylique limiteur de chaîne.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.
Les séquences polyamides à bouts de chaînes diamines proviennent par exemple de la condensation de précurseurs de polyamides en présence d'une diamine limiteur de chaîne.The polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine.
Les polymères à blocs polyamides et blocs polyéthers peuvent aussi comprendre des motifs répartis de façon aléatoire. Ces polymères peuvent être préparés par la réaction simultanée du polyéther et des précurseurs des blocs polyamides. Par exemple, on peut faire réagir du polyétherdiol, des précurseurs de polyamide et un diacide limiteur de chaîne. On obtient un polymère ayant essentiellement des blocs polyéthers, des blocs polyamides de longueur très variable, mais aussi les différents réactifs ayant réagi de façon aléatoire qui sont répartis de façon aléatoire (statistique) le long de la chaîne polymère.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.
On peut aussi faire réagir du polyétherdiamine, des précurseurs de polyamide et un diacide limiteur de chaîne. On obtient un polymère ayant essentiellement des blocs polyéthers, des blocs polyamides de longueur très variable, mais aussi les différents réactifs ayant réagi de façon aléatoire qui sont répartis de façon aléatoire (statistique) le long de la chaîne polymère.It is also possible to react polyetherdiamine, polyamide precursors and a chain-limiting diacid. A polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly which are distributed randomly (statistically) along the polymer chain.
La quantité de blocs polyéther dans ces copolymères à blocs polyamides et blocs polyéthers représente en général 10 à 70% en poids du copolymère.The amount of polyether blocks in these polyamide block copolymers and polyether blocks generally represents 10 to 70% by weight of the copolymer.
Les blocs polyétherdiols sont soit utilisés tels quels et copolycondensés avec des blocs polyamides à extrémités carboxyliques, soit aminés pour être transformés en polyéther diamines et condensés avec des blocs polyamides à extrémités carboxyliques. Ils peuvent être aussi mélangés avec des précurseurs de polyamide et un limiteur de chaîne diacide pour faire les polymères à blocs polyamides et blocs polyéthers ayant des motifs répartis de façon statistique.The 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.
Parmi les polymères à fonctions amide commerciaux, on peut par exemple citer les PEBAX® , VESTAMID® qui sont des PEBA.Among the polymers with commercial amide functions, PEBAX®, VESTAMID® which are PEBAs may for example be mentioned.
A titre d'agent de dispersion, on peut citer les copolymères à blocs polyesters et blocs polyéthers sont des polyétheresters à blocs. Ils sont constitués de blocs polyéthers souples qui sont les restes de polyétherdiols et de segments rigides (blocs polyesters) qui résultent de la réaction d'au moins un diacide carboxylique avec au moins un motif diol court allongeur de chaîne. Les blocs polyesters et les blocs polyéthers sont reliés par des liaisons esters résultant de la réaction des fonctions acides de l'acide avec les fonctions OH du polyétherdiol. Le diol court allongeur de chaîne peut être choisi dans le groupe constitué du neopentylglycol, du cyclohexanediméthanol et des glycols aliphatiques de formule HO(C^)nOH dans laquelle n est un entier valant de 2 à 10. Avantageusement les diacides sont des acides dicarboxyliques aromatiques ayant de 8 à 14 atomes de carbone. Jusqu'à 50 % en mole de l'acide aromatique dicarboxylique peut être remplacé par au moins un autre acide aromatique dicarboxylique ayant de 8 à 14 atomes de carbone, et/ou jusqu'à 20 % en mole peut être remplacé par un acide aliphatique dicarboxylique ayant de 2 à 12 atomes de carbone. A titre d'exemple d'acides aromatiques dicarboxyliques on peut citer l'acide téréphtalique, isophtalique, bibenzoïque, naphtalène dicarboxylique, l'acide 4,4'-diphénylenedicarboxylique, le bis(p-carboxyphényl) méthane, l'éthylène bis p-benzoïque acide, l'acide 1-4 tétraméthylène bis(p- oxybenzoïque), l'acide éthylène bis (para oxybenzoïque), l'acide 1 ,3- triméthylène bis (p-oxybenzoïque). A titre d'exemple de glycols on peut citer l'éthylène glycol, le 1 ,3 triméthylène glycol, le 1 ,4-tétraméthylèneglycol, le 1 ,6- hexaméthylène glycol, le 1 ,3 propylène glycol, le 1 ,8 octaméthylèneglycol, le 1 ,10-decaméthylène glycol et le 1 ,4-cyclohexane diméthanol. Les copolymères à blocs polyesters et blocs polyéther sont par exemple des copolymères ayant des motifs polyéthers dérivés de polyétherdiols tels que le PEG, le PPG ou le PTMG, des motifs diacide carboxylique tels que l'acide téréphtalique et des motifs glycol (éthane diol) ou butane diol, 1-4. L'enchaînement des polyéthers et des diacides forme les segments souples alors que l'enchaînement du glycol ou du butane diol avec les diacides forme les segments rigides du copolyétherester. De tels copolyétheresters sont par exemple décrits dans les brevets EP 402 883 et EP 405227. Ces polyétheresters sont des élastomères thermoplastiques ; ils peuvent contenir des plastifiants.As a dispersing agent, mention may be made of 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. Advantageously, 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. Examples of aromatic dicarboxylic acids that may be mentioned 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). By way of example of glycols, mention may be made of ethylene glycol, 1,3-trimethylene glycol, 1,4-tetramethylene glycol, 1,6-hexamethylene glycol, 1,3-propylene glycol and 1,8 octamethylene glycol. 1,10-decamethylene glycol and 1,4-cyclohexane dimethanol. 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. The linking of 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. Such copolyetheresters are for example described in patents EP 402 883 and EP 405227. These polyetheresters are thermoplastic elastomers; they may contain plasticizers.
Parmi les poly éther ester à blocs commerciaux, on peut par exemple citer ainsi que les ARNITEL®, HYTREL®, LOMOD®. Le pré-mélange peut être réalisé par voie solvant ou par voie fondue.Amongst the commercial polyether ester esters, mention may be made, for example, of ARNITEL®, HYTREL®, LOMOD®. The premix can be made by solvent or melt.
La voie solvant consiste à solubiliser l'agent de dispersion dans un solvant et à incorporer les NTC dans cette solution. A partir de cette solution contenant des NTC en dispersion, on peut préparer tout type d'objets de forme et de taille choisies, notamment de films, par remplissage par exemple d'un moule de dimensions choisies et évaporation du solvant.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.
A titre d'exemples de solvants des PEBA, on peut par exemple citer les mélanges d'au moins un solvant des blocs polyéthers, tel que benzène, chloroforme, dichlorométhane, éthanol et tétrahydrofurane, et d'au moins un solvant des blocs polyamides, tels que diméthylformamide, diméthylsulfoxyde, hexafluoroisopropanol (HFIP), crésol.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.
La solution d'agent de dispersion, de solvant et de NTC est préparée à des températures pouvant généralement aller de 0 à 100 0C, de préférence proches de la température ambiante (pour des raisons économiques) et inférieures aux températures d'ébullition des solvants ou des mélanges de solvants mis en œuvre.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.
La quantité de solvant mise en œuvre dépend de la solubilité de l'agent de dispersion et peut représenter jusqu'à 90 parties en poids de la masse totale de la solution. On préfère cependant ne pas trop « diluer » les solutions d'agent de dispersion dans la mesure où l'étape suivante va consister à éliminer le solvant.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.
Les dispersions de NTC dans les solutions d'agent de dispersion sont stables en durée et en température (plusieurs mois à température ambiante), ce qui est un avantage en cas de stockage avant incorporation de ces dispersions dans des matériaux polymères.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.
La seconde façon de préparer le pré-mélange selon l'invention consiste à opérer par voie fondue : on chauffe l'agent de dispersion jusqu à fusion complète et on introduit simultanément et/ou après sa fusion les NTC.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.
A titre d'exemples d'appareillage, on peut citer tout appareil de mélangeage utilisable pour les agents de dispersion selon l'invention, tel que malaxeur, mélangeur interne, extrudeuse mono ou double vis, bus, les mélangeur de type ultraturax, mélangeur à ultrasons ou tout type d'outil de mélange connu par l'homme de l'art.By way of examples of apparatus, mention may be made of 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.
La présente invention a également pour objet les matériaux polymères comprenant au moins un pré-mélange tel que défini précédemment et une matrice polymère.The present invention also relates to polymeric materials comprising at least one premix as defined above and a polymer matrix.
Avantageusement la proportion de NTC dans le matériau polymère mélange est de 1 à 20 parties en poids. Par matrice polymère on entend toute composition à base de polymère(s) de toute nature : thermoplastique ou thermodurcissable, rigide ou élastomérique, amorphe, cristalline et/ou semi-cristalline, homopolymère, copolymère, ...qui sont compatibles avec au moins l'un des blocs de l'agent de dispersion ; ces compositions peuvent être des mélanges d'un ou plusieurs différents polymères avec divers additifs, adjuvants et/ou charges classiquement ajoutés aux polymères, tels que stabilisants, plastifiants, catalyseurs de polymérisation, colorants, pigments, lubrifiants, ignifugeants, renforts et/ou charges, solvants de polymérisation, ...Advantageously, the proportion of CNTs in the mixed polymer material is from 1 to 20 parts by weight. By 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, ...
La présente invention concerne également le procédé de préparation des matériaux polymères comprenant le pré-mélange selon l'invention décrit ci- dessus avec une matrice polymère compatible avec ledit pré-mélange. On peut opérer par exemple par voie fondue ou par voie solvant.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.
Le procédé de préparation peut utiliser différentes technologies telles que celles utilisées pour les caoutchoucs, les polymères, les liquides, selon la nature des polymères présents dans le matériau polymère final. On peut citer les mélangeurs internes, les extrudeuses mono ou double vis, les bus, les mélangeurs du type ultraturax, les mélangeurs à ultrasons ou tout type d'outil de mélange connu par l'homme de l'art.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. There may be mentioned internal mixers, single or twin screw extruders, buses, ultraturax type mixers, ultrasonic mixers or any type of mixing tool known to those skilled in the art.
Les matériaux polymères précédemment décrits peuvent être obtenus directement par mélange à l'état fondu du ou des matrices polymères et du prémélange, ce dernier faisant office de mélange-maître ou master batch comme décrit dans WO 91/03057 ou US 5.646.990, EP 692.136 ou US 5.591.382 US 5.643.502 ou US 5.651.922, US 6.221.283.The previously described 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.
Les matériaux polymères précédemment décrits peuvent également être obtenus par voie solvant, en solubilisant le pré-mélange et la matrice polymère dans un ou plusieurs solvants suivie d'une étape d'élimination du ou des solvants, par exemple par évaporation. A titre d'exemple de polymères compatibles avec les agents de dispersion, on peut citer o les polymères à fonctions amide, on peut citer les polymères issus de la condensation : - d'un ou plusieurs aminoacides, tels les acides aminocaproïques, amino-7-heptanoïque, amino-11-undécanoïque (PA-11 ) et amino-12- dodécanoïque (PA-12) d'un ou plusieurs lactames tels que caprolactame (PA- 6), oenantholactame et lauryllactame ;The polymer materials 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. By way of example of 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;
- d'un ou plusieurs sels ou mélanges de diamines telles que l'hexaméthylènediamine, la dodécaméthylènediamine, la métaxylylènediamine, le bis-p aminocyclohexylméthane et la triméthylhexaméthylène diamine avec des diacides tels que les acides isophtalique, téréphtalique, adipique, azélaïque, subérique, sébacique et dodécanedicarboxylique ;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;
- ou des mélanges de certains de ces monomères ce qui conduit à des copolyamides, par exemple le PA-6/12 par condensation du caprolactame et du lauryllactame.or mixtures of some of these monomers which leads to copolyamides, for example PA-6/12 by condensation of caprolactam and lauryllactam.
A titre d'exemple de polyamides aliphatiques résultant de la condensation d'une diamine aliphatique ayant de 6 à 12 atomes de carbone et d'un diacide aliphatique ayant de 9 à 12 atomes de carbone on peut citer : - le PA 6-12 résultant de la condensation de l'hexaméthylène diamine et de l'acide 1 ,12-dodecanedioïque,By way of example of 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,
A titre d'exemples de polyamides aliphatiques résultant de la condensation d'une diamine aliphatique ayant de 6 à 12 atomes de carbone et d'un diacide aliphatique ayant de 9 à 12 atomes de carbone et des aminoacides on peut citer :As examples of 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:
- le PA 6/6,6/12 résultant de la condensation de caprolactame et d'hexaméthylène diamine et d'acide adipique et de lauryllactame- PA 6 / 6,6 / 12 resulting from the condensation of caprolactam and hexamethylenediamine and adipic acid and lauryllactam
Le polymère à fonctions amide peut être plastifié. S'agissant du ou des plastifiants, ils sont en général choisis parmi les dérivés de benzène sulfonamide, tels que le n-butyl benzène sulfonamide (BBSA), l'éthyl toluène sulfonamide ou le N-cyclohexyl toluène sulfonamide; les esters d'acides hydroxy-benzoïques, tels que le parahydroxybenzoate d'éthyl-2 hexyle et le parahydroxybenzoate de décyl-2 hexyle ; les esters ou éthers du tétrahydrofurfuryl alcool, comme l'oligoéthylèneoxytétrahydrofurfurylalcool ; et les esters de l'acide citrique ou de l'acide hydroxy-malonique, tels que l'oligoéthylèneoxy malonate. Un plastifiant particulièrement préféré est le n- butyl benzène sulfonamide (BBSA). Le ou les plastifiants peuvent être introduits dans le polyamide pendant la polycondensation ou ultérieurement. La proportion de plastifiant peut en général aller jusqu'à 30 % en poids du polymère à fonctions amide.The amide functional polymer can be plasticized. As regards the plasticizer (s), 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. A particularly preferred plasticizer is n-butyl benzene sulfonamide (BBSA). 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.
Le polymère à fonctions amide peut également être un copolymère à blocs polyamides et blocs polyéthers (PEBA) tel que défini précédemment. o des polyuréthanes, constitués de blocs polyéthers souples qui sont des restes de polyétherdiols et de blocs rigides (polyuréthanes) qui résultent de la réaction d'au moins un diisocyanate avec au moins un diol court. Le diol court allongeur de chaîne peut être choisi parmi les glycols cités plus haut dans la description des polyétheresters. Les blocs polyuréthanes et les blocs polyéthers sont reliés par des liaisons résultant de la réaction des fonctions isocyanates avec les fonctions OH du polyétherdiol.The amide-functional polymer may also be a copolymer with polyamide blocks and polyether blocks (PEBA) as defined above. 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.
On peut encore citer les polyesteruréthannes par exemple ceux comprenant des motifs di isocyanates, des motifs dérivés de polyesters diols amorphes et des motifs dérivés d'un diol court allongeur de chaîne. Ils peuvent contenir des plastifiants.Mention may also be made of 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.
A titre d'exemple de polyuréthannes thermoplastiques commerciaux, on peut par exemple citer les ELASTOLLAN® de Elastogran Bayer. o des polymères à fonctions éther, on peut citer les polyoxyalkylènes et notamment le polyoxyméthylène (POM), les copolymères à blocs poly-(oxyde propylène- oxyde éthylène) et le polyphénylèneoxyde (PPO).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).
On peut également citer les polyalkylène glycols qui sont des polyéthers terminés par des fonctions hydroxyle, tel que le polyéthylène glycol (PEG), le polypropylène glycol, le polytétraméthylène glycol (PTMG) ainsi que les copolymères à blocs polyesters et blocs polyéthers définis précédemment.Mention may also be made of 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.
Parmi les polymères à fonctions éther commerciaux, on peut par exemple citer les ALCON®, HOSTAFORM qui sont du POM, les ARNITEL®, HYTREL®, LOMOD® qui sont des poly éther ester à blocs ainsi que les PEBAX®, VESTAMID® qui sont des poly éther ester amide à blocs. o des poiymères à fonctions dérivés d'acide de type ester, et notamment les polymères de type (alkyl) acrylate ou polymères acryliques, les homo-et copolymères d'un ou plusieurs (alkyl)acrylates d'alkyle, qui sont notamment décrits dans KIRK OTHMER, Encyclopedia of Chemical Technology, 4ème édition, vol 1 , pages 292-293 et vol 16, pages 475-478 et notamment les (co)polymères de méthacrylate de méthyle (PMMA).Among the polymers with commercial ether functions, mention may be made, for example, of ALCON®, HOSTAFORM which are POM, ARNITEL®, HYTREL®, LOMOD® which are polyether block ester as well as PEBAX®, VESTAMID® which are polyether block amide ester. 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).
On peut aussi citer les copolymères d'un ou plusieurs (alkyl)acrylates d'alkyle et d'au moins un monomère choisi parmi l'acrylonitrile, le butadiène, le styrène, l'isoprène.Mention may also be made of copolymers of one or more alkyl (alkyl) acrylates and of at least one monomer chosen from acrylonitrile, butadiene, styrene and isoprene.
On peut aussi citer les polymères contenant des motifs dérivés d'un ou plusieurs esters vinyliques d'acides carboxyliques saturés tels que par exemple l'acétate ou le propionate de vinyle. On peut par exemple citer les copolymères d'éthylène et d'acétate de vinyle, commercialisés notamment sous les dénominations EVATANE®, ELVAX® , ULTRATHENE®. o des polycarbonates o les élastomères EPR (éthylène - propylène - rubber) et les les élastomères EPDM (éthylène - propylène - diène) éventuellement maléisés, o les copolymères de butadiène et d'acrylonitrile, ou caoutchouc nitrile (NBR) comprenant éventuellement des fonctions carboxyliques, o des polymères à fonctions vînyle, homo- et copolymères, qui dérivent notamment de monomère(s) vinylique(s), tel que le chlorure de vinyle. A titre d'exemple de polymères vinyliques on peut citer le polyclorure de vinyle (PVC), le PVC surchloré, éventuellement plastifiés, etcMention may also be made of polymers containing units derived from one or more vinyl esters of saturated carboxylic acids such as, for example, acetate or vinyl propionate. For example, 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. By way of example of vinyl polymers mention may be made of polyvinyl chloride (PVC), superchlorinated PVC, possibly plasticized, etc.
Les matériaux polymères selon l'invention peuvent avantageusement remplacer les matériaux polymères contenant des NTC de l'état de la technique et être utilisés dans de nombreux domaines, notamment en électronique (selon la température et leur structure, ils peuvent être conducteurs, semi-conducteurs ou isolants), en mécanique, par exemple pour le renfort des matériaux composites (les NTC sont cent fois plus résistants et six fois plus légers que l'acier) et électromécanique (ils peuvent s'allonger ou se contracter par injection de charge) On peut par exemple citer les matériaux destinés par exemple à l'emballage de composants électroniques, au blindage électromagnétique et à la dissipation antistatique, tels que les boîtiers de téléphone portable, les ordinateurs, les appareils électroniques embarqués sur les véhicules automobiles, ferroviaires et aériens, les instruments médicaux, les conduites d'essence (fuel line), les revêtements ou coating antistatiques, des thermistors, des électrodes, notamment pour supercapacités, 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). For example, 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.
ExemplesExamples
Les produits suivants ont été mis en œuvre :The following products have been implemented:
Agent de dispersionDispersion agent
PEBA1 comprenant des blocs polyéther en PTMG (2000g/mol) et des blocs PA-12 (600g/mol) sous forme de granulés de taille millimétriquePEBA1 comprising PTMG polyether blocks (2000 g / mol) and PA-12 blocks (600 g / mol) in the form of millimeter-sized granules
PEBA2 comprenant des blocs polyéther en PTMG (1000g/mol) et des blocs PA-11 (2000g/mol) sous forme de granulés de taille millimétriquePEBA2 comprising polyether PTMG blocks (1000 g / mol) and PA-11 blocks (2000 g / mol) in the form of granules of millimeter size
Particules de carbone On utilise des nanotubes de carbone obtenus selon le procédé décrit dans WO 03/002456 A2. Ces nanotubes ont un diamètre compris entre 10 et 30 nm et une longueur > 0,4 μm. Ils sont de type multiparoi (MWT) non purifiés et non fonctionnalisés et se présentent en totalité ou à plus de 98% sous forme distincte c'est-à-dire non agrégée. Matériau Polymère: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 μm. 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:
PA-12 de Tg = 35 0C et de Tf = 180 0C PA-11 de Tg = 45 °C et de Tf = 190 0CPA-12 of Tg = 35 0 C and Tf = 180 0 C PA-11 of Tg = 45 ° C and Tf = 190 0 C
(Tg, Tf : température de transition vitreuse et température de fusion mesurées par analyse enthalpique différentielle DSC)(Tg, Tf: glass transition temperature and melting temperature measured by differential scanning calorimetry analysis)
Préparation des pré-mélanges : Par voie solvant Dans un flacon contenant du CH2CI2, on introduit 10% en masse d'agent de dispersion 1/ ou 2/ et on laisse sous agitation à température ambiante jusqu'à ce que les granulés soient bien gonflés. Puis ensuite on ajoute du HFIP goutte à goutte jusqu'à ce que les granulés d'agent de dispersion se solubilisent.Preparation of premixes: Solvent In a flask containing CH 2 Cl 2 , 10% by weight of dispersion agent 1 / or 2 / and is stirred at room temperature until the granules are well inflated. Then HFIP is added dropwise until the dispersing agent granules solubilize.
Pour le PEBA1 , le ratio molaire du mélange de solvants CH2CI2/HFIP est 9/1 , il est égal à 3/1 pour le PEBA 2/.For PEBA1, 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 /.
On disperse ensuite les NTC dans la solution d'agent de dispersion préparée précédemment. Dans tout ce qui suit, la concentration massique en NTC est toujours exprimée par rapport à la quantité d'agent de dispersion qui représente 10 parties en poids de la masse totale de la solution.The CNTs are then dispersed in the dispersion agent solution previously prepared. In what follows, 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.
Ainsi une solution dite à « 10 % en poids en NTC contient un prémélange contenant 10 % en poids en.Thus a solution called "10% by weight of CNT contains a premix containing 10% by weight of.
Les dispersions qui ont été préparées sont à 0, 5, 10 et respectivement 20 % en poids en NTC.The dispersions which have been prepared are at 0, 5, 10 and respectively 20% by weight of CNT.
Chaque dispersion ainsi obtenue est introduite dans un flacon fermé et laissée au repos plusieurs semaines à température ambiante de manière à suivre sa stabilité à long terme.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.
Au bout de 3 mois, toutes les dispersions restent visuellement stables. Préparation de films par voie solvantAfter 3 months, all the dispersions remain visually stable. Solvent film preparation
Ces dispersions stables de nanotubes sont versées dans des moules en Teflon® d'environ 5 cm de diamètre puis le solvant est évaporé sous atmosphère saturée en solvant . On obtient des films d'épaisseur moyenne variant entre 100 et 200 μm. Aspect visuel des films Dès des concentrations très faibles en nanotubes, c'est-à-dire 1 % en poids de NTC dans le pré-mélange, les films présentent une teinte grise ; au-delà de 1 %, ils ne sont plus transparents. Pour des concentrations entres 1 et 5 % les films sont noirs, brillants, opaques et souples ; à partir de 10 % en poids de NTC, on observe une rugosité de surface importante et ils perdent de ce fait un peu de leur brillance.These stable dispersions of nanotubes are poured into Teflon® molds of about 5 cm in diameter and the solvent is then evaporated under a saturated solvent atmosphere. Films of average thickness varying between 100 and 200 μm are obtained. Visual appearance of the films From very low concentrations of nanotubes, that is to say 1% by weight of CNTs in the premix, the films have a gray tint; beyond 1%, they are no longer transparent. For concentrations between 1 and 5% the films are black, shiny, opaque and flexible; from 10% by weight of CNT, there is a significant surface roughness and they lose some of their brilliance.
Propriétés mécaniques : Des petites éprouvettes parallélépipédiques (17*5*0,3 mm3) sont découpées pour tester les propriétés mécaniques du matériau par analyse mécanique dynamique (DMA) à l'aide d'un appareil TA instrument (on travaille en tension dynamique à la fréquence de 1 Hz, avec une amplitude de déformation de 30 μm et une force de pré-charge de 0,02 N. L'intervalle de températures va de - 120 0C à + 150 0C)Mechanical Properties: Small parallelepiped specimens (17 * 5 * 0.3 mm 3 ) are cut to test the mechanical properties of the material by dynamic mechanical analysis (DMA) using a TA instrument instrument (one works in dynamic tension at the frequency of 1 Hz, with a strain amplitude of 30 μm and a pre-load force of 0.02 N. The temperature range is from -120 ° C. to + 150 ° C.
Les valeurs du module de conservation (E') pour les pré-mélanges à base de PEBA2 sont données dans le tableau ci-dessous (en MPa)The values of the conservation modulus (E ') for the premixes based on PEBA2 are given in the table below (in MPa)
Conductivité : on mesure la conductivité des pré-mélanges à base de PEBA1 et de PEBA2 ; on réalise des échantillons de 5 mm de largeur et d'éparisseur variant entre 100 et 400 μm. A chaque extrémité, les échantillons sont serrés entre 2 plaques de cuivre, de manière à laisser un entrefer de longueur 12,2 mm. Les plaques de cuivre sont reliées 2 à 2 à un générateur de courant qui délivre un courant continu de tension 9 V ; on mesure l'intensité du courant traversant le circuit à l'aide d'un ampèremètre.Conductivity: the conductivity of PEBA1 and PEBA2 premixes is measured; samples of 5 mm width and scatterer ranging from 100 to 400 μm 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.
Les résultats sont réunis dans le tableau ci-dessous.The results are summarized in the table below.
Préparation de films par voie fonduePreparation of films by molten route
Les granulés d'agent de dispersion sont d'abord introduits dans une mini- extrudeuse 3g de DACA suivis des nanotubes à l'aide d'un piston, et le tout est mélangé pendant environ 2 min. La vitesse est ajustée à 100 trs/min et la température à 1500C pour les pré-mélanges à base de PEBA1 et à 1800C pour les pré-mélanges à base de PEBA2. Aspect visuel des joncs et films réalisés à partir des joncs : Au toucher, tous les joncs sont brillants, souples et semblent homogènes. Les films sont noirs, brillants, opaques et souples ; à partir de 10 % en poids de NTC, ils deviennent plus ternes.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.
Dispersion des pré-mélanges dans des matériaux polymèresDispersion of premixes in polymer materials
A l'aide d'une mini extrudeuse 3g de DACA à 195 0C et avec un taux de cisaillement de 100 trs/min pendant 2 min, on extrude des joncs obtenus à partir de 10 parties en poids de film d'un des pré-mélanges à base PEBA1 décrit précédemment préalablement coupé en morceaux et de 90 parties en poids PA-12 ; les joncs sont parfaitement homogènes, lisses et brillants et présentent de bonnes propriétés mécaniques. Dans des conditions opératoires similaires (température de l'extrudeuseUsing a mini extruder 3g of DACA at 195 ° C. and with a shear rate of 100 rpm for 2 min, rods obtained from 10 parts by weight of film of one of the preforms were extruded. PEBA1-based blends previously described previously cut into pieces and 90 parts by weight PA-12; the rushes are perfectly homogeneous, smooth and shiny and have good mechanical properties. Under similar operating conditions (temperature of the extruder
200 0C), on extrude des joncs à partir de 10 parties en poids de film d'un des pré-mélanges à base PEBA2 décrit précédemment préalablement coupé en morceaux et de 90 parties en poids de PA-11 ; les joncs sont également parfaitement homogènes, lisses et brillants et présentent de bonnes propriétés mécaniques. 200 ° C.), 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.

Claims

REVENDICATIONS
1. Procédé de dispersion de nanotubes de carbone (NTC) au sein d'une matrice polymère consistant à : a) disperser et enrober les NTC par pré-mélange des NTC avec au moins un agent de dispersion. b) introduire le pré-mélange issu de l'étape a) dans une matrice polymère. A method for dispersing carbon nanotubes (CNTs) within a polymer matrix comprising: a) dispersing and coating the CNTs by premixing the CNTs with at least one dispersing agent. b) introducing the premix from step a) into a polymer matrix.
2. Procédé de dispersion de NTC au sein d'une matrice polymère selon la revendication 1 , caractérisé en ce que l'agent de dispersion est choisi parmi les copolymères à blocs polyamides et blocs polyéthers (PEBA) et/ou les copolymères à blocs polyesters et blocs polyéthers.2. Process for dispersing CNTs in a polymer matrix according to claim 1, characterized in that the dispersing agent is chosen from polyamide block and polyether block copolymers (PEBA) and / or block copolymers polyesters and polyether blocks.
3. Procédé de dispersion de NTC au sein d'une matrice polymère selon l'une quelconque des revendications précédentes, caractérisé en ce que les3. Process for dispersing CNTs within a polymer matrix according to any one of the preceding claims, characterized in that the
NTC représentent de 0,1 à 70 parties en poids, et avantageusement de 0,1 à 30 parties en poids, et encore plus avantageusement de 0,5 à 20 parties en poids de la masse totale du pré-mélange.NTC are from 0.1 to 70 parts by weight, and preferably 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.
4. Procédé de dispersion de NTC au sein d'une matrice polymère selon l'une quelconque des revendications précédentes, caractérisé en ce que le prémélange est préparé par solubilisation du ou des agents de dispersion dans un ou plusieurs solvants simultanément ou préalablement à l'introduction des NTC dans la solution, suivie de l'élimination du ou des solvants.4. Process for dispersing CNTs in a polymer matrix according to any one of the preceding claims, characterized in that the premix is prepared by solubilization of the dispersing agent (s) in one or more solvents simultaneously or beforehand. introduction of the CNTs into the solution, followed by removal of the solvent (s).
5. Procédé de dispersion de NTC au sein d'une matrice polymère selon l'une des revendications 1 à 3, caractérisé en ce que le pré-mélange est préparé par mélange des NTC avec le ou les agents de dispersion à l'état fondu suivie d'une étape de refroidissement du pré-mélange obtenu.5. Process for the dispersion of CNTs in a polymer matrix according to one of claims 1 to 3, characterized in that the premix is prepared by mixing the CNTs with the dispersing agent (s) in the molten state followed by a cooling step of the premix obtained.
6. Procédé de dispersion de NTC au sein d'une matrice polymère selon l'une quelconque des revendications précédentes, caractérisé en ce que Ia matrice polymère est une matrice polymère à base de polymère(s) compatibles avec au moins l'un des blocs d'au moins un agent de dispersion, seuls ou en mélange, et contenant éventuellement un ou plusieurs additifs, adjuvants et/ou charges classiquement ajoutés aux polymères, tels que stabilisants, plastifiants, catalyseurs de polymérisation, colorants, pigments, lubrifiants, ignifugeants, renforts et/ou charges, solvants de polymérisation.6. Process for dispersing CNTs in a polymer matrix according to any one of the preceding claims, characterized in that the polymer matrix is a polymer matrix based on polymer (s) compatible with at least one of the blocks. at least one dispersing agent, alone or as a mixture, and optionally containing one or more additives, adjuvants and / or fillers conventionally added to polymers, such as stabilizers, plasticizers, polymerization catalysts, dyes, pigments, lubricants, flame retardants, reinforcements and / or fillers, polymerization solvents.
7. Procédé de dispersion de NTC au sein d'une matrice polymère selon l'une quelconque des revendications précédentes, caractérisé en ce que la matrice polymère est à base d'un ou plusieurs polymères choisis parmi les polymères à fonctions amides et/ou les polyuréthanes et/ou les polymères à fonctions éther et/ou les polymères à fonctions dérivés d'acide de type ester et/ou les polycarbonates et/ou les élastomères EPR et/ou élastomères EPDM (éventuellement maléisés) et/ou les caoutchoucs nitriles (NBR) comprenant éventuellement des fonctions carboxyliques et/ou les polymères à fonctions vinyle,7. Process for dispersing CNTs in a polymer matrix according to any one of the preceding claims, characterized in that the polymer matrix is based on one or more polymers chosen from polymers with amide functional groups and / or polyurethanes and / or ether-functional polymers and / or ester-derived acid functional polymers and / or polycarbonates and / or EPR elastomers and / or EPDM elastomers (optionally maleised) and / or nitrile rubbers ( NBR) optionally comprising carboxylic functions and / or polymers with vinyl functions,
8. Procédé de dispersion de NTC au sein d'une matrice polymère selon l'une quelconque des revendications précédentes, caractérisé en ce que l'introduction du pré-mélange dans la matrice polymère est réalisée par voie fondue.8. Process for dispersing CNTs within a polymer matrix according to any one of the preceding claims, characterized in that the introduction of the premix into the polymer matrix is carried out by molten route.
9. Procédé de dispersion de NTC au sein d'une matrice polymère selon l'une quelconque des revendications précédentes, caractérisé en ce que l'introduction du pré-mélange dans la matrice polymère est réalisée par voie solvant, par solubilisation/dispersion du ou des pré-mélanges et de la matrice polymère dans un ou plusieurs solvants, suivie de l'élimination du ou des solvants.9. Process for dispersing CNTs in a polymer matrix according to any one of the preceding claims, characterized in that the introduction of the premix into the polymer matrix is carried out by solvent, by solubilization / dispersion of or premixes and the polymer matrix in one or more solvents, followed by removal of the solvent (s).
10. Pré-mélange susceptible d'être obtenu selon l'une des revendications 4 ou 5. 10. Premix obtainable according to one of claims 4 or 5.
11. Matériau polymère susceptible d'être obtenu selon l'une des revendications 1 à 9.11. The polymer material obtainable according to one of claims 1 to 9.
12. Utilisation d'un matériau polymère tel que défini à la revendication 11 comme agent de renfort et /ou comme modifiant des propriétés conductrices et/ou thermiques. 12. Use of a polymeric material as defined in claim 11 as a reinforcing agent and / or as modifying conductive and / or thermal properties.
13. Utilisation d'un matériau polymère selon la revendication 12 pour la réalisation : d'emballages de composants électroniques, le blindage électromagnétique et à la dissipation antistatique, tels que boîtiers de téléphone portable, ordinateurs, pour des appareils électroniques embarqués sur les véhicules automobiles, ferroviaires et aériens, - d'instruments médicaux,13. Use of a polymeric material according to claim 12 for carrying out: electronic component packaging, electromagnetic shielding and anti-static dissipation, such as mobile phone housings, computers, for on-board electronic devices on motor vehicles, rail and air vehicles, - medical instruments,
- de conduites d'essence (fuel line),- fuel lines (fuel line),
- des revêtements ou coating antistatiques,antistatic coatings or coatings,
- de thermistors,thermistors,
- d'électrodes, notamment pour supercapacités. - Electrodes, especially for supercapacities.
EP06764818A 2005-06-24 2006-06-22 Polymer materials containing carbon nanotubes, method for preparing same from a premix with a dispersant Withdrawn EP1893689A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0506439A FR2887554B1 (en) 2005-06-24 2005-06-24 POLYMER MATERIALS CONTAINING CARBON NANOTUBES, PROCESS FOR PREPARING THEM FROM PRE-MIXTURE WITH A DISPERSION AGENT
US72952405P 2005-10-24 2005-10-24
PCT/FR2006/001426 WO2006136715A1 (en) 2005-06-24 2006-06-22 Polymer materials containing carbon nanotubes, method for preparing same from a premix with a dispersant

Publications (1)

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

Family

ID=37090548

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06764818A Withdrawn EP1893689A1 (en) 2005-06-24 2006-06-22 Polymer materials containing carbon nanotubes, method for preparing same from a premix with a dispersant

Country Status (3)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3640280A1 (en) * 2018-10-19 2020-04-22 Evonik Operations GmbH Conductive moulding masses
RU2783077C1 (en) * 2018-10-19 2022-11-08 Эвоник Оперейшенс ГмбХ Electroconductive molding masses

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007008670A1 (en) * 2007-02-20 2008-08-21 Beck, Wolfgang, Dr.-Ing. Use of the viscosity-controlling carbon nanotubes in binder systems and solvent-free coating material with carbon nanotubes based on functional reactants for in-mold coating (IMC) and top coating, and process for the production thereof
FR2919856B1 (en) 2007-08-09 2010-03-12 Centre Nat Rech Scient GRAPHENE SOLUTIONS
EA201270707A1 (en) * 2010-03-02 2012-12-28 Тотал Ресерч Энд Текнолоджи Фелюи NANOCOMPOSITES WITH IMPROVED UNIFORMITY
FR2966815B1 (en) 2010-10-28 2013-05-31 Centre Nat Rech Scient METHOD OF PURIFYING CARBON NANOTUBES
DE102010043470A1 (en) * 2010-11-05 2012-05-10 Evonik Degussa Gmbh Composition of polyamides with low concentration of carboxylic acid amide groups and electrically conductive carbon
DE102010043473A1 (en) * 2010-11-05 2012-05-10 Evonik Degussa Gmbh Carbon nanotube-containing polyamide 12 composition
EP2673327A1 (en) * 2011-02-10 2013-12-18 FutureCarbon GmbH Adhesive material with carbon material and method for its production and use
FR2975219B1 (en) * 2011-05-11 2014-10-31 Arkema France METHOD FOR PRODUCING AN ELECTROMAGNETIC WAVE RADIATION ABSORBING MATERIAL, COMPRISING CARBON NANOPARTICLES, AND MATERIAL OBTAINED BY THE PROCESS
FR2995815B1 (en) 2012-09-26 2016-11-11 Peugeot Citroen Automobiles Sa PROCESS FOR THE PREPARATION OF A CARBON NANOTUBE-STRENGTHENED THERMOPLASTIC COMPOSITE MATERIAL
RU2554792C2 (en) * 2012-12-25 2015-06-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский химико-технологический университет им. Д.И. Менделеева (РХТУ им. Менделеева") Polymer composition for medical surgical instruments

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5591382A (en) * 1993-03-31 1997-01-07 Hyperion Catalysis International Inc. High strength conductive polymers
IL142254A0 (en) * 2001-03-26 2002-03-10 Univ Ben Gurion Method for the preparation of stable suspensions of single carbon nanotubes
WO2003049795A2 (en) * 2001-09-28 2003-06-19 Boston Scientific Limited Medical devices comprising nanocomposites
DE10301996A1 (en) * 2003-01-21 2004-07-29 Tuhh-Technologie-Gmbh Mixing of carbon nanotube reinforcement with polymers (especially polyesters) takes place before the end of the polycondensation used to produce the polymer
JP4222048B2 (en) * 2003-02-13 2009-02-12 東レ株式会社 Carbon nanotube-containing resin composite, method for producing the same, and highly elastic film
ES2437194T3 (en) * 2003-02-18 2014-01-09 Arkema France Use of carbon nanotubes in mixtures of polyamide and polyolefin
WO2005035651A1 (en) * 2003-10-10 2005-04-21 Japan Science And Technology Agency Finely particulate composite containing carbon compound encapsulated therein
IL160145A0 (en) * 2004-01-29 2004-06-20 Univ Ben Gurion Method for the preparation of dispersions of carbon nanotubes
US20050186378A1 (en) * 2004-02-23 2005-08-25 Bhatt Sanjiv M. Compositions comprising carbon nanotubes and articles formed therefrom

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006136715A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3640280A1 (en) * 2018-10-19 2020-04-22 Evonik Operations GmbH Conductive moulding masses
WO2020079161A1 (en) * 2018-10-19 2020-04-23 Evonik Operations Gmbh Conductive moulding compounds
RU2783077C1 (en) * 2018-10-19 2022-11-08 Эвоник Оперейшенс ГмбХ Electroconductive molding masses

Also Published As

Publication number Publication date
MX2008000330A (en) 2008-03-19
WO2006136715A1 (en) 2006-12-28

Similar Documents

Publication Publication Date Title
EP1893689A1 (en) Polymer materials containing carbon nanotubes, method for preparing same from a premix with a dispersant
FR2887554A1 (en) Composition (pre-mixture), useful to prepare polymer material, which is useful e.g. as reinforcing agent, comprises carbon nanotubes and dispersion agent comprising e.g. poly(ether-block-amide) copolymer
EP2561011B1 (en) Thermoplastic and/or elastomeric composite material based on carbon nanotubes and graphenes
US9312043B2 (en) Polyamide composition containing electrically conductive carbon
KR101239594B1 (en) Process for preparing precomposites based on nanotubes, particularly carbon nanotubes
JP5466952B2 (en) Processing and performance aids for carbon nanotubes
US20030158323A1 (en) Electrically conductive, optically transparent polymer/carbon nanotube composites and process for preparation thereof
US20110233479A1 (en) Process for preparing an elastomeric composite material
FR2937324A1 (en) PROCESS FOR THE PREPARATION OF A COMPOSITE MATERIAL BASED ON NANOTUBES, IN PARTICULAR CARBON
KR101295351B1 (en) Dispersant Composition for Carbon Nanotubes, Carbon Nanotube Composite Comprising the Dispersant Composition and Polymer Composite Material Produced Using the Carbon Nanotube Composite
EP1954752A1 (en) Pulverulent composition based on carbon nanotubes, methods of obtaining them and its uses, especially in polymeric materials.
FR2973382A1 (en) COMPOSITE MATERIAL COMPRISING CARBON NANOTUBES AND HEART-ECORCE STRUCTURE PARTICLES
JP6076484B2 (en) Thermoplastic polymer bonded with carbon nanomaterial and method for producing the same
JP2004182768A (en) Resin composition and method for producing the same
US9957386B2 (en) Antistatic thermoplastic starch alloys
JP5154760B2 (en) Polyether ester amide elastomer resin composition and process for producing the same
JP5499341B2 (en) Conductive resin composition and molded body produced from the composition
JP6918597B2 (en) Semi-conductive resin composition and seamless belt for electrophotographic using it
JP6590708B2 (en) Method for producing semiconductive resin composition
JP6598669B2 (en) Semiconductive resin composition and electrophotographic seamless belt using the same
Uzunpinar Carbon nanofiller reinforced epoxy nanocomposites

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20071210

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE

Owner name: ARKEMA FRANCE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20101231