EP2344575A1 - Procédé de préparation d'un matériau composite thermoplastique à base de nanotubes, notamment de carbone - Google Patents
Procédé de préparation d'un matériau composite thermoplastique à base de nanotubes, notamment de carboneInfo
- Publication number
- EP2344575A1 EP2344575A1 EP09760201A EP09760201A EP2344575A1 EP 2344575 A1 EP2344575 A1 EP 2344575A1 EP 09760201 A EP09760201 A EP 09760201A EP 09760201 A EP09760201 A EP 09760201A EP 2344575 A1 EP2344575 A1 EP 2344575A1
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- EP
- European Patent Office
- Prior art keywords
- nanotubes
- weight
- plasticizer
- polymer
- thermoplastic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/29—Feeding the extrusion material to the extruder in liquid form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0038—Plasticisers
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
Definitions
- thermoplastic composite material based on nanotubes, in particular carbon
- the present invention relates to a process for the preparation of composite materials based on nanotubes, in particular carbon, the composite materials thus obtained, as well as their use for the manufacture of composite products.
- Carbon nanotubes have particular crystalline structures, tubular, hollow and closed, composed of atoms regularly arranged in pentagons, hexagons and / or heptagons, obtained from carbon.
- CNTs generally consist of one or more coiled graphite sheets.
- One-sided nanotubes Single Wall Nanotubes or SWNTs
- Multi Wall Nanotubes or MWNTs are thus distinguished.
- CNTs are commercially available or can be prepared by known methods. There are several methods of synthesis of CNTs, including electrical discharge, laser ablation and chemical vapor deposition or CVD (Chemical Vapor Deposition) which ensures the production of large quantities of carbon nanotubes and therefore obtaining them at a cost price compatible with their massive use.
- This process consists precisely in injecting a source of carbon at relatively high temperature over a catalyst which may itself consist of a metal such as iron, cobalt, nickel or molybdenum, supported on an inorganic solid such as alumina, silica or magnesia.
- Carbon sources can include methane, ethane, ethylene, acetylene, ethanol, methanol or even a mixture of carbon monoxide and hydrogen (HIPCO process).
- the CNTs have both excellent stiffness (measured by the Young's modulus), comparable to that of steel, while being extremely light. In addition, they have excellent electrical and thermal conductivity properties that allow to consider using them as additives to impart these properties to various materials, including macromolecular.
- Some solutions have been proposed to facilitate the dispersion of CNTs in a polymer matrix. These include sonication, which has only a temporary effect, or ultrasonication which has the effect of partially cutting the nanotubes and creating oxygenated functions that can affect some of their properties.
- Another solution consisted in carrying out a dispersion of NTC in a solvent and a monomer and carrying out an in situ polymerization leading to the production of functionalized NTC. This solution is however complex and can be expensive depending on the products used.
- the grafting operations may damage the structure of the nanotubes and, consequently, their electrical and / or mechanical properties.
- the composite material obtained contains 7 to 15% of CNT and is intended to be used as such in the form of a tube or to be shaped in the form of granules. It would therefore be desirable to have a means of dispersing larger amounts of CNTs in any polymer matrix, and not just a polyamide matrix, so that NTC-heavy masterbatches capable of preparing to be used for the manufacture of various mechanical and electronic parts in different polymers.
- the subject of the present invention is thus a process for preparing a composite material containing from 10 to 50% by weight of nanotubes, comprising:
- thermoplastic polymer (c) mixing the molten thermoplastic polymer and the nanotubes, the method further comprising adding at least one plasticizer to the mixer, in a weight ratio of 10 to 400% by weight, relative to the weight of nanotubes used. at least 50% of the weight of the plasticizer being introduced upstream of or into the melting zone of the polymer, it being understood that, in the case where the plasticizer, the thermoplastic polymer and the nanotubes are introduced simultaneously or successively into the same hopper
- the polymer is in the form of a powder / granule mixture ranging from 10:90 to 100: 0, preferably predominantly in powder form.
- the process according to the invention is carried out in a mixer which is advantageously a compounding device.
- compounding device an apparatus conventionally used in the plastics industry for the melt blending of thermoplastic polymers and additives in order to produce composites.
- the polymeric composition and the additives are mixed using a high shear device, for example a co-rotating twin-screw extruder or co-kneader.
- the melt generally comes out of the apparatus in solid physical form agglomerated, for example in the form of granules, or in the form of rods which, after cooling, are cut into granules.
- co-mixers ® BUSS MDK 46 examples of suitable co-mixers according to the invention are co-mixers ® BUSS MDK 46 and those of the series BUSS ® MKS or MX, sold by
- BUSS AG which all consist of a screw shaft provided with fins, arranged in a heating sleeve optionally consisting of several parts and whose inner wall is provided with kneading teeth adapted to cooperate with the fins to produce shear the kneaded material.
- the shaft is rotated and provided with an oscillating movement in the direction axial, by a motor.
- co-kneaders may be equipped with a granule manufacturing system, adapted for example to their outlet orifice, which may consist of an extrusion screw or a pump.
- the co-kneaders which can be used according to the invention preferably have an L / D screw ratio ranging from 7 to 22, for example from 10 to 20, while the co-rotating extruders advantageously have an L / D ratio ranging from 15 to 56, for example from 20 to 50.
- the compounding step is generally carried out at a temperature ranging from 30 to 32O 0 C, for example from 70 to 300 ° C.
- This temperature which is greater than the glass transition temperature (Tg) in the case amorphous thermoplastic elastomers and at the melting temperature, in the case of semi-crystalline thermoplastic polymers, is a function of the polymer specifically used and generally mentioned by the supplier of the polymer.
- the nanotubes that may be used according to the invention may be carbon nanotubes (hereafter CNTs) or nanotubes based on boron, phosphorus or nitrogen, or nanotubes containing several of these elements or at least one of them. of these elements in combination with carbon. It is advantageously carbon nanotubes. They may be of the single-wall, double-wall or multi-wall type.
- the double-walled nanotubes can in particular be prepared as described by FLAHAUT et al in Chem. Corn. (2003), 1442.
- the multi-walled nanotubes may themselves be prepared as described in WO 03/02456.
- the nanotubes used according to the invention usually have a mean diameter ranging from 0.1 to 200 nm, preferably from 0.1 to 100 nm, more preferably from 0.4 to 50 nm and better still from 1 to 30 nm. nm, for example from 3 to 30 nm, and advantageously a length of more than 0.1 microns and advantageously from 0.1 to 20 microns, for example about 6 microns. Their length / diameter ratio is advantageously greater than 10 and most often greater than 100.
- These nanotubes therefore comprise in particular nanotubes known as "VGCF" (carbon fibers obtained by chemical vapor deposition or Vapor Grown Carbon Fibers).
- the carbon nanotubes according to the invention are preferably multi-walled carbon nanotubes and may for example comprise from 5 to 15 sheets and more preferably from 7 to 10 sheets.
- crude carbon nanotubes is especially commercially available from Arkema under the trade name Graphistrength® ® C100.
- the nanotubes may be purified and / or treated (in particular oxidized) and / or milled before being used in the process according to the invention. They can also be functionalized by solution chemistry methods such as amination or reaction with coupling agents.
- the CNTs are advantageously in the form of a powder.
- the grinding of the nanotubes may in particular be carried out cold or hot and be carried out according to known techniques used in apparatus such as ball mills, hammers, grinders, knives, gas jet or any other grinding system. likely to reduce the size of the entangled network of nanotubes. It is preferred that this grinding step is performed according to a gas jet grinding technique and in particular in an air jet mill.
- the purification of the nanotubes may be carried out by washing with a sulfuric acid solution, or another acid, so as to rid them of any residual mineral and metal impurities from their preparation process.
- the weight ratio of the nanotubes to the sulfuric acid may especially be between 1: 2 and 1: 3.
- the purification operation may also be carried out at a temperature ranging from 90 to 120 ° C., for example for a period of 5 to 10 hours. This operation may advantageously be followed by rinsing steps with water and drying the purified nanotubes.
- Another way of purifying the nanotubes, intended in particular to remove the iron and / or magnesium they contain, is to subject them to a heat treatment at more than 1,000 0 C.
- the oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite containing from 0.5 to 15% by weight of NaOCl and preferably from 1 to 10% by weight of NaOCl, for example in a weight ratio of nanotubes to sodium hypochlorite ranging from 1: 0.1 to 1: 1.
- the oxidation is advantageously carried out at a temperature of less than 60 ° C. and preferably at ambient temperature, for a duration ranging from a few minutes to 24 hours. This oxidation operation may advantageously be followed by filtration and / or centrifugation, washing and drying steps of the oxidized nanotubes.
- the nanotubes be used in the process according to the invention in the raw state. It has indeed been demonstrated that a preliminary surface treatment of the nanotubes was not necessary. Without being bound by this theory, the Applicant believes that the plasticizer, which is introduced into the process according to the invention before contacting the nanotubes with the molten polymer, is absorbed on the surface of the nanotubes, which has the effect of:
- nanotubes obtained from raw materials of renewable origin in particular of plant origin, as described in document FR 2 914 634.
- the amount of nanotubes used according to the invention represents from 10 to 50% by weight, preferably between 15% and up to 50% by weight, for example between 5% and up to 40% by weight, and more preferably from 20 to 50% by weight, for example from
- the nanotubes (raw or crushed and / or purified and / or oxidized and / or functionalized by a non-plasticizing molecule) are brought into contact with at least one thermoplastic polymer.
- thermoplastic polymer means a polymer which melts when the heater and that can be put and shaped in the molten state.
- This thermoplastic polymer may especially be chosen from: homo- and copolymers of olefins such as acrylonitrile-butadiene-styrene copolymers, styrene-butadiene-alkyl methacrylate (or SBM) copolymers; polyethylene, polypropylene, polybutadiene and polybutylene; acrylic homo- and copolymers and alkyl poly (meth) acrylates such as poly (methyl methacrylate); homo- and copolyamides; polycarbonates; polyesters including poly (ethylene terephthalate) and poly (butylene terephthalate); polyethers such as polyphenylene ether, polyoxymethylene, polyethylene oxide or polyethylene glycol and polyoxypropylene; polystyrene; copolymers of styrene and maleic anhydride; polyvinyl chloride; fluorinated polymers such as polyvinylidene fluoride, polytetrafluoroethylene and
- the polymer is chosen from homo- and copolyamides.
- PA homopolyamides
- PA-6, PA-II and PA-12 obtained by polymerization of an amino acid or a lactam, PA-6.6, PA-4.6, PA-6.10, PA-6.12, PA-6.14, PA 6-18 and PA-10.10 obtained by polycondensation of a diacid and a diamine, as well as aromatic polyamides such as polyarylamides and polyamides; polyphthalamides.
- PA He, PA-12, aromatic PA are in particular available from the company Arkema under the trade name Rilsan ®.
- Copolyamides can be obtained from various starting materials: (i) lactams, (ii) aminocarboxylic acids or (iii) equimolar amounts of diamines and dicarboxylic acids. Obtaining a copolyamide requires choosing at least two different starting materials from those mentioned above. The copolyamide then comprises at least these two units. It can thus be a lactam and an aminocarboxylic acid having a different number of carbon atoms, or two lactams having different molecular weights, or a lactam combined with an equimolar amount of a diamine and a dicarboxylic acid.
- the lactams (i) may in particular be chosen from lauryllactam and / or caprolactam.
- the aminocarboxylic acid (ii) is advantageously chosen from ⁇ , ⁇ -amino carboxylic acids, such as 11-aminoundecanoic acid or 12-aminododecanoic acid.
- the precursor (iii) may in particular be a combination of at least one aliphatic, cycloaliphatic or aromatic C 6 -C 36 dicarboxylic acid, such as adipic acid, azelaic acid, sebacic acid, brassylic acid, n-dodecanedioic acid, terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid with at least one aliphatic, cycloaliphatic, arylaliphatic or aromatic diamine C 4 -C 22 / - such as hexamethylenediamine, piperazine, 2-methyl-1,5-diaminopentane, m-xylylenediamine or p-xylylenediamine; it being understood that said diacid (s) carboxylic (s) and diamine (s) are used, when present, in equimolar amount.
- Such copolyamides are in particular marketed under the trade name Plate
- the polymer may be chosen from styrene-butadiene-alkyl methacrylate, especially C 1 -C 8 (or SBM) copolymers, in particular:
- Such copolymers are especially available in powder form from the company ARKEMA under the trade name Nanostrength® E41; 2) core-shell type copolymers consisting of a core coated with one or more barks, the core of which contains a homo- or copolymer of butadiene, styrene and / or alkyl methacrylate, especially C 1 to C Cs, especially a copolymer of butadiene and styrene, and at least one bark, and preferably each of the barks, contains a homo- or copolymer of styrene and / or alkyl methacrylate, in particular Ci-Cs.
- the heart can be coated with an inner bark made of polystyrene and an outer bark of PMMA.
- core-shell copolymers are in particular described in WO 2006/106214.
- a core-bark SBM copolymer that can be used in the present invention is especially marketed by the company Arkema under the trade name Durastrength® E920.
- the polymeric composition used according to the invention may contain, in addition to the thermoplastic polymer, various additives, intended in particular to promote the subsequent dispersion of the composite material in a liquid formulation, such as polymeric dispersants, in particular carboxymethyl cellulose, acrylic polymers, the polymer sold by LUBRIZOL under the trade name Solplus® DP310 and functionalized amphiphilic hydrocarbons, such as the product marketed by TRILLIUM SPECIALTIES under the trade name Trilsperse® 800, surfactants such as sodium dodecylbenzene sulphonate, and their mixtures.
- the polymeric composition may also contain fillers, for example graphene-based fillers other than nanotubes (especially fullerenes), silica or calcium carbonate.
- this polymeric composition is brought into contact with the aforementioned nanotubes and with at least one plasticizer.
- plasticizer is meant, in the sense of the present invention, a compound which, introduced into a polymer, increases its flexibility, decreases its glass transition temperature (Tg), increases its malleability and / or its extensibility.
- plasticizers that can be used according to the invention, mention may be made in particular of the alkyl esters of phosphates, of hydroxybenzoic acid (in which the alkyl group, preferably linear, contains from 1 to 20 carbon atoms), of lauric acid, of azelaic acid and pelargonic acid, arylphosphates, phthalates, especially dialkyl or alkylaryl, in particular alkylbenzyl, linear or branched alkyl groups, independently containing from 1 to 12 carbon atoms, nitrile resins, - poly (butylene terephthalate) cyclized and mixtures thereof, such as the CBT ® resin
- adipates especially dialkyl, for example di (2-ethylhexyl), sebacates, especially dialkyl and in particular dioctyl, glycol or glycerol benzoates, dibenzyl ethers, chloroparaffins, functionalized amphiphilic hydrocarbons, such as the product marketed by TRILLIUM SPECIALTIES under the trade name Trilsperse® 800, propylene carbonate, sulphonamides, in particular alkyl sulphonamides, aryl sulphonamides and arylalkyl sulphonamides, the aryl group of which is optionally substituted with at least one alkyl group containing 1 to 12 carbon atoms, such as benzene sulfonamides and toluene sulfonamides, said sulfonamides being N-substituted or N, N-disubstituted by at least
- plasticizers those preferred for use in the present invention include sulfonamides; aryl phosphates; phthalates, nitrile resins and their mixtures.
- plasticisers include: N-butylbenzenesulfonamide (BBSA), N-ethylbenzenesulfonamide (EBSA), N-propylbenzenesulfonamide (PBSA), N-butyl-N-dodecylbenzenesulfonamide (BDBSA), N , NOT- dimethyl benzenesulfonamide (DMBSA), para-methylbenzene sulfonamide, ortho-toluenesulfonamide, para-toluenesulfonamide, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), neopentyl glycol bis (diphenyl phosphate), dioctyl phthalate glycol
- BBSA N
- the plasticizer may be used in a proportion of 10 to 400% by weight, preferably 50 to 200% by weight, and more preferably 75 to 150% by weight, relative to the weight of nanotubes used. It can thus represent, for example, from 5 to 80% by weight and more generally from 10 to 30% by weight, relative to the total weight of the composite material.
- plasticizer used according to the present invention will be a function of the chemical nature of the matrix to be reinforced by the nanotubes.
- Table 1 gives, as an indication, some examples of particularly suitable plasticizer / polymer matrix combinations.
- the present invention also relates to methods applied to given polymer / plasticizer couples.
- thermoplastic polymer (c) mixing the molten thermoplastic polymer and the nanotubes, the method further comprising adding at least one plasticizer to the mixer, selected from: sulfonamides, hydroxybenzoates, phthalates, adipates and phosphates, in a weight ratio of 10 to 400% by weight, relative to the weight of nanotubes used, at least 50% of the weight of the plasticizer being introduced upstream of or in the melting zone of the polymer, it being understood that, in the when the plasticizer, the thermoplastic polymer and the nanotubes are introduced simultaneously or successively into the same feed hopper of the mixer, the polymer is in the form of a mixture powder / granules ranging from 10:90 to 100: 0, preferably predominantly in powder form.
- plasticizer selected from: sulfonamides, hydroxybenzoates, phthalates, adipates and phosphates
- thermoplastic polymer (c) mixing the molten thermoplastic polymer and the nanotubes, the method further comprising adding at least one plasticizer to the mixer, selected from phosphate alkyl esters, aryl phosphates and phthalates, in a weight ratio of 10 to 400% by weight, relative to the weight of nanotubes used, at least 50% of the weight of the plasticizer being introduced upstream of or in the melting zone of the polymer.
- at least one plasticizer selected from phosphate alkyl esters, aryl phosphates and phthalates, in a weight ratio of 10 to 400% by weight, relative to the weight of nanotubes used, at least 50% of the weight of the plasticizer being introduced upstream of or in the melting zone of the polymer.
- thermoplastic polymer melting the thermoplastic polymer, and (c) mixing the molten thermoplastic polymer and the nanotubes, the method further comprising adding at least one plasticizer to the mixer, selected from phthalates and nitrile resins, in a weight ratio of 10 to 400% by weight, based on the weight of nanotubes used, at least 50% of the weight of the plasticizer being introduced upstream of or in the melting zone of the polymer.
- at least one plasticizer selected from phthalates and nitrile resins
- thermoplastic polymer (c) mixing the molten thermoplastic polymer and nanotubes, the method further comprising adding at least one plasticizer to the mixer, selected from glycols, in a weight ratio of 10 to 400% by weight, relative to weight of nanotubes used, at least 50% of the weight of the plasticizer being introduced upstream of or in the melting zone of the polymer.
- at least one plasticizer selected from glycols, in a weight ratio of 10 to 400% by weight, relative to weight of nanotubes used, at least 50% of the weight of the plasticizer being introduced upstream of or in the melting zone of the polymer.
- At least 50% of the weight of the plasticizer used is introduced into the mixer upstream of or in the melting zone of the polymer.
- the plasticizer is introduced wholly or partly at the beginning of the polymer melting zone.
- the plasticizer, the thermoplastic polymer and the nanotubes may alternatively be introduced simultaneously or successively into the same feed hopper of the mixer. It is generally preferred to introduce all the plasticizer into this hopper.
- the aforementioned materials can be introduced successively, in any order, either directly into the hopper, or into a suitable container where they are homogenized before being introduced into the hopper.
- the polymer is in the form of a powder / granule mixture ranging from 10:90 to 100: 0, preferably the polymer is predominantly in powder form, rather than granules.
- the Applicant has in fact demonstrated that this results in a better dispersion of the nanotubes in the polymer matrix, and a better conductivity of the composite material obtained.
- This second embodiment of the invention is well suited to solid plasticizers. These can possibly be introduced into the feed hopper of the mixer in the form of pre-composite with the nanotubes.
- a pre-composite containing 70% by weight of cyclized poly (butylene terephthalate) plasticizer and 30% by weight of multi-walled nanotubes, is for example commercially available from the company ARKEMA under the trade name Graphistrength® C M12-30.
- the nanotubes and the plasticizer can be introduced into the hopper or the aforementioned container in the form of pre-composite.
- a pre-composite may for example be obtained according to a method involving:
- the first step above can be carried out in conventional synthesis reactors, paddle mixers, fluidized bed reactors or in Brabender mixers, Z-arm mixer or extruder. It is generally preferred to use a conical mixer, for example of the HOSOKAWA Vrieco-Nauta type, comprising a rotating screw rotating along the wall of a conical tank.
- a conical mixer for example of the HOSOKAWA Vrieco-Nauta type, comprising a rotating screw rotating along the wall of a conical tank.
- a pre-composite may be formed from the liquid plasticizer and the thermoplastic polymer, before mixing with the nanotubes.
- a composite material is obtained.
- the subject of the invention is also the composite material that can be obtained according to the process described above.
- This composite material can either be used as is, or be used as a masterbatch and thus diluted in a polymer matrix to form a composite product.
- the invention also relates to the use of the composite material described above for the manufacture of a composite product and / or to confer at least one electrical, mechanical and / or thermal property to a polymer matrix.
- the composite product may contain from 0.5 to 5% by weight of nanotubes, for example.
- the polymer matrix generally contains at least one polymer chosen from random, thermosetting, rigid or elastomeric, crystalline, amorphous or semicrystalline random or gradual homo- or copolymers.
- Preferably used according to the invention at least one thermoplastic polymer and / or an elastomer, which may in particular be chosen from those listed above.
- the polymer matrix can include, in particular, a polymer such as poly (chlorine chloride). vinyl) or PVC.
- the polymer matrix may further include various adjuvants and additives such as lubricants, pigments, stabilizers, fillers or reinforcements, anti-static agents, fungicides, flame retardants and solvents.
- adjuvants and additives such as lubricants, pigments, stabilizers, fillers or reinforcements, anti-static agents, fungicides, flame retardants and solvents.
- the composite product obtained can be used for the manufacture of devices for transporting or storing fluids, such as pipes, tanks, off-shore pipes or hoses, for example , in order to prevent the accumulation of electrostatic charges.
- this composite product can be used for the manufacture of compact or porous electrodes, including supercapacitors or fuel cells.
- the composite material obtained according to the invention can be used to viscosify and / or thicken a liquid formulation, containing or not a polymer matrix.
- This liquid formulation then contains at least one solvent of the thermoplastic polymer.
- the thermoplastic polymer is a water-soluble poly (ethylene glycol)
- the liquid formulation may contain water.
- the invention thus provides a means for viscosifying and / or thickening a liquid formulation containing at least one solvent of the thermoplastic polymer, in particular a composition of ink, varnish, paint, putty, bituminous product or concrete, for example . It therefore also relates to the aforementioned use of the composite material described above.
- the composite material according to the invention can be used to produce conductive fibers (obtained in particular by molten route) or conductive mono- or multilayer films, that is to say having general an electrical resistivity of 10 1 to 10 8 Ohm. cm. It has indeed been demonstrated that the process according to the invention makes it possible to obtain composite materials that can be converted into fibers or extruded films having a better electrical conductivity and mechanical properties that are as good as those of the prior art, probably because of the absence of aggregates of nanotubes generating defects in these fibers and films and / or greater mobility nanotubes. These fibers can in particular be used in the manufacture of conductive textiles. In these applications, it is preferred that the plasticizer be chosen from: cyclic oligobutyl (or polybutylene) terephthalates, functionalized amphiphilic hydrocarbons, alkyl sulfonamides and mixtures thereof.
- FIG. 1 illustrates the resistivity curve as a function of the temperature of a composite product obtained according to the invention and a comparative composite product based on PA-12;
- FIG. 2 illustrates the resistivity versus temperature curve of a composite product obtained according to the invention and a comparative composite product, based on PA-6; and
- FIG. 3 illustrates the resistivity versus temperature curve of a composite product obtained according to the invention and a comparative composite product based on polycarbonate.
- the ingredients of Formulation IA all solid, were introduced into a single hopper.
- the ingredients of formulation IB were partly introduced into the same hopper (polyamide and nanotubes) and partly injected with a gravimetric dosing pump into the first zone of the co-kneader (BBSA), which corresponds to the beginning of the melting of the polymer.
- BBSA co-kneader
- formulation IA generates deposits in the co-kneader, contrary to the formulation IB.
- the method according to the invention makes it possible to manufacture a composite material with a high dosage of nanotubes in milder conditions than a process which does not use a plasticizer. This process therefore makes it possible to continuously manufacture composite materials without degrading the polymer matrix or generating unacceptable pollution of the equipment.
- the composite product manufactured according to the invention (MB with BBSA) has electrical conduction properties at a lower temperature than the comparative composite product (MB without BBSA).
- the invention thus makes it possible to obtain composite products under milder process conditions, preserving the polymer matrix.
- the ingredients of formulation 3A all solid, were introduced into a single hopper.
- the ingredients of the formulation 3B were partly introduced into the same hopper (polyamide and nanotubes) and partly injected with a gravimetric dosing pump, on the one hand (10% BBSA) in the first zone of the co-kneader corresponding to the beginning of the melting of the polymer and, on the other hand (5% BBSA), in the second zone of the co-kneader, downstream of this melting zone.
- the formulation 3A was more viscous and resulted in a power consumption of 5.7-5.8 kW for the co-kneader, which exceeded after 10 h of compounding the nominal power indicated by the manufacturer (6.0 kW) , thus requiring to reduce the flow rate to 10 kg / h.
- the temperature of the material in the last zone of the co-kneader rose to about 32O 0 C.
- the method according to the invention makes it possible to continuously manufacture materials composites strongly dosed in NTC without degrading the polymer matrix nor polluting the equipment.
- the use of the composite material manufactured according to the invention makes it possible to reduce the manufacturing temperature of the composite product by 20 ° C., while giving the latter the same electrostatic dissipation properties.
- the ingredients of formulation 5A all solid, were introduced into a single hopper.
- the ingredients of the formulation 5B were partly introduced into the same hopper (polycarbonate and nanotubes) and partly injected with a gravimetric dosing pump, equipped with a liquid heating system at 80 ° C., in the first zone of the co-kneader corresponding to the beginning of the melting of the polymer.
- the temperature setpoints were similar for the two formulations (zone 1 / zone 2 of the co-kneader: 300/260 ° C. and 310/270 ° C.).
- These composite materials can be diluted up to 2-3% by weight of NTC in a polymer matrix based on polycarbonate, ABS resin or ABS / styrene copolymer, for the manufacture of conductive materials and flame retardants (that is to say having a VO index at UL94 fire test and LOI greater than 32%).
- the use of the composite material manufactured according to the invention makes it possible to reduce by 20 ° C. the manufacturing temperature of the composite product, while giving the latter the same properties of electrostatic dissipation.
- Example 3 was repeated except that the plasticizer was fully introduced into the co-kneader downstream of the PA-6 melting zone.
- a precomposite containing 50% by weight of propylene glycol and 50% by weight of carbon nanotubes was introduced into the first doser of a CLEXTRAL BC21 co-rotating twin-screw extruder.
- a mixture of powders consisting of 40% by weight of poly (ethylene glycol) (CLARIANT PEG 1500, 40% by weight of CLARIANT carboxymethyl cellulose and 20% by weight of dodecyl was introduced.
- benzene sodium sulfonate was introduced into the first doser of a CLEXTRAL BC21 co-rotating twin-screw extruder.
- the compounding was carried out at a set temperature of 100 ° C., with a rotational speed of the screw of 600 rpm and at a flow rate of 10 kg / h.
- the masterbatch obtained which contained (to be completed)% by weight of CNT, was conditioned in the solid state without granulation at the die outlet. It may be introduced into a solvent formulation after being impregnated for a few hours at room temperature with a mixture of solvents present in said formulation.
- the solid ingredients of the formulations 10A and 10B were in part (polymer and nanotubes) introduced into the same feed hopper and in part (plasticizer) injected with a gravimetric dosing pump into the first zone of the co-kneader corresponding to the melting of the polymer.
- the pump was equipped with a liquid heating system at 160 ° C. for formulation 8A and at 100 ° C. for formulation 8B.
- the temperature setpoints were similar for the two formulations (zone 1 / zone 2 of the co-kneader: 220/200 ° C.).
- the material temperature did not exceed 24O 0 C despite the high content of CNT (30%). It emerges from this example that the process according to the invention makes it possible to continuously manufacture composite materials with a high NTC content without degrading the polymer matrix.
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Abstract
Description
Claims
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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FR0857173A FR2937324B1 (fr) | 2008-10-22 | 2008-10-22 | Procede de preparation d'un materiau composite a base de nanotubes, notamment de carbone |
FR0951843A FR2937323B1 (fr) | 2008-10-22 | 2009-03-23 | Procede de preparation d'un materiau composite thermoplastique a base de nanotubes, notamment de carbone |
US23547109P | 2009-08-20 | 2009-08-20 | |
PCT/FR2009/052034 WO2010046606A1 (fr) | 2008-10-22 | 2009-10-22 | Procédé de préparation d'un matériau composite thermoplastique à base de nanotubes, notamment de carbone |
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EP2344575A1 true EP2344575A1 (fr) | 2011-07-20 |
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EP09760201A Withdrawn EP2344575A1 (fr) | 2008-10-22 | 2009-10-22 | Procédé de préparation d'un matériau composite thermoplastique à base de nanotubes, notamment de carbone |
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EP (1) | EP2344575A1 (fr) |
JP (1) | JP2012506475A (fr) |
KR (1) | KR20110057254A (fr) |
CN (1) | CN102264809A (fr) |
FR (2) | FR2937324B1 (fr) |
WO (1) | WO2010046606A1 (fr) |
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FR2937323A1 (fr) | 2010-04-23 |
WO2010046606A1 (fr) | 2010-04-29 |
FR2937323B1 (fr) | 2011-02-25 |
FR2937324B1 (fr) | 2012-03-16 |
KR20110057254A (ko) | 2011-05-31 |
CN102264809A (zh) | 2011-11-30 |
FR2937324A1 (fr) | 2010-04-23 |
JP2012506475A (ja) | 2012-03-15 |
US20110201731A1 (en) | 2011-08-18 |
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