EP2193160A2 - Verfahren zur herstellung von verbundmaterialien - Google Patents

Verfahren zur herstellung von verbundmaterialien

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Publication number
EP2193160A2
EP2193160A2 EP08837912A EP08837912A EP2193160A2 EP 2193160 A2 EP2193160 A2 EP 2193160A2 EP 08837912 A EP08837912 A EP 08837912A EP 08837912 A EP08837912 A EP 08837912A EP 2193160 A2 EP2193160 A2 EP 2193160A2
Authority
EP
European Patent Office
Prior art keywords
mixture
powder
thermoplastic
weight
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.)
Withdrawn
Application number
EP08837912A
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English (en)
French (fr)
Inventor
Patrick Piccione
Catherine Bluteau
Benoît BRULE
Alexander Korzhenko
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.)
Arkema France SA
Original Assignee
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
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2193160A2 publication Critical patent/EP2193160A2/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • 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
    • C08J3/22—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
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a method for manufacturing a composite material comprising: preparing a masterbatch based on carbon nanotubes, under specified conditions, and introducing said masterbatch into a thermoplastic polymer composition and or elastomeric.
  • Carbon nanotubes are known and possess particular crystalline structures, tubular, hollow and closed, composed of atoms arranged regularly in pentagons, hexagons and / or heptagons, obtained from carbon.
  • CNTs generally consist of one or more coiled graphite sheets.
  • SWNTs single wall nanotubes
  • Multi Wall Nanotubes or MWNTs Multi Wall Nanotubes
  • TCMs 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 application WO 86/03455 A1 of Hyperion Cataiysis International Inc. describes in particular the synthesis of CNTs. More particularly, the process comprises contacting a metal-based particle, such as in particular iron, cobalt or nickel, with a gaseous compound based on carbon, at a temperature of between 850 ° C. and 1200 ° C. C, the dry weight proportion of the carbon-based compound relative to the metal-based particle being at least about 100: i.
  • a metal-based particle such as in particular iron, cobalt or nickel
  • the CNTs have both excellent stiffness (measured by the Young's modulus), comparable to that of steel, while being extremely light.
  • 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, such as thermopiastics and elastomers.
  • Thermoplastics are an important class of synthetic materials used more and more in various applications.
  • thermoplastics are an ideal material, particularly for buildings (piping systems, pipes, etc.), packaging, packaging (bottles and flasks), electrical insulation, appliances, clothing, elastomers, their high elasticity makes them indispensable in the manufacture of mechanical parts, such as in the transport of electrical energy or in the field of hygiene.
  • CNTs are difficult to handle and disperse, because of their small size, their powderiness and possibly, when they are obtained by the CVD technique, their entangled structure, all the more important that the we are trying to increase their mass productivity in order to improve production and reduce the residual ash content.
  • the existence of strong Van der Waals interactions between the nanotubes also affects their dispersibility and the stability of the suspensions obtained.
  • CNTs significantly affects the performance of the composites they form with the polymer matrices into which they are introduced.
  • the poor dispersibility of carbon nanotubes is particularly observed in the case of thermoplastic and / or elastomeric polymer matrices, particularly when the polymer is used in the form of granules, as described in particular in document US 2004/026581.
  • JP2003-012939 also discloses a powdery masterbatch based on CNT and polyamide.
  • the subject of the present invention is therefore a process for manufacturing a composite material comprising: A- preparing a masterbatch based on carbon nanotubes (hereafter NTC) according to a process comprising:
  • masterbatches means concentrates of active material that are CNTs, which are intended to be subsequently incorporated into a polymer (compatible or not with the polymer already contained in these masterbatches).
  • a masterbatch in an agglomerated solid physical form has a number of advantages such as, in particular, the absence of fines, a good flexibility in the hoppers, a precise and lossless metering, easy handling, good dispersion, lower volatility and less sensitivity to moisture compared to powders, reduced handling risks, lower mass and volume, no precipitation and settling of solutions or suspensions as well as a clear reduction in transport risks.
  • the carbon nanotubes that can be used according to the invention can be of the single-walled, double-walled or multi-walled 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 masterbatch used according to the invention comprises from 2% to 30% by weight, preferably from 5% to 25% by weight and more preferably from 10% to 20% by weight of CNT, relative to the weight of the total pulverulent mixture. .
  • the composite obtained preferably comprises from 0.5% to 20% by weight, preferably from 0.5% to 10% by weight and more preferably from 0.5% to 5% by weight of CNT, relative to the weight of the mixture. total powder.
  • 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. 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 include nanotubes called "VGCF" nanotubes.
  • the multiwall carbon nanotubes 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 grinding of the nanctubes can be carried out in particular at cold or hot and be carried out according to known techniques used in devices 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 nanotubes to sulphuric acid can in particular 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.
  • 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 KaOCi and preferably from 1 to 10% by weight of NaOCl, by 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 below 60 ° C. and preferably at room temperature, for a duration ranging from a few minutes to 24 hours. This oxidation operation may advantageously be followed by steps of fi ltration and / or centrifugation, washing and drying of the oxidized nanotubes.
  • 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 and / or elastomeric polymeric matrix.
  • thermoplastic polymer matrix is intended to mean a polymer or a mixture of polymers which melts when heated and which can be shaped in the molten state.
  • thermopiastics offering a wide range of interesting properties. They can be made as flexible as rubber, as rigid as metal and concrete, or made as transparent as glass, for use in many pipe products and other components. They do not oxidize and have a high resistance to corrosion.
  • polyamide (PA) such as polyamide 6
  • PA-6 polyamide 11 (PA-II), polyamide 12 (PA-12), polyamide 6.6 (PA-6.6), polyamide 4.6 (PA-4.6), 6.10 polyamide (PA-6.10) and polyamide 6.12 (PA-6.12), some of these polymers being sold in particular by Arkema under the name Rilsan 0 and preferred being those of fluid grade such as Rilsan ® AMNO TLD.
  • PVDF polyvinylidene fluoride
  • ABS acrylonitrile butadiene styrene
  • AMMA acrylonitrile methyl methacrylate
  • CA cellulose acetate
  • E / P ethylene / propylene copolymer
  • EFE ethylene / tetrafluoroethylene copolymer
  • EVAC ethylene vinyl acetate
  • EVOH ethylene vinyl alcohol
  • MABS methyl cellulose
  • MBS methyl-methacrylate-butadiene-styrene
  • PAI polyamide imide
  • PBT polybutylene terephthalate
  • PC polycarbonate
  • PE polyethylene
  • PEN polyethersulfone
  • PET poly (ethylene terephthalate)
  • PETP poly (poly) terephthalate
  • PFA polyimide
  • PK polyketone
  • PMMA polymethyl methacrylate
  • PMMA polyethyl pentene
  • PMP polyoxymethylene or polyacetal
  • PP polypropylene
  • PPE poly (phenylene ether)
  • PPOX poly (propylene oxide)
  • PPS polyphenylene sulfide
  • PS polystyrene
  • PSU polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • PVAC polyvinyl acetate
  • PVC polyvinyl chloride
  • PVF polyvinyl fluoride
  • S / B poly (styrene) butadiene)
  • SMAH styrene maleic anhydride
  • VE vinyl ester resin
  • PEI polyetherimide
  • PCTFE polychlorotrifluoroethylene
  • PCTFE polyarylsulfone
  • the term "elastomeric or elastomeric polymer matrix” is intended to mean an elastic polymer, that is to say a polymer that supports very large deformations, much greater than 100% and (almost) completely reversible.
  • An elastomer is made up of long molecular chains that are gathered at rest in "balls". These chains are interconnected by crosslinking points, entanglements or polar bonds with mineral fillers, and form a network.
  • fluoroelastomers such as those sold under the trade names Kalrez u and Viton ° by the company DuPont Performance Eîastomers, natural or synthetic latex, chloroprene-based rubber such as that marketed under the trademark Neoprene D by the company DuPont Chemicals, polyacrylics, polybutadiene, polyether amide block, polyisobutylene, polyisoprene, polyurethane, silicones, natural rubber (styrene butadiene rubber or SBR), eiasuomers marketed under the trademarks Vistamaxx ", Vistaflex Thermoplastic Elastomers, Dytron Santoprene Thermoplastic Elastomers and '5 Thermopiastic Vuicanizates by ExxonMobil Chemical Company, etc.
  • fluoroelastomers such as those sold under the trade names Kalrez u and Viton ° by the company DuPont Performance Eîastomers, natural or synthetic latex, chloroprene
  • polymer according to the invention also covers oligomers, as well as alloys of thermoplastic polymers, of elastomers with one another, or with each other.
  • the masterbatch used according to the invention comprises from 95% to 70% by weight, and preferably from 90% to 80% by weight of polymer matrix, based on the weight of the total powder mixture.
  • the composite obtained according to the invention thus advantageously comprises from 99.5% to 80% by weight, and preferably from 99.5% to 95% by weight of polymer matrix, relative to the weight of the total powder mixture.
  • the average particle size of the polymeric matrix powder is preferably between
  • 0.1 ⁇ m and 1000 ⁇ m preferably between 10 ⁇ m and 800 ⁇ m, and even more preferably between 50 ⁇ m and 300 ⁇ m.
  • the average particle size of the polymer matrix powder is between 100 ⁇ m and 150 ⁇ m.
  • the first step of the process according to the invention consists in mixing the powders of CNT and of polymer matrix, which will then be implemented in the second stage.
  • the NTC and polymer powders may be mixed in a mixer which is either integrated with the processing apparatus or disposed upstream thereof.
  • This powder mixture can be produced in conventional synthesis reactors, paddle mixers, fluidized bed reactors or in Brabender mixers, z-arm mixer or extruder. According to a variant of the invention, it is thus possible to use a mixer with or without arms.
  • the pulverulent mixture of CNTs and at least one polymeric matrix may further comprise one or more other pulverulent fillers.
  • pulverulent fillers There may be mentioned in particular carbon blacks, activated carbons, silicas, metals, ceramic materials, glass fibers, pigments, clays, calcium carbonate, boron and / or nitrogen nanotubes and / or transition metals, metals, ceramic materials.
  • This first step of dry mixing of powders or dry-blend is preferably followed by a heat treatment step where the passage of the polymer in liquid or gaseous form takes place in order to ensure an intimate and homogeneous mixture of the polymer with the CNTs. .
  • This heat treatment consists of a rise in temperature of the powder so that its physicochemical properties are modified. This heat treatment is advantageously carried out in an extruder.
  • the second step of the process according to the invention consists of the implementation of the mixture in order to obtain agglomerated solid physical forms. This step can be carried out by any method known to those skilled in the art.
  • agglomeration fluidized bed which is a conventional method for obtaining granules from powder.
  • the fluidized powder is moistened until liquid bridges form between the particles.
  • Water, solutions, suspensions or melts can be sprayed to achieve the desired product quality. Thanks to this technology, the level of fines is considerably reduced, the fluidity and the dispersion capacity in the water are improved, the granules obtained are very aerated and dissolve very easily.
  • the agglomeration process by its action, solves the stability problems of the powdery mixtures.
  • Another method of implementation is spray granulation which is a simultaneous process.
  • the granules are formed during the evaporation of the fluid. These granules are harder and denser than by agglomeration.
  • a wet phase granulation process can be used which involves introducing the powder into a vertical granulator and moistening it thoroughly with spraying. The mixture is then vigorously stirred by a turbine into a nacheur. In this process where the powder is compressed, the result is granules denser than by agglomeration in a fluidized bed.
  • Another method that can be used is the compression injection process which consists of injecting a slab of molten material which is then compressed to fill a mold. A compressed solid product is then obtained.
  • Yet another useful and preferred method according to the invention is the compounding process which is a continuous process comprising mixing, cooling and granulating steps.
  • the mixture of NTC and polymer arrives at the top of an extruder or in a first segment thereof, in powder form, and is poured into the hopper to feed the screw of the extruder, which is preferably an extruder twin-screw or a co-kneader.
  • the screw of the extruder which is preferably an extruder twin-screw or a co-kneader.
  • the mixture is heated and softened by means of a worm which is in a sleeve (tube) heated to make the material malleable.
  • the screw drives the material to the outlet.
  • the exit head of the extruder gives shape to the outgoing material.
  • the tube or ring comes out continuously, it is cooled to be then cut into pellets.
  • thermoplastic and / or elastomeric powdery polymer, into which the masterbatch must be introduced is fed into a second segment of the extruder or mixer used for the manufacture of this masterbatch.
  • manufacture of the composite can be done continuously in the same apparatus.
  • solid physical form agglomerated in the context of the present invention the final mixture after its implementation according to the invention in hard form, for example substantially cylindrical, ovoid, rectangular or prismatic spherical.
  • granules, pellets and rollers can be cited as agglomerated solid physical forms.
  • the diameter of this agglomerated solid physical form may be between 1 mm and 10 mm, but more preferably between 2 mm and 4 mm.
  • the masterbatch obtained as described above is intended to be introduced into a thermoplastic and / or elastomeric polymer composition to form a composite material. It is generally preferable to use the same family of polymers as that of the thermoplastic and / or elastomeric polymer included in the masterbatch. Examples of usable polymers are those mentioned above. In some cases, it may, on the other hand, be advantageous to use a non-matrix compatible polymer in order to obtain a so-called "double percolation" effect.
  • the polymer is chosen from polyamides, poly (vinylidene fluoride), polycarbonate, polyetheretherketone, poly (phenylene sulphide), polyolefins, and mixtures thereof, and their copolymers.
  • the polymer composition, into which the masterbatch is introduced may further contain various additives and additives such as lubricants, plasticizers, pigments, stabilizers, fillers or reinforcements, anti-static agents, anti-fogging agents, fungicides, flame retardants and solvents.
  • additives and additives such as lubricants, plasticizers, pigments, stabilizers, fillers or reinforcements, anti-static agents, anti-fogging agents, fungicides, flame retardants and solvents.
  • the process according to the invention makes it possible to improve the dispersion of the anotubes in the polymer matrix and / or the mechanical properties (in particular tensile and / or impact strength) and / or electrical conductivity. and / or the thermal conductivity of the polymeric matrix.
  • Another advantage of said method is that it makes conductive composites comprising CNTs at lower rates of CNT compared to the prior art.
  • FIGS. 1 and 3 illustrate a dispersion of comparative composites
  • FIGS. 2 and 4 illustrate a dispersion of composites prepared according to the invention
  • FIG. 5 represents two percussion curves of a composite and composite composite prepared according to the invention.
  • a 15% BUSS 15D co-kneader of powdered NTC (Graphistrength ' 1 ClOO from Arkema) was mixed with 95% of Ramesan' AMNO TLD powder from Arkema (grade fluid polyamide) at a flow rate of 10 kg / h with a sheath temperature profile 250/250/250/220 0 C, a screw profile at 210 ° C, and a screw speed of 250 rpm, to obtain a composite material containing 5% by weight of CNT and 95% by weight of PAl2.
  • Photographs were then taken by optical microscope in transmitted light from 2 ⁇ m thick sections made parallel to the extrusion direction, at the rate of 6 plates per section, at a nominal magnification of 200 ⁇ . The percentage of the surface of these composite materials occupied by CNT aggregates was then evaluated. The average of the values obtained for each of the 6 snapshots was calculated.
  • a 20% BUSS 15D co-kneader of NTC powder (Graphistrength 0 C100 from Arkema) was mixed in 80% of polyamide-12 powder Rilsan c AMNO TLD of Arkema (grade of polyamide). fluid) at a flow rate of 10 kg / h with a sleeve temperature profile 250/250/250/210 0 C, a screw profile at 21O 0 C, and a screw speed of 280 rpm, to obtain a composite material containing 20% by weight of CNT and 80% by weight of PA12.
  • the kneading is carried out by two co-rotating screws (screw speed: 100 zr / min) at a temperature ⁇ e 23O 0 C during a duration of 10 min.
  • screw speed 100 zr / min
  • the injection is carried out at 230 ° C. in a mold preheated to 90 ° C. to obtain a pellet.
  • the resistivity measurement is carried out thanks to the four-wire measurement system for its precision and the stability of the measurement.
  • NTC / PVDF composites were prepared according to the protocol of Example 3 so as to obtain composites based on Kynar J 721 containing from 1% to 10% by weight of NTC (Graphistrength 0 C100 from Arkema).
  • the resistivity of the composites decreases as the level of CNT they contain increases.
  • that of the composites obtained according to the invention is always lower, from a CNT content of about 3.4% up to a CNT level of about 10%, to that of the composites obtained from granulated polymer, which reflects their better electrical conductivity and the better dispersion of CNTs in these composites according to the invention.
  • the use of powdered PVDF (Rynar "721) and not in granules ( ⁇ Kynar 720) leads to a significant improvement on conductivity of the injected pellets has a CNT content of 5%.
  • the resistivity measured on the composite obtained from powder is 454 ⁇ .cm whereas that measured for the composite based on granules is at least 100 times higher.
  • Table 3 compares the two DSM microextrusion mixing systems and Rheocord internal mixer as well as the two powder / granulate processing techniques at CNT levels of 2% and 5%.
  • Composition A is obtained by introducing into a Rhéocord Haake 90 mixer, 98% of PVDF (Kynar ° 720) in the form of granules which are melted and then 2% of NTC in the form of powder (Graphistrength 0 C100 of the Arkema company).
  • Composition B is obtained by manually mixing dry 2% of NTC in powder form (Graphistrength 0 C100 from Arkema) and 98% of PVDF (Kynar 720) in powder form and then using this mixture in a Rhéocord Haake 90 mixer.
  • the mixing conditions for the Rheocord are as follows: mixing temperature: 230 ° C. rotational speed of the Brabender type rotors: 100 rpm mixing time: 10 min
  • compositions A and B are compressed into pellets according to a process comprising the steps of:
  • Pellets having a diameter of about 2 cm and a thickness of about 0.1 cm are obtained.
  • the measurement of the resistivity can be performed.
  • Composition C is obtained by premixing dry 95% of PVDF (Kynar 720) in the form of granules and 5% of NTC in powder form (Graphistrength 0 C100 from Arkema) and then introducing this premix. in a microextruder model Micro 15 compounder 0 from the company DSM. The mixing is done by two co-rotating screws
  • composition D is obtained by dry pre-mixing manually 5% of NTC in the form of a powder (Graphistrength '3 C100 from Arkema) and 95% of PVDF (Kynar 720) in powder form, then introducing this precursor. mixing in a model of microextrudeur Micro 15 compounder 0 of society
  • compositions C and D are thus in the form of pellets by injection. Results:
  • Pellets made by compression (2% CNT) from Kynar® powder have a lower resistivity value than those obtained from Kynar * granules.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
EP08837912A 2007-09-24 2008-09-19 Verfahren zur herstellung von verbundmaterialien Withdrawn EP2193160A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0706664A FR2921391B1 (fr) 2007-09-24 2007-09-24 Procede de preparation de materiaux composites
PCT/FR2008/051690 WO2009047466A2 (fr) 2007-09-24 2008-09-19 Procédé de préparation de matériaux composites

Publications (1)

Publication Number Publication Date
EP2193160A2 true EP2193160A2 (de) 2010-06-09

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EP08837912A Withdrawn EP2193160A2 (de) 2007-09-24 2008-09-19 Verfahren zur herstellung von verbundmaterialien

Country Status (6)

Country Link
US (1) US20100201023A1 (de)
EP (1) EP2193160A2 (de)
JP (1) JP2010540687A (de)
CN (1) CN101848959A (de)
FR (1) FR2921391B1 (de)
WO (1) WO2009047466A2 (de)

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US20100201023A1 (en) 2010-08-12

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