US20060001013A1 - Conductive polyolefins with good mechanical properties - Google Patents

Conductive polyolefins with good mechanical properties Download PDF

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US20060001013A1
US20060001013A1 US10/508,637 US50863705A US2006001013A1 US 20060001013 A1 US20060001013 A1 US 20060001013A1 US 50863705 A US50863705 A US 50863705A US 2006001013 A1 US2006001013 A1 US 2006001013A1
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carbon nanotubes
polymeric matrix
matrix material
nanotubes
polymeric
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Marc Dupire
Janos Nagy
Jacques Michel
Christophe Pirlot
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Total Petrochemicals Research Feluy SA
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Total Petrochemicals Research Feluy SA
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Assigned to TOTAL PETROCHEMICAL RESEARCH FELUY reassignment TOTAL PETROCHEMICAL RESEARCH FELUY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DUPIRE, MARC, MICHEL, JACQUES, NAGY, JANOS B., PIRLOT, CHRISTOPHE
Publication of US20060001013A1 publication Critical patent/US20060001013A1/en
Priority to US12/332,090 priority Critical patent/US7863366B2/en
Abandoned legal-status Critical Current

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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
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742—Carbon nanotubes, CNTs
    • Y10S977/75—Single-walled
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742—Carbon nanotubes, CNTs
    • Y10S977/752—Multi-walled

Definitions

  • the present invention is concerned with reinforced and conductive polymers incorporating nanotubes, their method of preparation and their uses.
  • carbon nanotubes Depending on their diameter, helicity, and number of layers (single-wall v. multiple-wall) carbon nanotubes have electronic properties between those of conductors and semi-conductors. They may thus be added to an electrically insulating polymer to increase its conductivity.
  • WO 97/15934 discloses an electrically conductive polymer composition containing carbon nanotubes.
  • carbon nanotubes have great mechanical strength, being cited as having bending modulus values of from 1000-5000 GPa.
  • they have been mentioned in connection with new, highly efficient, fracture micromechanisms that would prevent pure brittle failure with a concomitant low strain.
  • carbon nanotubes have been envisaged for use in many applications in recent years (see P.
  • the present invention provides a polymeric material reinforced with single-wall carbon nanotubes (SWNT) or multi-wall carbon nanotubes (MWNT) and prepared by mixing in the molten state, characterised in that said carbon nanotubes are free of catalyst and support particles.
  • SWNT single-wall carbon nanotubes
  • MWNT multi-wall carbon nanotubes
  • the present invention also discloses a process for preparing said reinforced polymeric material that comprises the steps of:
  • the present invention further discloses the use of said partly purified nanotubes in order to produce a reinforced polymeric material having a good balance of electrical and mechanical properties.
  • the polymer is not particularly limited.
  • the polymer is preferably a polyolefin, such as a homopolymer or a copolymer of ethylene or of propylene or a blend thereof.
  • the polyolefin is a polymer of an olefin having 3 or more carbon atoms, such as polypropylene
  • the polyolefin may be atactic, isotactic or syndiotactic.
  • Other polymers that can be used in the present invention include polyesters such as PET and PEEKS, polyamides, PVC, and polystyrenes.
  • Carbon nanotubes can be produced by any method known in the art. They can be produced by the catalytic decomposition of hydrocarbons, a technique that is called Catalytic Carbon Vapour Deposition (CCVD). This method produces both SWNT and MWNT: the by-products are soot and encapsulated metal(s) nanoparticles.
  • CCVD Catalytic Carbon Vapour Deposition
  • Other methods for producing carbon nanotubes include the arc-discharge method, the plasma decomposition of hydrocarbons or the pyrolysis of selected polymers under selected oxidative conditions.
  • the starting hydrocarbons can be acetylene, ethylene, butane, propane, ethane, methane or any other gaseous or volatile carbon-containing compound.
  • the catalyst if present, is either pure or dispersed on a support.
  • the presence of a support greatly improves the selectivity of the catalysts but it contaminates the carbon nanotubes with support particles, in addition of the large amounts of soot and amorphous carbon produced by pyrolysis.
  • a purification step therefore becomes necessary in order to obtain pure carbon nanotubes.
  • the purification comprises two steps:
  • the second step can be prejudicial to the dispersion of the nanotubes in the matrix as it results in a partial oxidation of nanotubes, thereby modifying their polarity and consequently their ability to be mixed with apolar polymers such as polyethylene and polypropylene. It is therefore essential to control that preliminary treatment and the surface composition of the nanotubes in order to improve their dispersion in the polymer matrix and their linking properties: this is generally achieved by “functionalising” the nanotubes as described for example in J. Chen et al., Science, 282, 95-98, 1998; Y. Chen et al., J. Mater. Res., 13, 2423-2431, 1998; M. A. Hamon et al., Adv.
  • the functionalisation can be carried out by reaction for example with an alkylamine. It results in a better separation of the nanotubes in the polypropylene matrix thereby favouring the dispersion in the polymer matrix. If the functionalisation is carried out in both the nanotubes and the polymer matrix it promotes their covalent bonding, thereby improving the electrical and mechanical properties of the filled compound.
  • the electrical conductivity of polymers was typically obtained by the incorporation of electrically conductive particles as filler into the polymer.
  • the electrically conductive particles may comprise at least one of carbon black, carbon fibres, metallic particles, or particles coated with electrically conductive material.
  • the electrical conductivity of the composite material depends upon the concentration of the filler particles in the polymer. At low filler concentrations, the filler particles form clusters wherein the particles touch each other but the clusters are individual and separated from each other. With such a concentration range and such morphology, the composite is considered to be an electrically insulative material. However, the electrical conductivity generally increases with increasing filler concentration. With a yet further increase in the filler concentration, the particulate clusters start to touch each other, thereby forming an electrically conductive body in the polymer matrix. In a very narrow range of increasing particulate concentration, the electrical resistivity of the composite suddenly drops, and the material becomes electrically conductive. Such a concentration range is known as the “percolation threshold”. Above the percolation threshold, any further increase in the filler concentration results in a further decrease of the electrical resistivity.
  • the concentration value at the percolation threshold depends on the type and geometry of the filler particles.
  • the more spherical the particles the higher the percolation threshold.
  • highly structured carbon black particles i.e. particles of a complex shape, usually made from spheres merged into each other, provide composites with a much lower percolation threshold.
  • Carbon nanotubes as used in the present invention are characterised by a very large aspect ratio of at least 100, preferably of at least 500 and more preferably of at least 1000.
  • the nanotubes can be either single-wall carbon nanotubes (SWNT) or multiple-wall carbon nanotubes (MWNT).
  • SWNT contain a hollow core of up to 5 nm across and typically have a length in the range of 1 to 50 microns.
  • MWNT contain a hollow core of up to 200 nm across, preferably, up to 100 nm and more preferably of up to 50 nm and typically they have a length in the range of 1 to 200 microns, preferably, of 1 to 100 microns and more preferably of 1 to 50 microns.
  • nanotubes Because of the large aspect ratio of the nanotubes, it is possible to obtain good conduction properties at low to moderate loading, providing that adequate dispersion in the polymer matrix can be achieved.
  • the nanotubes In the prior art there is an overlap between the definitions of nanotubes and nanofibres, the nanotubes being generally considered as the small end of the range, both in length and diameter.
  • the functionalisation treatment may break the nanotubes lengthwise.
  • Carbon nanotubes are further characterised by a very high bending modulus in the range of 1000 to 5000 GPa and by a very efficient fracture micro-mechanism that prevents pure brittle failure under low strain.
  • the carbon nanotubes are partly purified if necessary, i.e., if support and catalyst particles remain in the nanotubes. They are typically washed with an appropriate agent such as for example fluorhydric acid in order to remove the catalyst and the catalyst support. They can optionally be further purified to remove the pyrolytic carbon by an oxidising treatment typically carried out with KMnO 4 .
  • the amorphous carbon is oxidised faster than the carbon nanotubes, thereby minimising the alteration of the nanotubes' composition.
  • the nanotubes are then dispersed in the polymer matrix by any method that allows a thorough dispersion of the carbon nanotubes in the polymer matrix.
  • the dispersion of the filler can be achieved either with a Brabender internal mixer or with a twin-screw extruder or with any high shear device.
  • the nanotubes are dispersed by mixing in the molten state.
  • the properties of the filled polymer can be further improved by orienting the nanotubes within the polymer such that their longitudinal axes are more aligned with each other than would otherwise be the case.
  • Orienting is intended to mean a degree of disentangling of the carbon nanotubes and/or a degree of aligning of the carbon nanotubes. Not only are the nanotubes oriented, but also the individual polymer molecules undergo a degree of orientation in the present method. Orientation of the nanotubes leads to a greater homogeneity and less tangling in the resulting blends, and a consequent significant improvement in the mechanical properties of the blends.
  • superior tensile modulus and tenacity can be achieved by the present blends as compared with known blends, whilst still retaining a relatively high toughness and good electrical properties.
  • the orientation can be carried out by stretching the polymer/nanotube mixture either in the solid state or in the molten state.
  • the composites containing these aligned nanotubes have mechanical properties that are similar to those of composites containing continuous carbon fibres but they have much better processing capabilities permitting the high throughput production of high quality, complex shaped composites.
  • the quantity of carbon nanotubes added to a given quantity of polymer is not particularly limited. Typically less than 50% wt. of carbon nanotubes is added to the polymer. Preferably 30% wt. or less and more preferably 20% wt. or less of nanotubes is added. It is most preferred that 5% wt. or less of nanotubes is added.
  • a very small quantity of nanotubes is capable of beneficially affecting the properties of a polymer, such that very small quantities can be used, depending on the intended use of the polymer. However, for most applications it is preferred that 0.1% wt. of nanotubes or greater is added, more preferably 1 wt % or greater.
  • additives typically introduced into polymers can be included in the present reinforced polymers, provided that the additives do not prevent the enhanced mechanical properties of the present polymer being obtained.
  • additives such as pigments, anti-oxidants, UV-protectors, lubricants, anti-acid compounds, peroxides, grafting agents and nucleating agents can be included.
  • Carbon black can also be added to the nanotubes/polymer composition.
  • the reinforced composites according to the present invention can be used in applications that require electrical conductivity or dissipation of static electricity such as for example, electrically dissipative parts for automotive applications, conductive video disks, conductive textiles, stand shields for wires and cables, cable jacketing, hospital tiles, computer tapes or mine belting.
  • FIG. 1 represents the Transmission Electron Microscopy of multi-wall carbon nanotubes, partly purified, dispersed in a PP matrix.
  • the filler amounts are respectively 4 wt % for (a) and 10 wt % for (b).
  • FIG. 2 represents the electrical volume resistivity expressed in ⁇ .cm as a function of the filler amounts expressed in wt % of filler based on the weight of the polymer for polypropylene filled respectively with carbon nanotubes, with carbon nanofibres and with carbon black and for polyethylene filled carbon black.
  • FIG. 3 represents the elastic modulus expressed in MPa as a function of the electrical volume resistivity expressed in ⁇ .cm for pure polypropylene and for polypropylene filled respectively with carbon nanotubes and with carbon black.
  • FIG. 4 represents the stress expressed in kPa as a function of the strain expressed in % respectively for polypropylene filled with 4 wt % of carbon nanotubes and for polypropylene filled with 12 wt % of carbon black.
  • FIG. 5 represents a graph of the resistivity expressed in ⁇ .cm as a function of carbon nanotubes amounts expressed in wt % for partly purified nanotubes, for fully purified nanotubes and for fully purified nanotubes that have been submitted to a specific functionalising treatment described in the examples.
  • the carbon nanotubes used in the examples according to the present invention were produced by CCVD following the method of patent application no 01870150.8. They were multiple-wall carbon nanotubes having an internal diameter of about 4 nm, an external diameter of about 13 nm and a length of 10 microns; they contained on average about 13 graphitic layers. They were washed with fluorhydric acid in order to remove the catalyst and the catalyst support, while leaving the graphitic particles and amorphous carbon in place.
  • the polymer used was an isotactic polypropylene having a melt flow index MI2 of 35 as measured following the method of standard test ISO 1133 at a temperature of 230° C. and under a load of 2.16 kg.
  • the amounts of carbon nanotubes added to the polymer matrix were expressed in wt %, based on the weight of the polymer.
  • the following additives were also added: 1500 ppm of anti-oxidant (1 part of Irganox® 1010 and 2 parts of Irgafos® 168), 500 ppm of calcium stearate and 400 ppm of glycerol monostearate.
  • the isotactic polypropylene powder, the nanotubes and the additives were melt compounded using a Brabender internal mixer.
  • Injection moulded tensile bars were produced as follows. 1.6 g of the blended material was introduced into the mixing chamber of a MiniMax moulder, that was heated at a temperature of 220° C. The mixture was maintained at 220° C. for one minute under a nitrogen atmosphere and the axial rotor was rotated at 60 rpm for 2 minutes, resulting in further blending of the nanotubes and polypropylene.
  • the electrical measurements were carried out using a point contact four-point probe device having the following characteristics: the radius of the probes was 100 microns, the spacing between the probes was 1 mm, the weight was 40 mg, the current intensity was 0.01 to 50 microA and the maximum voltage was 100 V.
  • the isotactic polypropylene was used without filler and with various amounts of a conductive carbon black sold under the name Ensaco® 250G by Erachem Comilog.
  • the compounding was carried out in a twin-screw extruder with 5000 ppm of the anti-oxidant described here-above.
  • Polyethylene (PE) is expected to present the same behaviour as polypropylene (PP).
  • the electrical and mechanical properties of the filled polypropylene are displayed in Table I and in FIGS. 2 and 3 for various amounts and nature of fillers.
  • the level of electrical resistivity obtained with a commercial high density polyethylene (HDPE) is also displayed on FIG. 2 .
  • a polypropylene filled with carbon nanofibres is included in FIG. 2 .
  • the carbon nanofibres are sold under the name Pyrograph-III® by Applied Sciences, Inc. They were prepared by the vapour-grown carbon fibre (VGCF) method and had a cross section varying from 20 to 200 nm. They were purified and functionalised. Purification was conducted by refluxing in dichloromethane for 5 days at a temperature of 35° C. followed by oxidation in air at 550° C.
  • the resilience of a product is linked to the area under its stress-strain curve.
  • Two polypropylene composites filled respectively with 4 wt % of carbon nanotubes and with 12 wt % of carbon black and having similar electrical volume resistivities of between 15 and 20 ⁇ .cm have been compared for resilience.
  • the results are displayed in FIG. 4 .
  • the areas under the stress-strain curves are respectively of 2.6.10 6 Nm/m 3 for the PP filled with carbon black and of 4.10 6 Nm/m 3 for the PP filled with carbon nanotubes, thus clearly showing the improved resilience of the polypropylene filled with carbon nanotubes.
  • a first orientation was conducted by stretching the samples under slow strain rate (10%/min with a gauge length of 10 mm) at a temperature of 110° C.: the elongation was limited to a stretch ratio (SR) of 3, the stretch ratio being defined as the ratio (L ⁇ L 0 )/L 0 wherein L and L 0 are respectively the lengths of the samples after and before the drawing step.
  • the samples were then allowed to come back to room temperature. Tensile testing measurements were performed at room temperature.
  • the first purification step with fluorhydric acid was followed by an oxidation step performed with KMnO 4 . That second purification step removed all pyrolytic carbon.
  • the conductivity measurements of the polypropylene filled with the fully purified carbon nanotubes are much lower than those obtained with the partly purified carbon nanotubes. It is further observed that the fully purified carbon nanotubes have a poor dispersion in the polymer and reduced mechanical properties. It is believed that the KMnO 4 treatment creates oxidised and thus polar functions at the surface of the nanotubes. It induces their limited dispersion in a hydrophobic polymer matrix, and consequently a high percolation threshold.
  • the compatibility of the fully purified carbon nanotubes with the polymer matrix can be improved by functionalising the carbon nanotubes using an acid/base-type reaction with an alkylamine.
  • the amine reacts with the carboxyl functions of the nanotubes to create a pending alkyl chain that can interact with the non-polar structure.
  • Fully purified nanotubes were re-oxidised with nitric acid, followed by reaction with octylamine: the presence of nitrogen chemically linked to the nanotubes after the functionalisation reaction was confirmed by X-Ray Photoelectron Spectroscopy.
  • the electrical results are displayed in FIG. 5 and the electrical and mechanical results are displayed in Table III, all for the same polypropylene as in the other examples.

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US20070265379A1 (en) * 2003-05-22 2007-11-15 Zyvex Corporation Nanocomposites and methods thereto
US20080194737A1 (en) * 2002-05-02 2008-08-14 Zyvex Performance Materials, Llc Polymer and method for using the polymer for solubilizing nanotubes
US20080306202A1 (en) * 2007-06-08 2008-12-11 Xerox Corporation Intermediate transfer members comprised of hydrophobic carbon nanotubes
US20090023851A1 (en) * 2007-06-23 2009-01-22 Bayer Materialscience Ag Process for the production of an electrically conducting polymer composite material
US20090121196A1 (en) * 2005-01-05 2009-05-14 Arkema France Use of carbon nanotubes for the production of a conductive organic composition and applications of one such composition
US20090162777A1 (en) * 2007-12-20 2009-06-25 Xerox Corporation Electrically resistive coatings/layers using soluble carbon nanotube complexes in polymers
US20100113414A1 (en) * 2004-10-07 2010-05-06 Boehringer Ingelheim International Gmbh Thiazolyl-dihydro-indazoles
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US20110184115A1 (en) * 2007-08-24 2011-07-28 Total Petrochemicals Research Feluy Reinforced and Conductive Resin Compositions Comprising Polyolefins and Poly(hydroxy carboxylic acid)
US20140127017A1 (en) * 2011-07-05 2014-05-08 Hafmex Invest Oy The surface structure of windmill rotors for special circumstances
US9082744B2 (en) 2013-07-08 2015-07-14 International Business Machines Corporation Method for aligning carbon nanotubes containing magnetic nanoparticles in a thermosetting polymer using a magnetic field
US9090004B2 (en) 2013-02-06 2015-07-28 International Business Machines Corporation Composites comprised of aligned carbon fibers in chain-aligned polymer binder
US20160015100A1 (en) * 2009-06-03 2016-01-21 Glt Technovations, Llc Material for use with a capacitive touch screen
US9493723B2 (en) 2013-08-30 2016-11-15 Halliburton Energy Services, Inc. High-temperature lubricants comprising elongated carbon nanoparticles for use in subterranean formation operations
US9528066B2 (en) 2013-08-30 2016-12-27 Halliburton Energy Services, Inc. High-temperature lubricants comprising elongated carbon nanoparticles for use in subterranean formation operations
RU2668037C2 (ru) * 2016-11-17 2018-09-25 МСД Текнолоджис С.а.р.л. Окрашенный проводящий термопластичный полимер и способ его получения

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