WO2006114495A2 - Structure cellulaire a base de polymere comprenant des nanotubes de carbone, son procede de preparation et ses applications - Google Patents
Structure cellulaire a base de polymere comprenant des nanotubes de carbone, son procede de preparation et ses applications Download PDFInfo
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- WO2006114495A2 WO2006114495A2 PCT/FR2006/000821 FR2006000821W WO2006114495A2 WO 2006114495 A2 WO2006114495 A2 WO 2006114495A2 FR 2006000821 W FR2006000821 W FR 2006000821W WO 2006114495 A2 WO2006114495 A2 WO 2006114495A2
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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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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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
Definitions
- the present invention relates to a polymeric cellular structure comprising carbon nanotubes (CNTs), its method of preparation and its applications in the manufacture of lightened structure.
- CNTs carbon nanotubes
- Polymeric foams are attracting increasing interest. Thanks to their unique microcellular structure, these expanded plastics have superior mechanical properties, such as impact resistance, hardness and fatigue life when compared to raw polymer. These excellent properties allow them to continually find utilities in a very large number of applications.
- the polystyrene foams produced in extrusion plate form using supercritical fluids (so-called direct gassing process) find applications in the field of food packaging, thermal insulation and household refrigeration (refrigerators )
- the thermal conductivity of the foam depends on several parameters: the intrinsic density of the polymer, the size of the cells, the number of cells, the density of the foam and the thermal conductivity of the expansion gas that one seeks to keep inside the cells. In general, the gas tends to diffuse through cell walls resulting in a decrease in the insulation rate. The management of these various parameters makes it possible to obtain high performance foam.
- carbon nanotubes are known and used for their excellent properties of electrical and thermal conductivity as well as their mechanical properties. They are thus more and more used as additives to bring to these materials, especially those of polymeric type, expanded or not, these electrical, thermal and / or mechanical properties (WO 03/085681, WO 91/03057, US5744235, US5445327, US54663230).
- carbon nanotubes are found in many fields, in particular in electronics (depending on the temperature and their structure, they can be conductors, semiconductors or insulators), in mechanics, for example for the reinforcement of composite materials (carbon nanotubes are a hundred times stronger and six times lighter than steel) and electromechanical (they can expand or contract by charge injection).
- carbon nanotubes in polymer compositions intended for the packaging of electronic components, the manufacture of fuel lines (fuel line), antistatic coatings or coatings, in thermistors, electrodes may be mentioned. for super-abilities, etc.
- conductive organic compositions are generally known which are generally formulations based on polymeric substances of which at least one component is semi-crystalline in nature, for example polyethylene, and which contains conductive additives, the best known being black carbon (J. of PoI Sci.
- the object of the invention is to propose new polymeric cellular structures comprising carbon nanotubes.
- the subject of the invention is a cellular polymeric structure comprising carbon nanotubes, in particular a structure in which the percentage by weight of carbon nanotubes in the polymer structure is less than 60%, preferably between 10 and 50%, or preferably between 0.1 and 3%.
- the average size of the cells is less than 150 microns, preferably between 20 and 80 microns.
- the empty volume is at least 50%, preferably between 50% and 99%.
- the apparent density is less than 100 kg / m 3 , preferably between 10 and 60 kg / m 3 .
- the polymer is chosen from the group consisting of thermoplastic or thermosetting (co) polymers, elastomers and resins, preferably chosen from PVDF, EVA, PEBA, PA or even better the chosen polymer is a polystyrene or a polyurethane.
- the structure according to the invention comprises the residues of a blowing agent, in particular the blowing agent is chosen from the group consisting of organic or inorganic liquid or gaseous compounds, solid chemical components. capable of generating cells by decomposition, gaseous compounds or a mixture thereof.
- a blowing agent is chosen from the group consisting of organic or inorganic liquid or gaseous compounds, solid chemical components. capable of generating cells by decomposition, gaseous compounds or a mixture thereof.
- the walls of the cells also comprise pores.
- the invention also relates to the use of a structure as described above in the fields of food packaging, insulation, lightweight structural materials, the manufacture of membranes, electrodes.
- the invention also relates to the process for preparing a polymeric cell structure comprising the steps of a) preparing the polymer / NTC composite mixture; b) solubilization during which the blowing agent is introduced which solubilizes in the mixture; c) subjecting the mixture to chemical or physical conditions to create cells in the polymerized structure.
- the blowing agent used in the process is a supercritical gas, preferably supercritical CO 2 or a fluorinated gas chosen from chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs).
- the mixture of step c) is subjected to decompression to create the cells.
- the polymer resulting from step c) is subjected to carbonization followed by a step of graphitization at a temperature above 1000 ° C.
- FIG. 1 shows the evolution of the viscosity as a function of the shear gradient of different NTC / polystyrene lacqrenel450 mixture marketed by Total Petrochemicals.
- Figures 2 and 3 show the evolution of the cell diameter and the density of the foam as a function of different% of incorporated CNT and as a function of the expansion temperature used in the foaming process.
- Figure 4 shows the orientation of the CNTs during expansion via the biaxial flow of the molten polymer.
- the invention provides a cellular polymeric structure comprising carbon nanotubes.
- the carbon nanotubes used in the invention have a shape ratio (L / D) greater than or equal to 5 and preferably greater than or equal to 50 and advantageously greater than or equal to 100.
- the carbon nanotubes generally have a tabular structure of diameter less than 100 nm, preferably between 0.4 and 50 nm and / or in general of length greater than 5 times their diameter, preferably greater than 50 times their diameter and advantageously from 100 to 100000 or from 1000 to 1000 10000 times their diameter.
- Carbon nanotubes consist of an allotropic variety of carbon in a sp 2 configuration consisting of a long single, double or multi-walled tube of aromatic rings contiguous to each other, aggregated or not.
- the nanotube When the nanotube consists of a single tube, we speak of mono-wall, two tubes we speak of double walls. Beyond that, we will talk about multi walls.
- the outer surface of the nanotubes may be uniform or textured.
- nanotubes can be chemically or physically treated to purify or functionalize them in order to give them new properties of dispersion, and interaction with the components of the formulation such as polymer matrices, elastomers, thermosetting resins, oils, greases, water-based or solvent-based formulations such as paints, adhesives, varnishes.
- the carbon nanotubes can be prepared by various methods, such as the Electric Arc method (C. Journet et al in Nature (London), 388 (1997) 756, the CVD gas phase method, Hipco (P. Shinv et al. in Chem Phys Lett, 1999, 313, 91), the method of
- the polymeric cellular structure comprises one or more polymers chosen from polymers and copolymers, in particular thermoplastics, thermosetting polymers, thermoplastic resins, acrylic polymers and methacrylic polymers.
- styrenic polymers polyolefms, polyurethanes, copolymers of ethylene such as Evatanes and Lotryl marketed by Arkema, and rubbers such as those used in sealing.
- thermoplastic resins examples include: acrylonitrile-butadiene-styrene (AB S), acrylonitrile-ethylene / propylene-styrene (AES), methylmethacrylate-butadiene-styrene (MBS), acrylonitrile-butadiene-methylmethacrylate-styrene (ABMS ), acrylonitrile-n-butylacrylate-styrene (AAS), polystyrene modified gums, resins of: polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, cellulose acetate, polyamide, polyester, polyacrylonitrile, polycarbonate, polyphenyleneoxide, polyketone, polysulphone, polyphenylenesulphide, resins: fluorinated, silicone, polyimide, polybenzimidazole.
- ABS acrylonitrile-butadiene-styrene
- AES acryl
- thermosetting resins examples include resins based on phenol, urea, melamine, xylene, diallylphthalate, epoxy, aniline, furan, polyurethane, etc.
- thermoplastic elastomers of PVC, urethane, polyester, polyamide (PA) type thermoplastic elastomers of polybutadiene type such as 1,2-polybutadiene or trans-1,4-polybutadiene resins
- polyethylene type elastomers such as methylcarboxylate-polyethylene, ethylene-vinyl acetate (EVA), ethylene-ethylacrylate copolymers, chlorinated polyethylene, fluorinated-type thermoplastic elastomers such as polyvinylidene fluorides (PVDF), polyether esters and polyether amides such as polyetherblock polyamine (PEBA) etc.
- PVDF polyvinylidene fluorides
- PEBA polyetherblock polyamine
- polystyrene sulfonate PSS
- polystyrene sulfonate PSS
- poly (1-vinylpyrrolidone-co-vinyl acetate poly (1-vinylpyrrolidone-co-acrylic acid
- poly (1-vinylpyrrolidone-co-dimethylaminoethyl methacrylate) polyvinyl sulfate
- dextran dextran sulfate
- gelatin bovine serum albumin
- poly (methyl methacrylate-co-ethyl acrylate) polyallyl amino, and combinations thereof.
- Polymers chosen from PVDF, EVA, PEBA and PA are preferably used.
- the cellular polymeric structure is porous.
- the structure has a total void volume or a total pore volume of at least 50%, preferably greater than 80% and preferably greater than 92% or more preferably between 50 and 99%.
- the pores or cells of the structure may be open or fe ⁇ inflated depending on the intended application.
- the average cell size or pores dso is defined by the mean diameter of
- the average diameter of the d 5 o cells is less than 150 microns, preferably less than 100 microns, preferably less than 80 microns and more preferably less than 10 microns.
- the average diameter of the dso cells is between 5 and 80 microns, preferably between 30 and 50 microns.
- the porosity value is defined by the ratio of the void volume to the geometric volume of the structure. It can be connected to the true density of notions have vr, which is the theoretical density of the bulk material and bulk density of app (or "bulk density” in English) of material comprising pores accessible or not.
- vr the theoretical density of the bulk material and bulk density of app (or "bulk density” in English) of material comprising pores accessible or not.
- the structure has an apparent density of less than 100 kg / m 3 , preferably between 10 and 60 kg / m 3 .
- the density is measured by a pyknometer.
- the process for preparing a polymeric cellular structure namely the foaming process, is well known in the field of polymeric foams.
- the foaming process may be of a physical nature based on the use of blowing agents selected from the group consisting of organic compounds or liquid or gaseous inorganic compounds or mixtures thereof.
- the blowing agent is chosen from the group of volatile organic compounds consisting of hydrocarbons, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs).
- the blowing agent is chosen from the group of inorganic compounds constituted by gases, in particular nitrogen, helium, carbon dioxide, supercritical fluids, in particular CO 2 , hydrocarbons, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) ...
- the foaming process can also be of a chemical nature based on the use of a blowing agent chosen from among chemical components capable of generating cells by decomposition. It is also possible to use in the foaming processes both physical and chemical expansion agents as described above.
- the first phase is the preparation phase of a polymer / NTC composite mixture.
- This mixture can be prepared by melting in an internal mixer, for example of the Haak type. The mixture thus obtained is ground.
- This method of preparation is given by way of example for the demonstration of the invention. All methods of preparation of composite based on polymers, resins and elastomers can be used. Examples that may be mentioned are single or double screw extruders, buses, static mixers, etc.
- the mixture obtained may be used as or after dilution in a compatible matrix or not. In this case the first mixture is called master batch or master batch.
- the second phase is the solubilization phase during which the blowing agent is introduced which is solubilized in the mixture.
- the third phase is the creation phase of the cells in the polymer phase by subjecting the mixture to suitable chemical or physical conditions for the blowing agent to play its role.
- blowing agent is a supercritical fluid, for example
- the micro-cellular structures obtained have a% by weight of CNT in the polymer structure greater than 0.05%, preferably greater than 0.1%, or even more preferably between 0.1% and 3%.
- the percentage by weight of carbon nanotubes introduced into the structure is less than 60%, preferably less than 50%, more preferably between 10 and 50% or even between 0, 1 and 15%.
- the process described above can be followed by a step during which the polymer is carbonized followed by a high temperature graphitization step (greater than 1000 ° C.).
- the level of CNT in the polymer is greater than 2% by weight relative to the polymer, preferably between 5 and 60% or between 10 and 50%.
- a lightened carbonaceous material having a double porosity is thus obtained: that resulting from the foaming stage with the same diameter as the cells and a second associated with the voids left by the departure of the polymer and which is in the cell walls.
- This second porosity which is much smaller, for example less than 5 microns, can be modulated by associating another charge with CNTs such as graphite or any type of electrically or thermally or electrically conductive filler.
- the choice of the NTC rate with respect to the additional charge can vary from 0 to 100%, it will depend on the intended application and the porosity.
- the invention has the advantage that the lightened materials obtained have an equivalent density compared to polymeric cellular materials without carbon nanotubes while having much smaller cell sizes. This allows in particular to aim to improve the mechanical properties, insulation or conduction of lightened material.
- the presence of the CNTs in the polymer has the advantage of acting as a nucleating agent during the foaming process and thus to favor the production of smaller cells than those of a foam without, CNT. It is thus possible to achieve a reduction of more than 30% in the average diameter dso of the cells in the polymer structures according to the invention compared to that of the foams without NTC and at the same apparent density.
- the electrical and / or thermal insulation or electrical and / or thermal conductor properties of the lightweight materials comprising the polymeric cell structures according to the invention depend on the levels of incorporated carbon nanotubes. It will therefore be up to those skilled in the art to choose the right rate of NTC to meet its specifications.
- the lightweight structures with simple porosity according to the invention can be used in the following applications: packaging, insulation, lightweight materials, sealing etc.
- the materials with double porosity can find applications of the manufacture of electrodes, membranes, ... in the energy storage markets such as batteries, supercapacities.
- the structures according to the invention may also contain residues of the blowing agent used in the foaming process.
- This blowing agent which remains in the cells generally has an impact on the conductivity properties of the lightened material.
- the presence of oriented NTCs in the cell walls can only slow down the diffusion of the expansion gas. Examples
- Carbon nanotubes obtained according to the method described in PCT patent WO 03/002456 A2 are used. These nanotubes have a diameter of between 10 and 30 nm and a length of> 0.4 ⁇ m. They are present in the final composition in dispersed form in order to take advantage of the properties of CNTs.
- Polystyrene 1450 is produced by the company Total Petrochemcials.
- the first is the fusion phase.
- the polymer or composite is placed at high temperature in a reactor of the autoclave type (generally between 190.degree. C. and 200.degree. PS) under vacuum to prevent degradation of the polymer; a vacuum pump is connected to the reactor inlet valve via a flexible pipe.
- the duration of the melting phase is generally about 2 hours.
- the second phase is the solubilization phase.
- the temperature set point is set for the solubilization phase.
- the CO 2 is conveyed using a pump equipped with a cooler.
- the inlet valve is opened by setting the setpoint to the working pressure and opening the pump air supply valve.
- the pump starts and the pressure rises in the autoclave. When the working pressure is reached, the inlet valve closes automatically.
- the duration of the solubilization phase is generally about 17 hours.
- the CO 2 under high pressure is in a supercritical state and will solubilize in the polystyrene to a concentration corresponding to the saturation concentration for the working pressure and temperature.
- the third phase is the decompression or foaming phase of the composite polymer.
- the temperature setpoint is set at room temperature to start cooling the autoclave generally by vortexing.
- a set point is set to open the outlet valve which causes depressurization at a speed imposed by the pressure and the pipe configuration. This results in nucleation and cell growth that causes foam formation.
- the interior of the autoclave can be cooled by a more efficient method at the end of the depressurization. The reactor is opened quickly to recover the foams.
- Various cellular structures according to the invention are prepared according to the method described above, with variable nanotube contents of 0 to 1%.
- Figure 1 shows the evolution of the viscosity as a function of the shear gradient.
- the rheological analysis of the various NTC / polystyrene 1450 mixtures shows the increase of the low shear rate viscosity. This increase is beneficial for obtaining a micro-cellular structure.
- Figures 2 and 3 show the evolution of the cell diameter and the density of the foam according to the different% by weight of CNT incorporated and the expansion temperature used in the foaming process. From the results shown in the graphs of Figures 2 and 3 and in Table I it is clear that 5 to 0.5% by weight of CNT added to PS 1450, is decreased cell diameter of 51% in average relative to the PS 1450 pure and this while keeping a constant density. This result reflects the effect of nucleation of CNTs which results in an increase in the number of cells. Increasing the amount of carbon nanotubes in the polymer matrix has no effect on nucleation. On the other hand, it can make it possible to manage the thermal conductivity and the electrical conductivity and the mechanical rigidity.
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP2008508251A JP2008539295A (ja) | 2005-04-27 | 2006-04-14 | カーボンナノチューブを含むポリマーをベースにした気泡構造と、その製造方法および使用 |
EP06743695A EP1877474A2 (fr) | 2005-04-27 | 2006-04-14 | Structure cellulaire a base de polymere comprenant des nanotubes de carbone, son procede de preparation et ses applications |
US11/910,747 US20110039089A1 (en) | 2005-04-27 | 2006-04-14 | Polymer-based cellular structure comprising carbon nanotubes, method for its production and uses thereof |
Applications Claiming Priority (4)
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FR0504231 | 2005-04-27 | ||
FR0504231A FR2885131B1 (fr) | 2005-04-27 | 2005-04-27 | Structure cellulaire a base de polymere comprenant des nanotubes de carbone, son procede de preparation et ses applications |
US75488805P | 2005-12-29 | 2005-12-29 | |
US60/754,888 | 2005-12-29 |
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WO2006114495A2 true WO2006114495A2 (fr) | 2006-11-02 |
WO2006114495A3 WO2006114495A3 (fr) | 2007-01-25 |
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PCT/FR2006/000821 WO2006114495A2 (fr) | 2005-04-27 | 2006-04-14 | Structure cellulaire a base de polymere comprenant des nanotubes de carbone, son procede de preparation et ses applications |
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US (1) | US20110039089A1 (fr) |
EP (1) | EP1877474A2 (fr) |
JP (1) | JP2008539295A (fr) |
KR (1) | KR20080003843A (fr) |
FR (1) | FR2885131B1 (fr) |
WO (1) | WO2006114495A2 (fr) |
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WO2008091308A2 (fr) * | 2007-01-19 | 2008-07-31 | Dow Global Technologies Inc. | Mousse polymère contenant de longs nanotubes de carbone |
WO2009092785A1 (fr) * | 2008-01-25 | 2009-07-30 | Nmc S.A. | Compositions de mousse ignifuge |
WO2010063888A1 (fr) * | 2008-12-02 | 2010-06-10 | Valtion Teknillinen Tutkimuskeskus | Couche de catalyseur pour applications électrochimiques |
WO2011042800A1 (fr) | 2009-10-07 | 2011-04-14 | Polimeri Europa S.P.A. | Compositions de nanocomposites polymères de thermoplastique expansible à capacité d'isolation thermique améliorée |
WO2011055198A1 (fr) | 2009-11-03 | 2011-05-12 | Polimeri Europa S.P.A. | Procédé de préparation de plaquettes de graphène nanométriques qui présentent une dispersibilité élevée dans des matrices polymères de faible polarité et compositions polymères relatives |
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KR101470524B1 (ko) | 2009-06-30 | 2014-12-08 | 한화케미칼 주식회사 | 혼화성이 증대된 복합탄소소재 및 이의 연속적인 제조 방법 |
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US6640420B1 (en) * | 1999-09-14 | 2003-11-04 | Tyco Electronics Corporation | Process for manufacturing a composite polymeric circuit protection device |
US6593384B2 (en) * | 2000-05-25 | 2003-07-15 | Trexel, Inc. | Polymer foam processing with low blowing agent levels |
FR2816626A1 (fr) * | 2000-11-13 | 2002-05-17 | Atofina | Materiau composite polymerique conducteur a resistance auto-controlee par la temperature |
EP1352022A4 (fr) * | 2000-12-04 | 2004-03-24 | Nova Chem Inc | Particules cellulaires moussees d'une composition polymere expansible |
FR2826646B1 (fr) * | 2001-06-28 | 2004-05-21 | Toulouse Inst Nat Polytech | Procede de fabrication selective de nanotubes de carbone ordonne en lit fluidise |
AU2004267408B2 (en) * | 2003-08-15 | 2009-01-08 | Nova Chemicals (International) S.A. | Process for processing expandable polymer particles and foam article thereof |
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2005
- 2005-04-27 FR FR0504231A patent/FR2885131B1/fr not_active Expired - Fee Related
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2006
- 2006-04-14 EP EP06743695A patent/EP1877474A2/fr not_active Withdrawn
- 2006-04-14 WO PCT/FR2006/000821 patent/WO2006114495A2/fr active Application Filing
- 2006-04-14 JP JP2008508251A patent/JP2008539295A/ja not_active Withdrawn
- 2006-04-14 US US11/910,747 patent/US20110039089A1/en not_active Abandoned
- 2006-04-14 KR KR1020077024780A patent/KR20080003843A/ko not_active Application Discontinuation
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JPH0369573A (ja) * | 1989-08-07 | 1991-03-25 | Dainippon Ink & Chem Inc | 炭素繊維断熱材 |
US6258864B1 (en) * | 1999-01-20 | 2001-07-10 | Cabot Corporation | Polymer foam containing chemically modified carbonaceous filler |
WO2003085681A1 (fr) * | 2002-04-01 | 2003-10-16 | World Properties, Inc. | Mousses polymeres et elastomeres electroconducteurs et leurs procedes de fabrication |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008091308A2 (fr) * | 2007-01-19 | 2008-07-31 | Dow Global Technologies Inc. | Mousse polymère contenant de longs nanotubes de carbone |
WO2008091308A3 (fr) * | 2007-01-19 | 2009-02-19 | Dow Global Technologies Inc | Mousse polymère contenant de longs nanotubes de carbone |
WO2009092785A1 (fr) * | 2008-01-25 | 2009-07-30 | Nmc S.A. | Compositions de mousse ignifuge |
WO2010063888A1 (fr) * | 2008-12-02 | 2010-06-10 | Valtion Teknillinen Tutkimuskeskus | Couche de catalyseur pour applications électrochimiques |
WO2011042800A1 (fr) | 2009-10-07 | 2011-04-14 | Polimeri Europa S.P.A. | Compositions de nanocomposites polymères de thermoplastique expansible à capacité d'isolation thermique améliorée |
WO2011055198A1 (fr) | 2009-11-03 | 2011-05-12 | Polimeri Europa S.P.A. | Procédé de préparation de plaquettes de graphène nanométriques qui présentent une dispersibilité élevée dans des matrices polymères de faible polarité et compositions polymères relatives |
Also Published As
Publication number | Publication date |
---|---|
FR2885131A1 (fr) | 2006-11-03 |
EP1877474A2 (fr) | 2008-01-16 |
WO2006114495A3 (fr) | 2007-01-25 |
JP2008539295A (ja) | 2008-11-13 |
KR20080003843A (ko) | 2008-01-08 |
US20110039089A1 (en) | 2011-02-17 |
FR2885131B1 (fr) | 2008-03-07 |
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