Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
  • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
  • H01M4/623—Binders being polymers fluorinated polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • 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
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
• • 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
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
  • Y10T428/1393—Multilayer [continuous layer]
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31507—Of polycarbonate
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

• the invention relates to a functionalized PVDF which is obtained by irradiation grafting of at least one unsaturated polar monomer on a PVDF, as well as to a mixture comprising this functionalized PVDF and a non-PVDF. amended.
• the functionalized PVDF or the mixture has the particularity of adhering to many materials such as thermoplastic polymers or inorganic materials, which makes it possible to obtain multilayer structures.
• the invention also relates to these multilayer structures and to a coextrusion process in which a layer of the functionalized PVDF or mixture is coextruded.
• PVDF is known to offer excellent mechanical stability properties, a very high chemical inertness, as well as a good resistance to aging. These qualities are exploited for various fields of application. For example, the manufacture of extruded or injected parts for the chemical engineering industry or microelectronics, the use in the form of a sealing sheath for the transport of gases or hydrocarbons, the production of films or coatings. allowing protection in the architectural field and the production of protective elements for electrotechnical purposes. However, it is also known that it is difficult to adhere the PVDF to other materials.
• the European applications EP 1484346, EP 1537989, EP 1541343 or the international applications WO 2006/045630 or WO 2006/042764 describe a process for modifying a fluoropolymer, in particular PVDF, making it possible to adhere the fluoropolymer to thermoplastic polymers. or inorganic materials.
• the method comprises irradiation grafting an unsaturated polar monomer.
• the Applicant has found that membership can be greatly increased if the fluoropolymer that is modified by this process is a particular PVDF copolymer with certain thermal and mechanical characteristics.
• the Applicant has also found that it is possible to obtain a higher coextrusion line speed in the presence of this functionalized PVDF.
• European application EP 1101994 discloses a gasoline tube comprising a layer of a functionalised fluoropolymer.
• the latter may be a fluoropolymer functionalized by radiation grafting.
• EP 1484346, EP 1537989, EP 1541343 and EP 1637319 describe a process for modifying a fluorinated polymer, especially PVDF, comprising grafting under irradiation an unsaturated polar monomer.
• PVDF can be a homo- or copolymer.
• the international application WO 2006/045630 describes a mixture of a functionalized PVDF and a flexible fluorinated polymer having a viscosity ⁇ between 100 and 1500 Pa s, a crystallization temperature Tc between 50 and 120 ° C.
• the functionalized PVDF is preferably obtained by radiation grafting and preferably comprises more than 80 mol% of VDF, or even better it is a homopolymer.
• Application EP 1508927 describes examples of functionalized PVDF used alone or as a mixture.
• KYNARFLEX ® grades are used
• the modified KYNARFLEX ® 2801 is a VDF-HFP copolymer and has the following characteristics: 11% HFP, a ⁇ y between 20 and 34 MPa, a Tc of 116.8 ° C and a viscosity v of the order of
• the KYNAR ® 761 is a PVDF homopolymer.
• the 2801 grade is more viscous than the PVDF which is modified according to the invention.
• the PVDF After the irradiation step, the PVDF has a certain degree of crosslinking due to the fact that cross-linking nodes are created between the PVDF chains: this has the effect of further increasing the melt viscosity, which makes the functionalized PVDF more difficult to transform and implement, whether in the molten state or in solution in a solvent.
• the invention relates to a copolymer of VDF and at least one monomer copolymerizable with VDF having a VDF content by weight of at least 50%, preferably at least 75%, onto which is grafted by irradiation with less an unsaturated polar monomer characterized in that the copolymer of VDF present before grafting the following characteristics:
• a crystallization temperature Tc (measured by DSC according to the ISO 11357-3 standard) ranging from 50 and 120 ° C., preferably from 85 to
• a threshold stress ⁇ y ranging from 10 to 40 MPa, preferably from 10 to 30 MPa;
• a viscosity v in the molten state (measured with a capillary rheometer at 230 ° C. at 100 sec -1 ) ranging from 100 to 1500 Pa s, preferably from 400 to
• the VDF copolymer exhibits, before grafting, a tensile Young's modulus ranging from 200 to 1000 MPa, preferably from 200 to 600 MPa.
• the invention also relates to a mixture comprising this modified copolymer and a PVDF.
• This modified copolymer or mixture may be associated with a thermoplastic polymer, an elastomer or an inorganic material.
• the comonomer can be, for example, vinyl fluoride (VF), trifluoroethylene, chlorotrifluoroethylene (CTFE),
• TFE tetrafluoroethylene
• HFP hexafluoropropene
• thermoplastic PVDF polyvinylene
• VDF-HFP copolymers whose HFP weight content varies from 4 to 22%, preferably from 10 to 20% (content calculated before grafting the unsaturated polar monomer), are preferred.
• PVDF also has the following characteristics (before grafting):
• a crystallization temperature Tc (measured by DSC according to the ISO 11357-3 standard) ranging from 50 and 120 ° C., preferably from 85 to 110 ° C.;
• a threshold stress ⁇ y (measured at 20 ° C.) ranging from 10 to 40 MPa, preferably from 10 to 30 MPa;
• a melt viscosity ⁇ (measured by capillary rheometer at 230 ° C. at 100 sec -1 ) ranging from 100 to 1500 Pa s, preferably from 400 to 1200 Pa s.
• tensile Young's modulus (ASTM D-638) which preferably ranges from 200 to 1000 MPa, preferably from 200 to 600 MPa.
• PVDF that is modified initially present lower a viscosity v, which means that after modification, the viscosity of the functionalized PVDF is also less than the modified KYNARFLEX 2801. This facilitates the implementation of functionalized PVDF whether in the molten state or in solution in a solvent.
• the functionalized PVDF or the mixture have, compared to the functionalized PVDFs of the prior art, the following advantages:
• Grades KYNARFLEX ® 2500 and 2750 sold by Arkema are examples of PVDF suitable for the invention: characteristics KYNARFLEX ® 2500 VDF-HFP copolymer having 19% HFP Tc: 87.4 ° C ⁇ y: 15 MPa v: 1000 Pa.s tens Young modulus: 220 MPa.
• the functionalized PVDF this is obtained by the grafting under irradiation of at least one unsaturated polar monomer on the PVDF defined above.
• the process comprises the following steps: a), the PVDF is premixed with at least one unsaturated polar monomer by all the melt mixing techniques known from the prior art.
• the mixing step is carried out in any mixing device such as extruders or kneaders used in the thermoplastics industry.
• an extruder will be used to form the mixture into granules.
• the grafting takes place on a mixture (in the mass) and not on the surface of a powder as described, for example, in US Pat. No. 5,576,106.
• the proportion of PVDF is, by weight, between 80 to 99.9% by weight. %, preferably from 90 to 99% for 0.1 to 20%, preferably 1 to 10% unsaturated polar monomer, respectively.
• the mixture is irradiated (irradiation ⁇ or ⁇ ) in the solid state using an electronic or photonic source under an irradiation dose of between 10 and 200 kGray, preferably between 10 and 150 kGray.
• the mixture may for example be packaged in polythene bags, the air is removed and the bags are closed.
• the dose is between 2 and 6 Mrad and preferably between 3 and 5 Mrad. Irradiation with a cobalt-60 bomb is particularly preferred.
• the content of unsaturated polar monomer which is grafted is, by weight, between 0.1 and 5% (that is to say that the unsaturated polar monomer grafted corresponds to 0.1 to 5 parts for 99.9 to 95%).
• parts of PVDF advantageously from 0.5 to 5%, preferably from 0.9 to 5%. This content depends on the initial content of the unsaturated polar monomer in the mixture to be irradiated. It also depends on the effectiveness of the grafting, and therefore the duration and energy of the irradiation.
• the unsaturated polar monomer which has not been grafted, and the residues released by the grafting, in particular the HF, can then optionally be removed. This last step may be necessary if the ungrafted unsaturated polar monomer is likely to hinder adhesion or for toxicology problems.
• This operation can be carried out according to techniques known to those skilled in the art. Vacuum degassing may be applied, possibly by applying heating at the same time.
• the functionalized PVDF in a suitable solvent such as, for example, N-methylpyrrolidone, then to precipitate it in a non-solvent, for example in water or in an alcohol, or to wash the PVDF functionalized with a solvent inert with respect to the fluoropolymer and grafted functions.
• a suitable solvent such as, for example, N-methylpyrrolidone
• a non-solvent for example in water or in an alcohol
• a solvent inert for example, when grafting maleic anhydride, it can be washed with chlorobenzene.
• the grafting by irradiation takes place at "cold", typically at temperatures below 100 ° C., or even 50 ° C., so that the mixture to be irradiated is not in the molten state, as for one conventional grafting process in extruder.
• An essential difference is that the grafting takes place in the amorphous phase and not in the crystalline phase while homogeneous grafting occurs in the case of grafting in the melt extruder.
• the unsaturated polar monomer is therefore not distributed identically on the PVDF chains in the case of radiation grafting and in the case of grafting in an extruder.
• the functionalized PVDF therefore has a different distribution of the unsaturated polar monomer on the PVDF chains compared to a product that would be obtained by grafting in an extruder.
• Unsaturated carboxylic acids having 4 to 10 carbon atoms and their functional derivatives, particularly their anhydrides, are particularly preferred unsaturated monomers.
• unsaturated monomers are methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, undecylenic acid, allylsuccinic acid, and the like.
• cyclohex-4-ene-1,2-dicarboxylic acid 4-methyl-cyclohex-4-ene-1,2-dicarboxylic acid, bicyclo (2,2,1) hept-5-ene 2,3-dicarboxylic acid, x-methylbicyclo (2,2,1-hept-5-ene-2,3-dicarboxylic acid, zinc, calcium or sodium undecylenate, maleic anhydride, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, difluoromaleic anhydride, crotonic anhydride, glycidyl acrylate or methacrylate, allyl glycidyl ether, vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane vinyl triacetoxysilane, ⁇ -methacryloxypropyltrimethoxysilane.
• unsaturated monomers include C 1 -C 8 alkyl esters or glycidyl ester derivatives of unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylate and the like.
• amide derivatives of unsaturated carboxylic acids such as acrylamide, methacrylamide, maleic monoamide, maleic diamide, N - monoethylamide maleic, N, N - diethylamide maleic, N - maleic monobutylamide, N, N - dibutylamide maleic, furamic monoamide, furamic diamide, fumaric N-monoethylamide, N, N-diethylamide fumaric, fumaric N-monobutylamide and N, N-dibutylamide furamic; imide derivatives of unsaturated carboxylic acids such as maleimide, N-butylmale
• maleic anhydride is used.
• This monomer indeed offers the following advantages: it is solid and can be easily introduced with the fluoropolymer granules before mixing in the molten state, - being solid, it is also more easily handled (it is particularly volatile),
• the functionalized PVDF may be used alone or in admixture with another PVDF, which may be a homo- or copolymer PVDF.
• this other PVDF is chosen so that the two PVDF are compatible and that the mixture has only one melting peak by DSC.
• the other PVDF is a copolymer of VDF and at least one monomer copolymerizable with VDF having a VDF content by weight of at least 50%, preferably at least 75% and which has the same thermal and mechanical characteristics specified above.
• the mixture comprises, by weight, from 1 to 99%, preferably from 50 to 99%, of the functionalized PVDF for 99 to 1%, and preferably 1 to 50%, of another PVDF, respectively.
• the mixture can be prepared in a melt using a mixing tool suitable for thermoplastics, for example using an extruder.
• the functionalized PVDF or the mixture may be associated with a thermoplastic polymer, an elastomer or an inorganic material.
• the invention also relates to a multilayer structure comprising at least one layer comprising at least one functionalized PVDF or the mixture and:
• At least one layer comprising at least one thermoplastic polymer and / or at least one elastomer, at least one layer of an inorganic material.
• each layer is defined as broadly as possible by the expression "layer comprising a polymer X”.
• the multilayer structure is also defined in parallel by "layer of the polymer X”.
• Multilayer structure with a thermoplastic polymer layer This structure can be prepared for example by the coextrusion, rotational molding or extrusion blow molding technique. It can take the form of a film, a tube, a container or a hollow body.
• thermoplastic polymers examples include:
• Polyamides for example PA 6, 11, 12, 6, 6, ...
• Polymers comprising predominantly (> 50% by weight) ethylene or propylene.
• PE polyolefins
• PP polyolefins
• vinyl chloride-based polymers such as PVC (soft, rigid), chlorinated PVC (CPVC) or vinylidene chloride (eg PVDC);
• ABS acrylonitrile-butadiene-styrene copolymer
• SAN styrene-acrylonitrile copolymer
• Acrylic polymers especially homo- or copolymer PMMA
• PPO polyphenylene oxide
• polyurethanes Styrene-based polymers and copolymers, especially impact polystyrene or crystal as well as styrene-diene block copolymers of the SBS type;
• Fluoropolymers such as, for example, PVDF, PTFE, copolymers of TFE and HFP, copolymers of ethylene and TFE, copolymers of ethylene and chlorotrifluoroethylene, polyvinyl fluoride.
• the polyolefin may be a polyethylene of the MDPE (medium density), HDPE (high density), LDPE (low density), LLDPE (linear low density), polyethylene prepared by metallocene type or more generally monosite type or else cross-linked polyethylene (PEX). It may be a homo- or copolymer.
• the copolymer may in particular be a copolymer having a comonomer content greater than 5% by weight, for example an ethylene-octene copolymer of the ENGAGE ® type.
• CBO olefin elastomers blocks
• Thermoplastic elastomers which according to the definition proposed in NUPAC in 2002 are melt-processable copolymers and which have a continuous elastomeric phase reinforced by a dispersion of vitreous or crystalline domains which act as junction points in a limited temperature range.
• elastomers-thermoplastics mention will be made especially TPO.
• elastomers mention may be made of:
• nitrile rubber eg acrylonitrile-butadiene copolymer
• Copolyether amides and copolyester amides eg PEBAX grades marketed by ARKEMA.
• the adhesion between the functionalized PVDF layer or the mixture and the thermoplastic or elastomeric polymer layer is not sufficient, at least one layer of an adhesion binder may be placed between these two layers.
• the adhesion binder advantageously has chemical functions which react with those present on the functionalized PVDF. For example, if acid anhydride functions have been grafted onto PVDF, the adhesion binder advantageously comprises epoxide or hydroxy functions.
• the adhesion binder layer may be optionally split. That is to say between the thermoplastic polymer layer and the layer of functionalized PVDF or mixture can be providing a 1 st layer of binder and a 2 nd layer of another binder, the two layers of binder being arranged against each other.
• a multilayer structure mention may be made of the one comprising arranged in the order one against the other: a layer comprising at least one thermoplastic polymer and / or at least one elastomer;
• At least one layer of an adhesion binder A layer comprising the functionalized PVDF or the mixture;
• a layer comprising a fluoropolymer, preferably a PVDF homo- or copolymer.
• the thermoplastic polymer layer is the outer layer or the inner layer.
• the thermoplastic polymer is a polyethylene, which is in the form of a tube or a container and which is used for the transport or storage of a chemical that may damage the polyolefin the polyethylene layer being the outer layer.
• the chemical may be, for example, a hydrocarbon (gasoline, fuel, etc.) or a corrosive product (acid, base, hydrogen peroxide, etc.).
• the functionalized PVDF layer or mixture and / or the fluoropolymer layer protects the polyolefin layer. In the case of a hydrocarbon, it avoids the swelling of the polyolefin.
• Another example of a multilayer structure comprises arranged in order one against the other:
• a layer comprising a fluoropolymer, preferably a homo- or copolymer PVDF;
• a layer comprising the functionalized PVDF or the mixture
• At least one layer of an adhesion binder is optionally at least one layer of an adhesion binder
• a layer comprising at least one thermoplastic polymer and / or at least one elastomer; Optionally at least one layer of an adhesion binder;
• a layer comprising the functionalized PVDF or the mixture
• a layer comprising a fluoropolymer, preferably a PVDF homo- or copolymer.
• thermoplastic polymer is a polyethylene, which is in the form of a tube or a container and which is used for the transport or storage of a chemical product. likely to damage the polyolefin.
• the chemical may be, for example, a hydrocarbon (gasoline, fuel, etc.) or a corrosive product (acid, base, hydrogen peroxide, etc.).
• the functionalised PVDF or mixture layers and / or the optional layers of the fluoropolymer serve to protect the polyethylene inner layer. In the case of a hydrocarbon, they also prevent the swelling of polyethylene.
• inorganic material By inorganic material is meant: "a metal;
• the layer comprising the functionalized PVDF or the mixture therefore constitutes a protective coating for the inorganic material.
• the inorganic material is coated with a composition comprising at least one functionalized PVDF or the mixture according to the invention.
• This composition protects for example against corrosion in all its forms. It may also optionally comprise at least one acrylic polymer, for example a PMMA. It may also optionally comprise one or more additives chosen from anti-UV agents, mineral fillers, pigments and / or dyes, conductive fillers such as carbon black or carbon nanotubes, etc.
• the metal can be for example iron, copper, aluminum, titanium, lead, tin, cobalt, silver, tungsten, nickel, zinc or an alloy (for example steel , carbon steels, nickel, chromium, nickel-chromium, chromium-molybdenum, silicon, stainless steel, cast iron, Permalloy, aluminum-magnesium, aluminum-silicon, aluminum-copper-nickel alloys - magnesium, aluminum-silicon-copper-nickel-magnesium, brass, bronze, silicon bronze, silicon brass, nickel bronze).
• an alloy for example steel , carbon steels, nickel, chromium, nickel-chromium, chromium-molybdenum, silicon, stainless steel, cast iron, Permalloy, aluminum-magnesium, aluminum-silicon, aluminum-copper-nickel alloys - magnesium, aluminum-silicon-copper-nickel-magnesium, brass, bronze, silicon bronze, silicon brass, nickel bronze).
• the metal may first undergo a physical and / or chemical pretreatment the purpose of which is to clean the metal surface and promote the adhesion of the functionalized PVDF layer or mixture.
• a physical and / or chemical pretreatment the purpose of which is to clean the metal surface and promote the adhesion of the functionalized PVDF layer or mixture.
• Possible pretreatments are: alkaline degreasing, solvent degreasing such as trichlorethylene, brushing, grinding, phosphating, chromating, anodizing (eg for aluminum and its alloys), anodizing chromic, silanization, abrasion, etching and in particular sulfochromic etching.
• a possible pretreatment may be to apply an adhesion promoter.
• the adhesion promoters have been described by Cassidy P. E. in the journal Ind. Eng. Chem. Prod. Res. Development, 1972, Volume 11, No.
• Pretreatment may also consist of a combination of these various pretreatments, including the combination of a physical pretreatment. and chemical.
• the metal can be in various forms and geometry such as for example in the form:
• An elongated surface such as, for example, a sheet, a plate or a sheet, a hollow body such as, for example, a container, a container, a bottle, a bottle, a chemical reactor,
• the coating can be applied in the molten state, in solution in a solvent or in powder form.
• a powder it is possible to use the bed technique fluidized by soaking a heated metal piece in a fluidized bed of the powder is usable or the electrostatic powder coating technique.
• the powder is introduced into a gun where it is conveyed by compressed air and passes through a nozzle raised to a high electrical potential generally between ten and a hundred kV.
• the applied voltage may be of positive or negative polarity.
• the flow rate of the powder in the gun is generally between 10 and 200 g / min, preferably between 50 and 120 g / min.
• the powder is charged with a certain amount of electricity, the particles of powders conveyed by the compressed air are applied to the metal part connected to the earth, that is to say say to a zero electrostatic potential.
• the particles of the powder are retained on this surface by their electrostatic charge and the electrostatic attraction forces are sufficient for the powder-coated object to be displaced and heated in an oven.
• the functionalized PVDF or the mixture can be used in the manufacture of positive or negative electrodes, in particular for lithium-ion batteries.
• the electroactive layer containing either mixed oxide fillers or carbon and / or graphite feeds and other ingredients for adjusting the electrical performance is generally carried out by dispersing the charges in a solvent in the presence of a polymeric binder fluorinated. The dispersion is then deposited on a metal collector by a "cast” method, the solvent is then evaporated to obtain a negative or positive electrode depending on the nature of the charge used.
• the performance of a battery greatly depends on the characteristics of the binder. A good binder makes it possible to produce sufficiently charged layers of electroactive ingredients which makes it possible to have a high specific capacity.
• the binder must also be stable against oxidation-reduction reactions during charge / discharge cycles and must also be insensitive to the electrolyte present in the battery.
• the electrolyte typically contains carbonate type solvents (ethyl carbonate, propylene) and a lithium salt (LiPF6, LiBF 4 ).
• carbonate type solvents ethyl carbonate, propylene
• LiPF6, LiBF 4 a lithium salt
• the functionalized PVDF may be replaced by functionalized PVDF or the mixture of the invention.
• the invention also relates to the use of the functionalized PVDF or the mixture according to the invention for the manufacture of a positive or negative electrode of a battery, preferably a lithium-ion battery.
• a positive or negative electrode for lithium-ion battery comprising the structure composed of a
• a layer 1-2 comprising the functionalized PVDF or the mixture of the invention.
• the metal is preferably aluminum for a positive electrode and copper for a negative electrode.
• the Applicant has found that it is possible with the coextrusion technique in which at least one layer comprising the coextrusion is coextruded.
• Functionalized PVDF or the mixture and at least one layer of a thermoplastic polymer to increase the coextrusion line speed (i.e. a multilayer structure speed coextruded in m / min) without impairing the quality of the adhesion between the functionalized PVDF layer (or mixture) and the layer (s) in contact.
• the invention also relates to the coextrusion method using the functionalized PVDF or the mixture of coextruding at least one layer of the functionalized PVDF or mixture and at least one layer of a thermoplastic polymer or an elastomer.
• KYNAR ® 720 PVDF homopolymer from Arkema with a melt index 20 g / 10 min (230 0 C, 5 kg) and melting temperature of 170 0 C with the following characteristics:
• OREVAC ® 18302 LLDPE-type polyethylene grafted with maleic anhydride with a melt index of 1 g / 10 min and a melting point of 124 ° C
• LOTADER ® AX 8840 copolymer of ethylene (92% by weight) and glycidyl methacrylate (8% by weight) from the company ARKEMA having a melt index of 5 according to ASTM D-1238.
• PEX obtained from a mixture of 95% by weight BORPEX ® ME-2510 and 5% MB-51, two products marketed by BOREALIS.
• the crosslinking is carried out by heating and is due to the presence of silane functions on the polyethylene.
• PVDF-1 VDF-HFP copolymer having 16% by weight of HFP with: Tc: 103 ° C. ⁇ y: 18 MPa v: 900 Pa.s Young's modulus traction: 360 MPa
• the PVDF-1 is mixed at 190 ° C. with 2% by weight of maleic anhydride. This mixture is done with all the wells of the extruder closed, with a screw speed of 200 rpm and a flow rate of 60 kg / h.
• the product which is pelletized is introduced into a bag having a sealed layer of aluminum. This bag is irradiated under 20 kgray. The product after irradiation was again passed into the extruder at 245 ° C under a maximum vacuum and at 200 rpm. The flow rate is 25 kg / h.
• the infrared analysis of the product after this devolatilization step shows a degree of grafting of
• Example 2 We use the conditions of Example 1 but with the Kynar 720 ® PVDF instead of -1.
• the infrared analysis of the product after devolatilization shows a degree of grafting of 0.50% and a free maleic anhydride level of 300 ppm. This product is called Functionalized PVDF 2.
• KYNAR ® 720 (130 ⁇ m) / functionalized PVDF 2 (50 ⁇ m) / LOTADER ® AX 8840 (50 ⁇ m) / PEX (780 ⁇ m).
• the PEX layer is the outer layer. All layers adhere to each other. Extrusion is carried out at 40 m / minute under the following conditions:
• KYNAR ® 720 130 microns
• functionalized PVDF 2 diluted to 50% in a VDF-HFP copolymer containing 16% HFP and having a viscosity at 230 0 C of 900 Pa.s at 100 s "1 (50 .mu.m) / LOTADER ® AX 8840 (50 ⁇ m) / PEX (780 ⁇ m).
• Extrusion is carried out at 40 m / minute.
• the PEX layer is the outer layer. All layers adhere to each other.
• the adhesion between the layers of PVDF mixture and Lotader ® 8840 is measured at 20 N / cm by circumferential peel after 5 days.
• the adhesion is adhesive type.
• Example 3 Is manufactured in the same conditions as in Example 3, a tube having the following structure: KYNAR ® 720 (130 microns) / functionalized PVDF 1 (50 .mu.m) / Lotader ® AX 8840 (50 .mu.m) / PEX (780 .mu.m).
• Extrusion is carried out at 40 m / minute.
• the adhesion is measured at 60 N / cm by circumferential peel after 5 days.
• the adhesion is of cohesive type in the layer of LOTADER ® 8840. Table I
• the LOTADER AX 8840 serves as an adhesion binder between the functionalized PVDF and the PEX.
• the extrusion is carried out at 230 ° C. on a film of 250 ⁇ m in total thickness.
• the adhesion is measured at 18 N / cm between functionalized PVDF 1 and EVOH.
• Example 7 (Comparative) A film is produced on CoIMn sheath extruder having the following structure:
• KYNAR ® 2500-20 50 ⁇ m
• functionalized PVDF 2 25 ⁇ m
• EVOH 25 ⁇ m
• the extrusion is carried out at 230 ° C on a film of 250 microns in total thickness.
• the adhesion is measured at 0.5 N / cm between functionalized PVDF 1 and EVOH.
• a threshold stress ⁇ y ranging from 10 to 40 MPa, preferably from 10 to 30 MPa;
• a melt viscosity ⁇ (measured by capillary rheometer at 230 ° C. at 100 sec -1 ) ranging from 100 to 1500 Pa s, preferably from 400 to 1200 Pa s.
• a multilayer structure comprising at least one layer comprising the copolymer as defined in any one of claims 1 to 5 or the mixture as defined in any one of claims 6 to 10 and: at least one layer comprising at least at least one thermoplastic polymer and / or at least one elastomer,
• At least one layer of an inorganic material At least one layer of an inorganic material.
• Multilayer structure comprising arranged in the order one against the other:
• a layer comprising at least one thermoplastic polymer and / or at least one elastomer
• At least one layer of an adhesion binder is optionally at least one layer of an adhesion binder
• a layer comprising the copolymer as defined in any one of claims 1 to 5 or the mixture as defined in any one of claims 6 to 10;
• a layer comprising a fluoropolymer, preferably a PVDF homo- or copolymer.
• Multilayer structure comprising arranged in the order against each other: Optionally a layer comprising a fluoropolymer, preferably a homo- or copolymer PVDF;
• a layer comprising the copolymer as defined in any one of claims 1 to 5 or the mixture as defined in any one of claims 6 to 10;
• At least one layer of an adhesion binder is optionally at least one layer of an adhesion binder
• a layer comprising at least one thermoplastic polymer and / or at least one elastomer
• At least one layer of an adhesion binder A layer comprising the copolymer as defined in any one of claims 1 to 5 or the mixture as defined in any one of claims 6 to 10;
• a layer comprising a fluoropolymer, preferably a PVDF homo- or copolymer.
• thermoplastic polymer is chosen from:
• Polyamides preferably PA 6, PA 11, PA 12 and PA 6.6;
• Polymers comprising more than 50% by weight of ethylene and / or propylene;
• Polymers comprising more than 50% by weight of vinyl chloride
• ABS acrylonitrile-butadiene-styrene copolymer
• SAN styrene-acrylonitrile copolymer
• PPO polyphenylene oxide
• Polymers and copolymers comprising more than 50% by weight of styrene; Fluoropolymers such as PVDF, PTFE, copolymers of
• TFE and HFP copolymers of ethylene and TFE, copolymers of ethylene and chlorotrifluoroethylene, polyvinyl fluoride.
• thermoplastic polymer is a polyolefin or a copolymer of ethylene and at least one comonomer of ethylene selected from alpha-olefins, preferably butene or octenes, vinyl esters of saturated carboxylic acids, preferably vinyl acetate or vinyl propionate, alkyl (meth) acrylates, preferably methyl acrylate, butyl acrylate or ethyl acrylate.
• the polyolefin is a polyethylene homo- or copolymer of the type medium density (DME), a HDPE (high density), a LDPE (low density), a LLDPE (linear low density) polyethylene prepared by a metallocene or more generally monosite type of catalysis or a crosslinked polyethylene (PEX).
• DME type medium density
• HDPE high density
• LDPE low density
• LLDPE linear low density polyethylene prepared by a metallocene or more generally monosite type of catalysis or a crosslinked polyethylene (PEX).
• At least one acrylic polymer is:
• Positive or negative electrode for lithium-ion battery comprising the structure consisting of a
• a layer 1-2 comprising the modified copolymer according to any one of claims 1 to 5 or the mixture as defined in any one of claims 6 to 10.
• Electrode according to claim 21 characterized in that the metal is aluminum or copper.

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• 2006
  • 2006-08-08 FR FR0653316A patent/FR2904828B1/fr not_active Expired - Fee Related
• 2007
  • 2007-07-07 US US12/376,654 patent/US20100255378A1/en not_active Abandoned
  • 2007-08-07 EP EP07823697A patent/EP2052002A2/fr not_active Withdrawn
  • 2007-08-07 JP JP2009523327A patent/JP5457180B2/ja not_active Expired - Fee Related
  • 2007-08-07 WO PCT/FR2007/051791 patent/WO2008017789A2/fr not_active Ceased
  • 2007-08-07 CA CA002660341A patent/CA2660341A1/fr not_active Abandoned
  • 2007-08-07 CN CNA2007800369847A patent/CN101522735A/zh active Pending
• 2009
  • 2009-03-04 NO NO20090985A patent/NO20090985L/no not_active Application Discontinuation

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