Classifications

• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • 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
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • 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
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/03—3 layers
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • 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
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/02—Composition of the impregnated, bonded or embedded layer
  • B32B2260/021—Fibrous or filamentary layer
• • 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
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/04—Impregnation, embedding, or binder material
  • B32B2260/046—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
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/02—Synthetic macromolecular fibres
  • B32B2262/0261—Polyamide fibres
  • B32B2262/0269—Aromatic polyamide fibres
• • 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
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/101—Glass fibres
• • 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
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/106—Carbon fibres, e.g. graphite fibres
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/102—Oxide or hydroxide
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/12—Mixture of at least two particles made of different materials
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/30—Particles characterised by physical dimension
  • B32B2264/303—Average diameter greater than 1µm
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/72—Density
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • 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
  • B32B2597/00—Tubular articles, e.g. hoses, pipes
• • 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
  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
  • C08F214/22—Vinylidene fluoride
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2265—Oxides; Hydroxides of metals of iron
  • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to the field of the transport of fluids for underwater oil exploitation, or "offshore" in English. More particularly, the invention relates to a composition comprising at least one fluoropolymer and at least one high density filler. The invention also relates to a thermoplastic composite tubular structure which comprises at least one outer layer consisting of said composition. The invention also relates to the method of manufacturing said composition, as well as to its applications as an outer layer for weighting thermoplastic composite tubes transporting fluids in the context of oil and gas exploration and exploitation.
• the oil and gas industry mainly distinguishes between two types of tubes: a first type to transport oil or gas from the level of the sea floor to the central well: these are the tubes called flow lines or "flow-lines” in English, and a second type for raising the oil or gas from the central well at the bottom of the sea to the floating platform on the surface: these are the riser tubes or "risers" in English English.
• thermoplastic composite tubular structures or “Thermoplastic Composite Pipes” (TCP) in English.
• Thermoplastic composite pipes use thermoplastic composite materials instead of steel to provide strength and rigidity to pipelines. These structures are composed of an internal polymeric coating aimed at ensuring watertightness and chemical resistance, a polymer layer reinforced with continuous fibers (glass, aramid, carbon, etc.) for mechanical strength, as well as an outer protective sheath.
• TCP offers a combination of high strength, flexibility and ease of termination, giving it the best qualities of conventional (strong but rigid) metal tubing and flexible tubing made from unbonded layers of helically applied metal wires and extruded thermoplastics (flexible but heavy, and very expensive to finish on site).
• Steel pipes comprising a layer acting as ballast, said layer being able to be located inside or outside the pipe, are known.
• Document FR 3007033 describes a composition of composite material for the neutralization of at least one acid compound from among carbon dioxide CO2 and hydrogen sulphide H2S, said composition comprising a mixture of a polymer material with a determined quantity of chemically active with said acid compound so as to irreversibly neutralize the corrosive effects of said acid compounds.
• the mass fraction of said chemically active products is between 4 and 40%, since, as indicated on page 14, 1.6-9, filler contents greater than 40% reduce the mechanical properties of composite materials.
• Document US 4606378 describes a subsea pipe comprising a steel pipe provided with a continuous weight coating in the form of a relatively thick layer of a composite material consisting of granules of a relatively heavy material embedded in a matrix plastic, said composite material being covered with a plastic tube.
• Said plastic matrix consists of a thermosetting resin such as epoxy, polyurethane or acrylic resin, while the heavy material incorporated in the plastic resin consists of a heavy metal ore, for example an iron ore such as magnetite or hematite, in the form of particles or granules.
• a composite material consisting of 85 to 95% by weight of magnetite in a matrix of 5 to 15% by weight of epoxy resin.
• thermoplastic composite pipes TCP
• TCP thermoplastic composite pipes
• the invention relates firstly to a composite material consisting of a thermoplastic fluorinated polymer matrix in which are incorporated particles of at least one inorganic filler compatible with said fluorinated polymer, said particles having a density of at least 3 g/ cm 3 , preferably at least 4 g/cm 3 , advantageously at least 5 g/cm 3 , the mass content of fillers being greater than 40% and ranging up to 70%, said particles having a defined size by a D50 of less than 20 im and by a D90 of less than 50 Lim.
• said fluorinated polymer is chosen from homopolymers of vinylidene fluoride (PVDF) and copolymers of vinylidene fluoride and at least one other comonomer, and mixtures thereof.
• PVDF vinylidene fluoride
• copolymers of vinylidene fluoride and at least one other comonomer and mixtures thereof.
• said fluorinated polymer is a mixture of a PVDF homopolymer and a copolymer of vinylidene difluoride (VDF) and hexafluoropropylene (HFP).
• said fluorinated polymer is a mixture of two VDF-HFP copolymers having different HFP levels.
• said filler is chosen from metal oxides such as iron(II) oxide (FeO), iron(III) oxide (Fc2O>), iron(II, III) oxide ) (Fe3O4 or FeO-Fe2O3), zinc oxide (ZnO), copper(I) oxide (Cu2O), copper(II) oxide (CuO), lead(II) oxide (PbO), nickel(II) oxide (NiO), aluminum(III) oxide (Al2O3), mixtures of these oxides and associated mineral compounds that may contain these metal oxides: magnetite, hematite, cuprite ...
• metal oxides such as iron(II) oxide (FeO), iron(III) oxide (Fc2O>), iron(II, III) oxide ) (Fe3O4 or FeO-Fe2O3), zinc oxide (ZnO), copper(I) oxide (Cu2
• said composite material contains from 50% up to 60% by weight of said filler.
• the invention also relates to a process for manufacturing said composite material, said process comprising a step of mixing the fluoropolymer and the inorganic filler, described above, in the molten state.
• Said method also comprises a step of extruding said composite material in the form of a tube or sheath intended to cover a thermoplastic composite tubular structure in order to weigh it down and thus allow it to be used in petroleum exploration and exploitation applications. and gas.
• the invention also aims to provide thermoplastic composite pipes (TCP) comprising at least one outer layer consisting of said composite material.
• TCP thermoplastic composite pipes
• the invention makes it possible to overcome the drawbacks of the state of the art.
• the invention provides a fluoropolymer-based composite material incorporating high density fillers to form a high density composition, greater than that of the fluoropolymer (for example, the density of PVDF is 1.78 g/cm 3 ), and greater than or equal to 2.15 g/cm 3 , preferably greater than or equal to 2.3 g/cm 3 , advantageously greater than or equal to 2.5 g/cm 3 , which makes it possible to manufacture a layer which, alone or with others, will subsequently cover a thermoplastic composite tubular structure (TCP) in order to weigh down the entire structure.
• TCP thermoplastic composite tubular structure
• Figure 1 includes images representing the external and internal appearance of extruded strips of VDF-HFP copolymers containing 50 or 60% by weight of magnetite.
• the invention relates to a composite material consisting of a thermoplastic fluorinated polymer matrix in which are incorporated particles of at least one inorganic filler compatible with said fluorinated polymer, said particles having a density of at least 3 g/cm 3 , preferably at least 4 g/cm 3 , advantageously at least 5 g/cm 3 , the mass content of fillers being greater than 40% and ranging up to 70%, said particles having a size defined by a D50 less than 20 iim and by a D90 less than 50 Lim.
• said composite material comprises the following characteristics, possibly combined.
• thermoplastic is meant here a non-elastomeric polymer.
• An elastomeric polymer is defined as being a polymer which can be stretched, at room temperature, to twice its initial length and which, after stress release, quickly returns to its initial length, within 10%, as indicated by the ASTM in Special Technical Publication No. 184.
• the fluorinated polymer contains in its chain at least one monomer chosen from compounds containing a vinyl group capable of opening to polymerize and which contains, directly attached to this vinyl group, at least one fluorine atom, a fluoroalkyl group or a fluoroalkoxy group.
• the fluoropolymer is chosen from homopolymers of vinylidene fluoride (PVDF) and copolymers of vinylidene fluoride and at least one other comonomer, and mixtures thereof.
• said comonomer is a fluorinated comonomer chosen from: hexafluoropropylene (HFP), perfluoro (methylvinyl) ether (PMVE), perfluoro (ethylvinyl) ether (PEVE), perfluoro (propylvinyl) ether (PPVE ), tetrafluoroethylene (TFE), perfluorobutylethylene (PFBE), chlorotrifluoroethylene (CTFE), fluoroethylenepropylene (FEP) and trifluoroethylene.
• HFP hexafluoropropylene
• PMVE perfluoro (methylvinyl) ether
• PEVE perfluoro (ethylvinyl) ether
• PPVE perfluoro (propylvinyl) ether
• TFE tetrafluoroethylene
• PFBE perfluorobutylethylene
• CTFE chlorotrifluoroethylene
• FEP fluoroethylene
• the comonomer is HFP.
• the copolymer comprises only VDF and HFP.
• these copolymers contain at least 50% by mass of VDF, advantageously at least 75% by mass of VDF and preferably at least 80% by mass of VDF.
• the VDF-HFP copolymer has a mass content of HFP greater than 10%, preferably greater than 15%. This makes it possible to lower the flexural modulus of the coating, which considerably increases the flexibility properties of the article according to the invention.
• said VDF-HFP copolymer is a random copolymer.
• This type of copolymer has the advantage of having a homogeneous distribution of the comonomer along the vinylidene fluoride chains.
• said VDF-HFP copolymer is a so-called “heterogeneous” copolymer, which is characterized by a non-homogeneous distribution of the comonomer along the VDF chains, due to the synthesis process described by the applicant, for example in the US 6,187,885.
• a heterogeneous copolymer has two (or more) distinct phases, with a phase rich in P VDF and a phase of copolymer rich in HFP comonomer.
• the heterogeneous copolymer consists of discontinuous, discrete and individual copolymer domains of comonomer-rich phase, which are homogeneously distributed in a continuous PVDF-rich phase. We then speak of a non-continuous structure.
• the heterogeneous copolymer is a copolymer having two (or more) continuous phases which are intimately linked together and cannot be physically separated. We then speak of a co-continuous structure.
• the heterogeneous copolymer can be made by forming an initial polymer that is rich in VDF monomer units, generally greater than 90 wt% VDF, preferably greater than 95 wt%, and in a preferred embodiment, a PVDF homopolymer, then adding a co-monomer to the reactor well into the polymerization to produce a copolymer.
• VDF-rich polymer and copolymer will form distinct phases resulting in an intimate heterogeneous copolymer.
• said fluorinated polymer is chosen from: i. a PVDF homopolymer; ii. a mixture of two PVDF homopolymers having different viscosities, or different molar masses, or different architectures, for example different degrees of branching; iii. a copolymer comprising vinylidene fluoride (VDF) units and one or more types of comonomer units compatible with vinylidene fluoride (hereinafter referred to as "VDF copolymer”); iv. a blend of a PVDF homopolymer and a VDF copolymer; v. a blend of two VDF copolymers.
• VDF vinylidene fluoride
• the fluorinated polymers used in the invention can be obtained by known polymerization methods such as polymerization in solution, in emulsion or in suspension. According to one embodiment, they are prepared by an emulsion polymerization process in the absence of fluorinated surfactant.
• said filler is chosen from metal oxides such as iron(II) oxide (FeO), iron(III) oxide (Fc2O>), iron(II, III) oxide ) (FesCL or FeO-Fe2O3), zinc oxide (ZnO), copper(I) oxide (Cu2O), copper(II) oxide (CuO), lead(II) oxide (PbO), nickel(II) oxide (NiO), aluminum(III) oxide (Al2O3), mixtures of these oxides and associated mineral compounds that may contain these metal oxides: magnetite, hematite, cuprite ...
• metal oxides such as iron(II) oxide (FeO), iron(III) oxide (Fc2O>), iron(II, III) oxide ) (FesCL or FeO-Fe2O3), zinc oxide (ZnO), copper(I) oxide (Cu2O), copper(II) oxide (CuO), lead(II) oxide (PbO), nickel(II) oxide (Ni
• All these compounds have a density of at least 3 g/cm 3 , preferably of at least 4 g/cm 3 , advantageously greater than 5 g/cm 3 , measured according to the ASTM D792 standard.
• the mass content of fillers varies from 50% up to 60%.
• the filler particles have a size defined by a D50 of less than 10 ⁇ m and by a D90 of less than 15 Lim.
• the inorganic fillers incorporated into the composite material according to the invention must be thermally stable up to 300°C. This thermal stability is measured by thermogravimetric analysis (TGA) under air or nitrogen flow. These fillers must be compatible with the fluoropolymer matrix. By “compatible” is meant here the ability of these inorganic fillers not to cause degradation of said matrix, in particular by means of a dehydrofluorination reaction.
• inorganic fillers can be incorporated directly into a fluorinated matrix.
• certain fillers such as titanium dioxide can catalyze a dehydrofluorination reaction of the fluorinated matrix, leading to a degradation of the mechanical properties (chain scission) and release of HF.
• any new charge is thus tested according to a safety protocol: a) mixture in the molten state of fluoropolymer and charge for 10 min at 230°C, b) measurement of mass loss by thermogravimetric analysis (isothermal for Ih at 250°C).
• the metal oxide is magnetite (FesCfi), which has a density of 5.2 g/cm 3 at 20°C.
• the composite material obtained has a density greater than 2.15 g/cm 3 , preferably greater than or equal to 2.3 g/cm 3 , advantageously greater than or equal to 2.5 g/cm 3 .
• the composite material is non-porous, that is to say that it has no porosity visible by means of an optical microscope.
• the composite material according to the invention has a ductile behavior even at -20° C., its deformation at the threshold being greater than 5%, measured according to the ASTM D638 standard.
• the invention also relates to a process for manufacturing said composite material, said process comprising a step of mixing the fluoropolymer and the inorganic filler, described above, in the molten state.
• this step is carried out using co-rotating twin-screw extruders, co-kneaders or internal mixers.
• fillers are preferably used in the form of particles whose size distribution is defined by the diameters D50 and D90.
• the D50 is the volume median diameter which is the particle size value that divides the population of particles examined exactly in half.
• the D90 is the median diameter by volume for which 90% of the population analyzed is below this value. These diameters are measured according to the ISO 9276 standard. In the present invention, a Malvern INSITEC particle size analyzer is used, and the measurement is made dry by laser diffraction on the load.
• the D50 is less than 20 Lim, preferably less than 10 Lim, while the D90 is less than 50 Lim, preferably less than 15 Lim.
• the D50 is greater than or equal to I Lim, and the D90 is greater than or equal to 5 Lim.
• These composite materials can then be used to cover a TCP structure by extrusion in order to weigh it down, in the context of oil and gas exploration and exploitation.
• the weighted polymer sheath is obtained by extruding said composite material in the form of a tube or sheath.
• This sheath is used to cover a TCP structure transporting fluids in the context of oil and gas exploration and exploitation, while maintaining the key properties of the fluoropolymer, such as temperature resistance or chemical resistance.
• the composite material according to the invention is sufficiently flexible so that the TCP can be rolled up, even at low temperatures.
• the invention also relates to a thermoplastic composite tubular structure comprising: an internal polymer layer, a polymer laminate reinforced with continuous fibers, chosen from among glass, aramid and carbon fibers, an external protective coating, the whole being surrounded by at least one outer polymer layer made from the composite material described above.
• said at least one outer layer has a thickness of at least 5 mm, preferably at least 10 mm and a density greater than or equal to 2.15 g/cm 3 , preferably greater than or equal to 2.3 g/cm 3 , advantageously greater than or equal to 2.5 g/cm 3 .
• This sheath covers a thermoplastic composite tubular structure in order to weigh it down and thus allow it to be used in oil and gas exploration and exploitation applications.
• PVDF-1 VDF-10% mass HFP copolymer having a mass melt flow index (MFR) of 4 at 230°C under a weight of 12.5 kg, and a viscosity in the molten state (230 °C, 100s 1 ) of 2350 Pa.s,
• PVDF-2 VDF-10% mass HFP copolymer having a mass melt flow index (MFR) of 8 at 230°C under a weight of 3.8 kg, and a viscosity in the molten state (230 °C, 100s 1 ) of 1000 Pa.s,
• PVDF-3 VDF-copolymer 18% by mass of HFP having a mass melt flow index (MFR) of 13 at 230°C under a weight of 3.8 kg, a viscosity in the molten state (230° C, 100s 1 ) of 800 Pa.s.
• the melt index was measured using a plastometer at a temperature of 230°C according to ISO 1133-1.
• the melt viscosity was measured using a rheometer equipped with a capillary die at a temperature of 230°C according to the ISO 11443 standard.
• the PVDF + Magnetite compositions are produced by mixing in the molten state on a Buss® co-kneader (diameter of 46 mm, L/D ratio of 15, flow rate of 20 kg/h, temperature of 220°C).
• the compositions thus produced are then extruded in the form of a strip 4 mm thick using a single-screw extruder (diameter of 30 mm, L/D ratio of 25, flow rate of 20 kg/h, temperature of 220° C. ) fitted with a 150mm wide flat die.
• the density measurements are carried out on granules according to the ASTM D792 standard according to the vertical thrust method. in tension
• Test temperature -20°C.
• thermal flowmeter FAM 50, TA Instruments
• HFM guarded fluxmeter method
• the attached Figure 1 illustrates the effect of the particle size distribution of magnetite in a PVDF-3 matrix on the external and core appearance of extruded strips 4 mm thick.
• composition D the incorporation of this Magnetite 2 up to 60% by weight (composition D) also makes it possible to achieve a density of 2.8 g/cm 3 , without visible defect in appearance.
• Composition E (PVDF-2 + 50wt% Magnetite 2) does not make it possible to obtain a deformation at the minimum threshold of 5% at -20°C.
• compositions A to D containing PVDF-3 the following results are observed: at 50% by weight (compositions A and B), the two qualities of magnetite make it possible to obtain a density of 2.5 g/cm 3 . However, the choice of Magnetite 2 clearly improves the yield and fracture strain properties, measured at -20°C.
• composition D comprising 60% by weight of Magnetite 2
• a density of 2.8 g/cm 3 is reached, while retaining a deformation at the threshold at -20°C greater than 5% at -20°C, thus good extrusion quality visible in Figure 1.
• composition C comprising 60% by weight of Magnetite 1
• necking and premature rupture of the samples are observed during the tensile test at ⁇ 20° C., which reflects an inhomogeneity in the dispersion of the material. This dispersion inhomogeneity is also visible in Figure 1. [Table 1]
• Composition F comprising a PVDF-1 which is more viscous than PVDF-3 and 50% by weight of Magnetite 2 also makes it possible to achieve a density of 2.5 g/cm 3 , as well as a higher threshold deformation at -20°C at 5%.
• Magnetite 2 For the same level of magnetite (50% by weight), an increase in thermal conductivity is observed with Magnetite 2, which can be linked to a better dispersion of Magnetite 2 in the volume of the material, and therefore to its distribution of smaller particle size.

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