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    • 专利摘要:
    The present invention relates to a process for treating a material based on polyamide (s) comprising fibers and / or silica fillers, by impregnation with at least one hydrophobic additive in supercritical CO2. It also relates to a material based on polyamide (s) comprising fibers and / or silica fillers and impregnated with at least one hydrophobic additive, obtained by such a process, and to its implementation as an electrically insulating component in a electrical apparatus, particularly in a circuit breaker.
    公开号:FR3058144A1
    申请号:FR1660457
    申请日:2016-10-27
    公开日:2018-05-04
    发明作者:Olivier Poncelet；Daniel Getto
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    Holder (s): COMMISSIONER OF ATOMIC ENERGY AND ALTERNATIVE ENERGIES Public establishment.
    Extension request (s)
    Agent (s): NONY CABINET.
    fo4J PROCESS FOR THE TREATMENT OF POLYAMIDE FILLED WITH SILICA BY IMPREGNATION IN SUPERCRITICAL CO2.
    FR 3 058 144 - A1
    The present invention relates to a process for treating a material based on polyamide (s) comprising fibers and / or silica fillers, by impregnation with at least one hydrophobic additive in supercritical CO2.
    It also relates to a material based on polyamide (s) comprising fibers and / or fillers of silica and impregnated with at least one hydrophobic additive, obtained by such a process, and to its use as an electrically insulating component in a electrical appliance, especially in a circuit breaker.
    i
    The present invention relates to a new mode of treatment of a polyamide article loaded with silica.
    In electrical devices, in particular medium or high voltage devices, the electrically insulating component or components may in particular be made of polyamides (for example polyamide 6,6 or polyphthalamide), comprising reinforcements, typically glass fibers and / or silica fillers. This is particularly the case for the dielectric part of medium voltage circuit breakers, formed from polyamide 6.6 loaded with 30 to 50% by weight of micrometric silica wires, sold by the Schneider Electric Company. These circuit breakers have a lifespan of more than 20 years. During the lifetime of the circuit breaker, thousands of breakdown tests are carried out, generally two per day, tests which mechanically stress the charged polymer very strongly. The combination of polyamide 6.6 with micrometric silica fibers has achieved the desired mechanical performance over the life of the circuit breaker and at a competitive cost.
    In medium or high voltage electrical devices, such as circuit breakers, the functions of electrical insulation and extinction of electric arcs are typically provided by an insulating gas which is confined inside the device.
    Currently, the gas most often used in this type of device is sulfur hexafluoride (SF 6 ). This inert gas has, in fact, a relatively high dielectric strength, good thermal conductivity and low dielectric losses. After being dissociated by an electric arc, it recombines quickly and almost completely. In addition, it is non-flammable and its price is moderate.
    However, sulfur hexafluoride presents a certain harmfulness from the environmental point of view. It thus has a global warming potential (GWP) of 22,800 (relative to CO 2 over 100 years) and a residence time in the atmosphere of 3,200 years, which places it among the gases with a strong tight.
    Consequently, the use of SF 6 will be regulated, or even prohibited, which has led manufacturers to seek alternatives to SF 6 .
    To replace SF 6; it has thus been proposed to use different alternative gaseous media which, while having good properties of electrical insulation and extinction of electric arcs, have a weak impact on the environment.
    Mention may be made, for example, of the gaseous media described in documents FR 2 988 215, FR 2 975 820 and FR 2 975 836, and in particular a mixture of dilution gases such as dry air and a fluoroketone.
    However, this change in the nature of the insulating gas of electrical devices is not without problems, in particular in terms of dielectric strength at the surface of the electrically insulating component or components.
    In fact, it is known that polyamides, such as polyamide 6,6, naturally have a great affinity for water. An uncharged polyamide can take up to 7% by mass of water. However, the presence of excess water greatly modifies the mechanical properties. Paradoxically, the exceptional mechanical properties of polyamide are due to the presence of water molecules of structure which play the role of plasticizer [1], A compromise was thus found by loading the polyamide with silica, typically micrometric fibers of silica. The maximum water uptake is then in the order of 2 to 3% by mass.
    However, the presence, on the surface of the molded or injected polyamide parts, of silica fibers, protruding at the surface of the electrically insulating component, causes “spike effects” which initiate the breakdown between the electrodes.
    However, this phenomenon is exacerbated depending on the nature of the atmosphere in which the circuit breaker is bathed. For example, the electrical rigidity of dry air compared to SF 6 is 2.3 times higher, but it is greatly degraded depending on the humidity level.
    Consequently, the current components based on polyamide loaded with silica cannot be used in a gaseous medium of dry air and / or fluoroketone type, due to the evolution of their dielectric properties.
    To remedy the drawbacks associated with the substitution of sulfur hexafluoride by other gaseous media in electrical devices, it appears necessary to limit the water uptake of polyamide parts loaded with silica.
    A first way to overcome these drawbacks would be to replace the polyamide 6,6, generally used, with an aromatic polyamide which is naturally more hydrophobic, but also more expensive. This also means carrying out lengthy qualification and approval tests, without guarantee that the mechanical properties will be equivalent to those of polyamide 6,6. Also, we can expect these aromatic polyamides to be very sensitive to UV rays emitted during breakdown tests and to degrade prematurely.
    Another alternative would be to modify, by an appropriate treatment, the injected or molded parts of polyamide loaded with silica, so as to limit the water uptake of the polymer matrix.
    The present invention specifically aims to propose an appropriate treatment to limit the uptake of polyamide-based materials loaded with silica.
    More particularly, the present invention proposes to implement supercritical carbon dioxide (also denoted “supercritical CO 2 ” or “sCCE”) as a vector for impregnating the polyamide-based material loaded with silica by a hydrophobic additive, such as than a silicone oil.
    Thus, the invention relates, according to a first of its aspects, to a process for treating a material based on polyamide (s) comprising at least fibers and / or silica fillers, by impregnation with at least one hydrophobic additive in supercritical CO2.
    The treatment method according to the invention is more particularly intended to reduce the water uptake of said material.
    The hydrophobic additive is advantageously a silicone oil soluble in supercritical CO2. It may also be a fluorinated compound, for example of the urea type. The hydrophobic additives which can be used for impregnating the material according to the invention are more particularly detailed in the following text.
    By "supercritical CO2" is meant in the sense of the invention the CO2 used at a temperature and a pressure higher than their critical value.
    Supercritical CO2 is generally used industrially in extraction or purification processes. More specifically, it corresponds to a fluid obtained by subjecting carbon dioxide to a temperature of at least 31 ° C and a pressure of at least 74 bar. It is particularly advantageous having regard to its cost, its ease of implementation, its non-flammability, its non-toxicity and its solvent properties.
    In addition, and unlike organic solvents, supercritical CO 2 does not require a recycling or treatment step after its use. In fact, carbon dioxide can be released in the form of a gas at the end of the treatment. Finally, the impregnation method according to the invention does not require an additional drying step after the impregnation treatment.
    Supercritical CO2 is already used as a solvent medium for the synthesis of polymers [2]. In addition, supercritical CO2 has been proposed, as an alternative to aqueous solvents, for dyeing textiles [3] or papers.
    However, to the knowledge of the inventors, the use of supercritical CO2 has never been proposed to reduce the uptake of water from the material of an electrically insulating component of an electrical device according to the invention, based on polyamide ( s) loaded with fibers and / or silica fillers.
    The treatment method according to the invention proves to be particularly advantageous for several reasons.
    First, as illustrated in the examples which follow, it makes it possible to significantly reduce the water uptake of said polyamide material (s) loaded with silica.
    Without wanting to be bound by theory, since supercritical CO2 is a dense gas, the CO2 molecules have no affinity for the water molecules trapped in the porosities of the polymer. On the other hand, they can mechanically "drive" them out of the polymer and empty the "hydrophilic" pores by filling them with the hydrophobic additive used, for example silicone oil. The polyamide swells easily in supercritical CO2, which can then diffuse into the polymer matrix by carrying the desired additive.
    The impregnation treatment according to the invention with the hydrophobic additive using supercritical CO2 thus advantageously allows hydrophobic treatment in depth of the material, and thus significantly increase the hydrophobicity of the material.
    By "impregnation" is meant that the treatment allows the presence of the hydrophobic additive within the material. The hydrophobic additive is more particularly “trapped” in the matrix or polymer network.
    More particularly, the treatment method according to the invention makes it possible to impregnate the material with the said hydrophobic additive (s) over a thickness extending from the surface of the material to a depth of at least 200 μm, in particular up to at least 300 µm in depth and more particularly up to at least 400 µm in depth. The impregnation of the material over such a thickness is sufficient to provide a lasting effect of protection against water and resistance to handling (resistance to scratches).
    The material impregnated with the hydrophobic additive, obtained at the end of the process of the invention, thus exhibits reduced water uptake compared to the untreated material. In other words, it has improved hydrophobicity.
    The "water uptake" reflects the greater or lesser amount of water that can be absorbed by the material. It can be expressed as the ratio of the increase in weight of the material after immersion in water compared to its initial weight. As detailed in the examples which follow, the water uptake can more particularly consist in placing the samples of material previously dried, under given relative humidity conditions and for a predefined period (for example immersion in water at 90 ° C. for three weeks) ; the material hydrates, which changes the mass of the sample from an initial value m (in the dried state) to a final value (m + ôm). Specifically, the “water uptake” of the material will denote the ratio ôm / rn expressed as a percentage.
    In particular, as illustrated in the examples which follow, the water uptake of the material is advantageously less than or equal to 1%, in particular less than or equal to 0.7% and more particularly less than or equal to 0.5%.
    As such, impregnation using supercritical CO 2 is more effective than impregnation by hydrostatic pressure.
    Also, compared to an impregnation treatment by hydrostatic pressure, the method of the invention using supercritical CO 2 is simpler for the treatment of parts of complex geometry, and requires a reduced amount of hydrophobic additive.
    On the other hand, the impregnation treatment is advantageously stable over time. In other words, the impregnated material retains over time its improved properties in terms of hydrophobicity, in other words of reduced water uptake.
    Consequently, the electrically insulating components produced from an impregnated material according to the invention have good properties, in particular in terms of dielectric strength at the surface, even if they are used with a gaseous medium other than SF 6 , as for example example a mixture of dry air and a fluoroketone.
    Finally, the impregnation treatment according to the invention of the components based on polyamide loaded with silica does not affect their mechanical properties.
    The invention thus relates, according to another of its aspects, to a material based on polyamide (s) comprising fibers and / or fillers of silica, and impregnated with at least one hydrophobic additive, obtained at the end of the process of impregnation of the invention.
    It also relates, according to another of its aspects, to an electrically insulating component, in particular used in an electrical appliance, formed in whole or in part of a material impregnated according to the process of the invention.
    Other characteristics, variants and advantages of the method according to the invention will emerge more clearly on reading the description and examples which follow, given by way of illustration and without limitation of the invention.
    In the following text, the expressions "between ... and ...", "ranging from ... to ..." and "varying from ... to ..." are equivalent and are intended to mean that the terminals are included, unless otherwise stated.
    Unless otherwise indicated, the expression "comprising / comprising a" must be understood as "comprising / comprising at least one".
    POLYAMIDE MATERIAL FILLED WITH SILICA
    As mentioned above, the material considered according to the invention is a material based on polyamide (s) comprising fibers and / or silica fillers.
    An impregnated material according to the invention can more particularly constitute all or part of an electrically insulating component, in particular used in an electrical device such as a circuit breaker.
    The process of the invention can, for example, be implemented directly on molded or injected parts that can be used directly as insulating electrical components in electrical devices, for example medium or high voltage electrical devices, as described in the following text. As such, the polyamide-based material can be of various shapes.
    It can be flat or not. It can for example be in the form of a film or a layer with a thickness of between 2 mm and 1 cm, in particular between 3 mm and 5 mm.
    By “material based on polyamide (s)”, it is meant to mean that the material contains by mass at least 50%, preferably at least 60%, of polyamide (s).
    The term "polyamide (s)" designates one or more polymer (s) containing amide functions resulting from a polycondensation reaction between carboxylic acids and amines.
    These polyamides can be homopolymers or copolymers, aliphatic (PA), semi-aromatic (polyphthalamide, PPA) or aromatic (PAA).
    By way of examples of polyamides according to the invention, mention may be made of polyamide 6, polyamide 6.6; polyamide 11, polyamide 12, polyamide 4.5; 6.10 and 6.12; semi-aromatic polyamides such as polyphthalamides, and their mixtures.
    According to a particular embodiment, the material is based on polyamide
    6.6.
    According to another particular embodiment, the material is based on polyphthalamide (or PPA), polyamide called "high performance" because of its excellent mechanical properties and resistance to high temperatures.
    The polyamide-based material according to the invention comprises at least silica fibers (also called "glass fibers"), silica fillers or a mixture of fibers and silica fillers.
    The fibers and / or silica fillers are micrometric in size. Typically, the silica fibers can have a diameter between 20 and 70 μm and a length of several hundred micrometers.
    These fibers and / or silica fillers present in the polyamide-based material of an electrically insulating component are known under the name "reinforcements". Preferably, these are micrometric fibers of silica.
    According to a particular embodiment, the material to be treated according to the invention is based on polyamide, in particular polyamide 6,6 or polyphthalamide, loaded with micrometric fibers of silica.
    The material to be treated can comprise fibers and / or fillers of silica, in particular silica fibers, in a mass proportion greater than or equal to 20%, in particular greater than or equal to 30%, and more particularly between 30 and 50 %, of the total mass of said material.
    Advantageously, the material comprises a mass proportion of silica fibers of approximately 50% of the total mass of the material. A high proportion of silica makes it possible to reduce the cost of the material, silica generally being less expensive than polyamides.
    The polyamide-based material may optionally further comprise reinforcements other than fillers and / or silica fibers.
    The nature of the reinforcements is chosen adequately so as not to affect the dielectric properties of the material.
    It can be for example organic fibers, such as polymeric fibers, for example polyester or aramid fibers.
    The fillers can be organic or mineral. Examples include hexagonal boron nitrides or alpha aluminas.
    The reinforcements can be made of a mixture of fibers and fillers.
    According to a particular embodiment, the polyamide material loaded with silica fibers is, prior to the impregnation treatment, subjected to a heat treatment conducive to the removal of the water adsorbed on the surface and at the feet of the micrometric silica fibers. which protrude at the surface of the polyamide material.
    This heat treatment can for example be carried out by subjecting the material to a temperature between 50 ° C and 100 ° C, in particular about 90 ° C.
    The duration of the heat treatment can be between 5 hours and 48 hours, in particular about 36 hours.
    HYDROPHOBIC ADDITIVE
    As mentioned previously, the process of the invention impregnates the material with one or more hydrophobic additives.
    It is understood that the nature of the hydrophobic additive is chosen with regard to its ability to be able to impregnate the material based on polyamide (s) under the conditions of impregnation in supercritical CO 2 according to the invention.
    By "hydrophobic" is meant to mean that the additive used has a solubility in water, at 25 ° C, less than 0.001% by weight.
    In particular, the hydrophobic additive used to impregnate the polyamide material has good solubility in supercritical CO2.
    By "soluble" in supercritical CO2 is meant that it is possible to dissolve said additive at the rate of at least 1 g of additive per 8 g of supercritical CO2.
    Preferably, the hydrophobic additive is such that the ratio of the mass of the dissolved additive to the mass of supercritical CO2 is between 1/10 and 1/8.
    Preferably, the hydrophobic additive is soluble in supercritical CO 2 for conditions of temperature below 130 ° C, in particular between 50 and 100 ° C and pressure between 250 and 450 bar.
    In fact, excessively high temperatures during the treatment of the parts treated according to the invention would be likely to cause deformation of the parts during the swelling of the polyamide material by the supercritical fluid. Also, excessively high pressures would make it difficult to use the autoclave for carrying out the impregnation treatment.
    According to a particularly preferred embodiment, the hydrophobic additive may have dielectric properties. In particular, in the case of the preparation of a material for which very good dielectric strength is required, the hydrophobic additive used is chosen from the compounds having good dielectric properties.
    Advantageously, the hydrophobic additive has a dielectric constant less than or equal to 3. This is particularly the case for silicone oils and fluorinated compounds described in the following text.
    ίο
    The dielectric constant can be measured by techniques known to those skilled in the art, for example via the use of a VEGACAL type capacitive probe calibrated with liquids of which the dielectric constant is known.
    Furthermore, advantageously, the hydrophobic additive used has a good affinity with the polyamide-based material.
    For example, the hydrophobic additive can establish interactions with the polyamide matrix of the hydrogen bond type or Van der Waals interactions.
    Such an affinity of the hydrophobic additive with the polymer matrix thus makes it possible to ensure that the hydrophobic additive remains within the polyamide matrix of the material impregnated according to the invention, in particular does not desorb from the matrix, for example during depressurization of the autoclave used for the impregnation treatment, and / or over time.
    Finally, advantageously, the hydrophobic additive has good stability over time in order to allow lasting hydrophobic treatment of the material.
    Preferably, the hydrophobic additive is present, at the temperature and pressure used for the impregnation, in the form of a more or less viscous fluid.
    In particular, the hydrophobic additive preferably has a viscosity at 25 ° C of between 20 mPa.s and 600 mPa.s, in particular between 50 mPa.s and 400 mPa.s. The viscosity can for example be measured using a BROOKFIELD viscometer.
    The hydrophobic additive used in the impregnation process according to the invention can be more particularly chosen from silicone oils and fluorinated compounds as described below.
    Silicone oils
    The hydrophobic additive can be chosen, according to a first alternative embodiment, from silicone oils, in particular silicone oils which are dielectric and soluble in supercritical CO 2 .
    Dielectric silicone oils are known for their use as dielectric fluids in electrical equipment.
    Preferably, the silicone oil has a viscosity, at 25 ° C, between 20 and 600 mPa.s, in particular between 20 and 400 mPa.s and preferably between 50 and 300 mPa.s. The viscosity can for example be measured using a BROOKFIELD viscometer.
    As hydrophobic silicone oils, linear silicone oils of the polydimethylsiloxane type can be used.
    Mention may, for example, be made of the linear silicone oils sold by the company Clearco, under the names “PSF Fluids” (for “Polydimethylsiloxane fluids” in English). These silicone oils have good dielectric properties. They can have viscosities at 25 ° C of between 0.65 cSt and 20 cSt (sold under the name "PSF-Low Viscosities"), between 50 cSt and 1000 cSt (sold under the name "PSF-Standard Viscosities") or between 5,000 cSt and 100,000 cSt (sold under the name "PSF-High Viscosities").
    The silicone oils can also be chosen from aromatic silicone oils.
    The silicone oil can be more particularly chosen from polyaryl / alkylsiloxanes, in particular from polyphenyl / alkylsiloxanes such as polyphenyl / methylsiloxane and polyphenyl / propylsiloxane.
    These oils advantageously have very good chemical stability, in other words good resistance to aging.
    Preferably, the silicone oil used is not very polar. In particular, it does not include terminal hydroxyl groups. Indeed, silicone oils carrying terminal OH functions form emulsions in supercritical CO 2 . These emulsions remain on the surface of the polyamide material, forming a gel which strongly foams when returned to ambient pressure and ambient temperature.
    According to a particularly preferred embodiment, the silicone oil used as hydrophobic additive is an oil of polyphenyl / alkylsiloxane type having the following structure (I):
    in which :
    R 1 represents a phenyl radical or a C 1 -C 6 alkyl radical, in particular a methyl or propyl radical, in particular a methyl radical;
    R 2 and R 3 represent, independently of each other, a C1-C6 alkyl radical, in particular a methyl or propyl radical, in particular a methyl radical; and n and p are such that the silicone oil has a viscosity at 25 ° C as specified above.
    In particular, the aromatic silicone oil can be chosen from poly (dimethylsiloxane-co-methylphenylsiloxane) (CAS No: 63148-52-7) and poly (dimethylsiloxane-co-diphenylsiloxane) oils (CAS No: 68083-14 -7).
    By way of examples, mention may be made of silicone oils of the polyphenyl / methylsiloxane type sold under the names “Silicone oil AR 200” and “Silicone oil AR 20” by the company Dow Corning, or under the grades “DPDM400” and “PM -125 Phenylmethyl "by Clearco.
    Fluorinated compounds
    According to another alternative embodiment, the hydrophobic additive can be chosen from hydrophobic fluorinated compounds soluble in supercritical CO 2 .
    It is known that supercritical CO 2 is an excellent solvent for fluorinated compounds.
    The fluorinated compounds are more particularly chosen from compounds having at least one hydrophobic hydrocarbon chain at least partially fluorinated, in particular totally fluorinated, having at least 6 carbon atoms, preferably at least 8 carbon atoms.
    Preferably, the fluorinated compounds have at least one hydrophobic hydrocarbon chain at least partially fluorinated and at least one group capable of ensuring attachment of the fluorinated compound with the polyamide network, in particular a group capable of interacting by hydrogen bonding or by Van interaction der Waals with polyamide chains.
    Such a group makes it possible to ensure that the hydrophobic additive remains in the polyamide matrix, even after depressurization of the autoclave and / or over time.
    Such a group may for example be a group -NH-C (O) -O (carbamate compounds), -NH-C (O) - (amide compounds) or -NH-C (O) -NH- (urea compounds) .
    Preferably, the hydrophobic hydrocarbon chain is a linear or branched, saturated or unsaturated, preferably saturated, aliphatic chain comprising at least 6 carbon atoms, said chain being at least partially fluorinated.
    In particular, the hydrophobic hydrocarbon chain can have at least 8 carbon atoms, in particular between 8 and 16 carbon atoms, preferably between 10 and 12 carbon atoms.
    Preferably, at least 2 carbon atoms out of 5 of the hydrocarbon chain, in particular at least 1 carbon atom out of 2 of the hydrocarbon chain carries one or two fluorine atoms.
    According to a particular embodiment, the hydrocarbon chain is completely fluorinated (so-called perfluorinated chain). The compounds having a perfluorinated chain are advantageously of lower cost than the compounds with partially fluorinated chain.
    The hydrophobic hydrocarbon chain of the fluorinated compound may also optionally carry one or more chlorine atoms.
    According to a particular embodiment, the fluorinated compound used as a hydrophobic additive according to the process of the invention has the following formula (II):
    in which :
    • R.2 represents:
    (a) a group -OR3 (carbamate type compounds) (b) a group -R 3 (amide type compounds); or (c) a group -NHR 3 (compounds of urea type);
    • at least one of Ri and R 3 represents a hydrophobic hydrocarbon chain, at least partially fluorinated, in particular as defined above;
    preferably, one of Ri and R 3 represents a hydrocarbon chain comprising at least 6 carbon atoms, in particular at least 10 carbon atoms, and in which at least 2 carbon atoms out of 5 of the hydrocarbon chain, in particular at least 1 out of 2 carbon atoms in the hydrocarbon chain carries one or two fluorine atoms;
    • the other of Ri and R 3 represents a Ci-20-alkyl or Ci-20-alkenyl group, optionally substituted, preferably a C6-2o-alkyl group, said group optionally carrying one or more chlorine atoms .
    Preferably, the fluorinated compound used as hydrophobic additive according to the process of the invention is of formula (II) above, in which R2 represents a group -OR 3 , a group -R 3 or a group -NHR 3 with R 3 representing hydrophobic hydrocarbon chain, at least partially fluorinated as defined above.
    The fluorinated compounds which can be used as hydrophobic additives according to the process of the invention can be obtained by synthetic methods known to those skilled in the art.
    For example, the fluorinated compounds of formula (II) above can be easily obtained by reaction between a compound of the isocyanate type Ri-N = C = O and a compound of the alcohol type (R 3 -0H), carboxylic acid (R 3 - COOH) or amine (R 3 -NH 2 ), according to the following reaction schemes:
    O (a) Ri-NCO + R 3 -0H -► R 1
    O (b) Ri-NCO + R 3 -COOH -► R — N ^ R 3 + CO 2 Ί H
    c) Ri-NCO
    R 3 -NH2
    By way of example, Example 3 which follows illustrates the impregnation of a material according to the invention in supercritical CO2 with a fluorinated compound of the urea type (Ndecyl-N ’-perfluorodecylurea).
    Of course, the invention is not limited to the hydrophobic additives specifically described above. Other hydrophobic additives can be envisaged as long as they are suitable for the impregnation in supercritical CO2 of the polyamide material loaded with silica.
    According to a particular embodiment, the hydrophobic additive (s) used according to the invention are distinct from the dyes.
    It is up to the person skilled in the art to adjust the amount of hydrophobic additive (s) used, in particular with regard to the volume of the polyamide-based material (s) to be treated.
    Typically, the amount of hydrophobic additive (s) used can be between 0.2 and 5% by weight relative to the mass of polyamide-based material to be impregnated, in particular between 0.5 and 3% by weight.
    IMPREGNATION TREATMENT
    The impregnation treatment in supercritical CO2 can be carried out using any device known to a person skilled in the art and suitable for the use of a supercritical solvent.
    Advantageously, the impregnation process is carried out in the absence of additional solvent. In other words, the only solvent present during the impregnation according to the invention is CO2 in the supercritical state.
    The use of supercritical CO2 thus avoids the use of organic solvent which should then be removed from the impregnated material obtained.
    The impregnation of the material with the hydrophobic additive using supercritical CO2 can thus be carried out via at least the steps consisting of:
    (i) have a polyamide-based material loaded with silica to be treated;
    (ii) maintaining the material to be treated in supercritical CO 2 in the presence of the hydrophobic additive, under conditions suitable for the impregnation of the material with the hydrophobic additive; and (iii) recovering the material impregnated with said hydrophobic additive.
    Typically, the impregnation process of the invention is implemented in a closed reactor, in particular an autoclave.
    Thus, according to a particular embodiment, the method of the invention comprises at least the following steps:
    - place a material based on polyamide (s) loaded with silica and at least one hydrophobic additive in an autoclave;
    - generate supercritical carbon dioxide in the autoclave;
    - maintain the material in the autoclave in the presence of supercritical CO2 and the hydrophobic additive in order to ensure the impregnation of the material by said hydrophobic additive;
    - recover the impregnated material by depressurization of the autoclave; and
    - optionally dry the material thus impregnated.
    The polyamide material is impregnated with the hydrophobic additive by maintaining the carbon dioxide in supercritical form. This allows a very rapid diffusion of the hydrophobic additive in the substrate, typically a few minutes.
    The impregnation temperature can in particular be between 50 ° C. and 150 ° C., and in particular between 80 and 120 ° C. and more particularly between 90 and 100 ° C.
    The pressure during impregnation can be between 80 and 450 bar, in particular between 150 and 400 bar, and more particularly between 200 and 350 bar.
    The duration of the impregnation treatment can be between 30 and 180 minutes, and in particular between 60 and 135 minutes.
    According to a particular embodiment, the impregnation treatment is carried out by maintaining the autoclave at a temperature between 80 and 100 ° C, at a pressure between 250 and 300 bar, and this for 60 to 120 minutes.
    The step which consists in depressurizing the autoclave consists more precisely in depressurizing up to atmospheric pressure and in evacuating carbon dioxide (preferably in the form of gas). It is advantageously carried out at a temperature which makes it possible to ensure the transition from supercritical CO 2 phase to CO2 gas, avoiding the liquid phase of CO2. This step is therefore advantageously carried out at a temperature between 45 and 85 ° C. In particular, it can be carried out at a temperature between 60 and 70 ° C.
    According to a particular embodiment, the depressurization temperature of the autoclave is advantageously the temperature at which the impregnation treatment is carried out.
    When evacuating the autoclave, the conditions are such that, advantageously, the autoclave does not contain liquid CO2.
    In general, the duration of depressurization of the autoclave is between 20 and 120 minutes, in particular between 30 and 90 minutes. This depressurization step being endothermic, it is carried out slowly to avoid thermal shocks.
    During the depressurization of the autoclave (evacuation step), carbon dioxide in the form of gas is expelled from the interior of the polyamide-based material, while the hydrophobic additive remains trapped in the material.
    The polyamide matrix is saturated with CO2 which will take several days before equilibrating with atmospheric CO2.
    After the expansion, the maximum residual mass of CO2 in the polyamide matrix is less than 5%.
    The last step makes it possible to recover the impregnated material, and optionally to separate it from the hydrophobic additive which has not impregnated the material. The residual hydrophobic additive can be advantageously recycled to impregnate new parts. The treatment process according to the invention thus makes it possible to minimize the residues.
    At the end of the impregnation according to the invention, the polyamide-based material loaded with silica more particularly comprises the said hydrophobic additive (s) in a mass content of between 0.2 and 5%, in particular between 0.5 and 2% and more particularly between 0.8 and 1.2%, relative to the total weight of the material.
    As indicated above, the method of the invention makes it possible to impregnate the material with the said hydrophobic additive (s) over a thickness extending from the surface of the material to a depth of at least 200 μm, in particular at least minus 300 µm and more particularly up to at least 400 µm in depth. Impregnation over such a thickness advantageously makes it possible to provide a lasting protective effect on water.
    As mentioned above, the material impregnated according to the invention advantageously has a reduced water uptake compared to the untreated material.
    The water uptake (ôm / m, evaluated after immersion in water at 90 ° C for 3 weeks) is advantageously less than or equal to 1%, in particular less than or equal to 0.8%, preferably less than or equal to 0.5%.
    APPLICATIONS
    As mentioned above, the polyamide-based material loaded with silica and treated according to the process of the invention may constitute all or part of an electrically insulating component, in particular used in electrical devices, in particular medium or high tension.
    The terms “medium voltage” and “high voltage” are used in their usual acceptance, namely that the term “medium voltage” designates a voltage which is greater than 1000 volts in alternating current and 1500 volts in direct current but which does not exceed not 52,000 volts in alternating current and 75,000 volts in direct current, while the term “high voltage” indicates a tension which is strictly higher than 52,000 volts in alternating current and in 75,000 volts in direct current.
    The invention thus relates, according to another of its aspects, to an electrically insulating component, formed in whole or in part of a material impregnated according to the method of the invention.
    The electrically insulating components can in particular be the pieces of current crossing surrounding the conductors (in English, “bushing”), the piece surrounding the fuse also called “fuse well”, the knife holder shaft also called “contact holder shaft "(In English," mobile shaft "), the beam (in English," insulator ") or even the sealed enclosure comprising in particular the gaseous medium ensuring electrical insulation and extinction of electric arcs likely to form within of said sealed enclosure.
    The present invention thus relates, according to another of its aspects, to the use of an electrically insulating component formed in whole or in part of a material impregnated according to the method described above, in an electrical appliance.
    It also relates to an electrical device, in particular a medium or high voltage electrical device, such as a circuit breaker, comprising an electrically insulating component formed in whole or in part of a material impregnated according to the method of the invention.
    This electrical device can in particular be a gas-insulated electrical transformer such as, for example, a power transformer or a measurement transformer. The electrical device can also be a gas-insulated line, overhead or underground, or a busbar for the transport or distribution of electricity. Finally, it can also be an electrical connection / disconnection device (also called breaking device) such as, for example, a circuit breaker, a switch, a disconnector, a fuse-switch combination, a grounding disconnector earth or a contactor.
    In general, these electrical devices are provided with a sealed enclosure in which there are at least one electrically insulating component, electrical components as well as a gaseous medium ensuring electrical insulation and extinction of electric arcs liable to form within this sealed enclosure.
    As mentioned above, this gaseous medium can be of various natures, as for example described in the documents FR 2 975 820, FR 2 988 215 and EP 3 023 996.
    In particular, it can comprise at least one fluoroketone, such as decafluoro-2-methylbutan-3-one (C5K). It can for example be a mixture of a carrier gas such as air, in particular dry air, and a fluoroketone.
    The treatment by impregnation of the process of the invention is of course implemented before the arrangement of said insulating electrical component in the sealed enclosure of the electrical appliance.
    The invention will now be described by means of the following examples, of course given by way of illustration and without limitation of the invention.
    EXAMPLES
    Materials and method
    Polyamide samples loaded with silica fibers
    The tests were carried out on samples of polyphthalamide loaded with micrometric silica fibers (50% by mass) of the GRIVORY HT2V-5H type supplied by the company Schneider Electric.
    All measurements were made on at least 6 samples (plates: 3 mm x mm x 65 mm).
    To characterize the polyamide samples used, the following experiments were carried out.
    Polyamide samples batch GRIVORY HT2V-5H were conditioned for hours at 90 ° C in an oven. The samples were weighed. The samples were then immersed in deionized water at 90 ° C for 3 weeks.
    After 3 weeks, the samples are dried and weighed.
    The water uptake (ratio of the increase in weight ôm of the material compared to its initial weight before immersion in water, average over the six samples) was measured by 2.3%.
    The same batch of GRIVORY HT2V-5H polyamide samples, conditioned 36 hours at 90 ° C in an oven, was put in steam (100 ° C) for 1 hour. The calculated water uptake is then 2%.
    These data are in accordance with those of the literature and those communicated by Schneider Electric.
    The protocol is that known as the “breakthrough curve”. The samples are placed in a high pressure reactor (300 bar) filled with a liquid and the "hydrostatic" pressure of this liquid is raised by the action of a temperature-controlled pump (20-25 ° C) . With a mass loading rate of 50% in silica fibers, the polyamide is studded with surface defects which allow glass fibers to emerge up to 50 microns above the plane. At the foot of these fibers, there are beads and or depressions 20 microns deep or more. These hollows allow water to penetrate deep. When these samples are immersed in a liquid and the pressure is increased, the liquid will fill these cavities, first the large cavities then the small ones. The capillary pressure prevents the penetration of the liquid. It is therefore necessary to increase the hydrostatic pressure so as to "pierce" this opposition. We thus progress in stages, each stage representing the breakthrough of a capillary radius domain.
    The impregnation treatment in supercritical CO 2 was carried out in an autoclave into which the hydrophobic additive is introduced.
    The autoclave is loaded with 500 g of liquid CO 2 by a pump until a pressure of 50 bar and a temperature of 5 ° C are reached. The reactor is then heated by the Joule effect so as to pass into the supercritical zone. The additive can be present in the reactor, or supplied pure by a pump in the reactor.
    EXAMPLE 1 (counterexample)
    Hydrostatic pressure impregnation with a silicone oil
    Six samples of polyamide batch GRIVORY HT2V-5H were pre-conditioned for 36 hours at 90 ° C.
    This pre-conditioning at 90 ° C for 36 hours eliminates the water adsorbed on the surface and at the feet of the micrometric fibers of silica which pierce the surface.
    The samples were subjected to a pressure of 250 bar in a silicone oil of polyphenyl / methylsiloxane type ("Silicone oil AR 200" sold by Aldrich) for 12 hours at room temperature.
    The samples were then dried.
    Water recovery test
    The samples were immersed in water at 90 ° C.
    After three weeks, the water uptake (calculated as the ratio of the increase in weight ôm of the material relative to its initial weight before immersion in water) is 1%.
    Without wishing to be bound by theory, when the samples are subjected to 250 bar, the silicone oil molecules are "pushed" inside the surface porosities of the polyamide loaded with silica fibers. However, the silicone oil being very hydrophobic, it cannot enter pores which would have remained hydrophilic despite the preconditioning ([1]).
    The six plates were stored in a desiccator at 90% RH (relative humidity) for one year at room temperature. The weight of the plates has not changed. The plates are dry to the touch.
    EXAMPLE 2 (according to the invention)
    Impregnation with a silicone oil using supercritical CO2
    Six samples of polyamide batch GRIVORY HT2V-5H, previously conditioned 36 hours at 90 ° C, were subjected to a pressure of 250 bar at 90 ° C of supercritical CO2 in the presence of 0.5 ml of silicone oil (Silicone oil AR 200 marketed by Aldrich) for 1 hour.
    The samples were then dried.
    Water recovery test
    The samples were immersed in water at 90 ° C.
    After three weeks, the water uptake, calculated as indicated above, is 0.2%.
    The six plates were stored in a desiccator at 90% RH (relative humidity) for one year at room temperature. The weight of the plates has not changed. The plates are dry to the touch.
    Conclusion
    The impregnation treatment using supercritical CO2 is more effective compared to a hydrostatic pressure impregnation treatment. It significantly reduces the water uptake of the polyamide-based material.
    The impregnated material retains over time its improved properties of low water uptake.
    In the same way, samples of polyamide loaded with silica fibers were treated with a silicone oil of lower kinematic viscosity (20 mPa.s instead of 200 mPa.s), the Silicone Oil AR 20 marketed by Aldrich.
    As in example 2, the impregnation with silicone oil in the atmosphere of supercritical CO 2 allowed hydrophobic treatment at the heart of the samples which limited the water uptake.
    Treatment in supercritical CO2 appears to be 3 to 5 times more effective than impregnation by hydrostatic pressure.
    The deposition by "dip-coating" at ambient pressure of silicone oil of the same grade forms a labile surface deposit which does not increase the hydrophobicity of the GRIVORY plates.
    It was also attempted to impregnate at 250 bar at 90 ° C under hydrostatic pressure, first increasing the temperature and then the pressure, but the GRIVORY plates tested were very deformed (flattened), the polymer having crept.
    EXAMPLE 3 (according to the invention)
    Impregnation with a fluorinated compound using supercritical CO2
    Synthesis of the fluorinated compound
    A urea derivative (N-decyl-N’-perfluorodecylurea) has been synthesized from perfluorodecylamine and decylisocyanate.
    The synthesis is carried out at 5 ° C in anhydrous ethyl ether (200 mL), followed by 5 hours of stirring at room temperature.
    The reaction medium concentrated to 20 ml is transferred to an open glass tube 4 cm in section and 5 ml in length. Concentrate to dryness. The amount of urea derivative recovered is 2 g.
    Impregnation using supercritical CO2
    The tube is placed in an autoclave of 600 ml of useful volume in which six polyamide batch lot GRIVORY HT2V-5H samples are also deposited, previously conditioned for 36 hours at 90 ° C.
    The autoclave is filled with liquid CO 2 (52 bar) and then heated to obtain a temperature of 100 ° C and a pressure of 300 bar. The impregnation treatment lasts two hours. The heating is then stopped and decompressed in two hours.
    Water recovery test
    The treated samples are weighed and placed in an oven in 90 ° C water for three weeks. They are removed from the oven, dried for half an hour at 60 ° C and then weighed again.
    The water uptake, calculated as described above, is 0.5%.
    Reference samples from the same batch of material, but not impregnated, took up about 2.3% water.
    References [1] Laredo et al., Macromolecules, 2003, 36 (26), 9840;
    [2] Cooper, J. Mater Chemistry 2000, 10, 207-234;
    [3] Tarek Abou Elmaaty et al., Fibers, 2015, 3, 309-322.
    权利要求:
    Claims (22)
    [1" id="c-fr-0001]
    1. Method for treating a material based on polyamide (s) comprising fibers and / or silica fillers, by impregnation with at least one hydrophobic additive in supercritical CO 2 .
    [2" id="c-fr-0002]
    2. Method according to claim 1, intended to reduce the water uptake of said material.
    [3" id="c-fr-0003]
    3. Method according to claim 1 or 2, wherein the material is based on polyamide 6,6 or polyphthalamide loaded with fibers and / or silica fillers, in particular loaded with micrometric fibers of silica.
    [4" id="c-fr-0004]
    4. Method according to any one of the preceding claims, in which the material comprises fibers and / or fillers of silica, in particular micrometric fibers of silica, in a mass proportion greater than or equal to 20%, in particular greater than or equal at 30% and more particularly between 30 and 50%, of the total mass of the material.
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, wherein said material forms all or part of an electrically insulating component, in particular used in an electrical device such as a circuit breaker.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, in which the hydrophobic additive is chosen from dielectric silicone oils soluble in supercritical CO 2 and hydrophobic fluorinated compounds soluble in supercritical CO 2 .
    [7" id="c-fr-0007]
    7. Method according to the preceding claim, wherein the dielectric silicone oil is chosen from linear silicone oils of polydimethylsiloxane type and aromatic silicone oils, in particular of polyphenyl / alkylsiloxane type and more particularly chosen from poly (dimethylsiloxane-co oils). -methylphenylsiloxane) and poly (dimethylsiloxane-codiphenyl sil oxane).
    [8" id="c-fr-0008]
    8. The method of claim 6, wherein the hydrophobic fluorinated compounds soluble in supercritical CO 2 comprise at least one hydrophobic hydrocarbon chain at least partially fluorinated, in particular fully fluorinated, comprising at least 6 carbon atoms, preferably at least 8 carbon atoms.
    [9" id="c-fr-0009]
    9. Method according to the preceding claim, wherein said hydrophobic fluorinated compound comprises, in addition to at least said hydrophobic hydrocarbon chain, at least one group capable of interacting by hydrogen bonding or by Van der Waals interaction with polyamide chains, in particular a group -NH-C (O) -O-, -NH-C (O) - or -NH-C (O) -NH-,
    [10" id="c-fr-0010]
    10. Method according to any one of the preceding claims, in which the said hydrophobic additive (s) are used in an amount between 0.2 and 5% by weight relative to the weight of the polyamide-based material, in particular included between 0.5 and 3% by weight.
    [11" id="c-fr-0011]
    11. Method according to any one of the preceding claims, comprising at least the steps consisting of:
    - Place a material based on polyamide (s) loaded with fibers and / or silica fillers and at least one hydrophobic additive in an autoclave;
    - generate supercritical carbon dioxide in the autoclave;
    - Maintain the material in the autoclave in the presence of supercritical CO2 and the hydrophobic additive in order to ensure the impregnation of the material by said hydrophobic additive;
    - recover the impregnated material by depressurization of the autoclave; and
    - optionally dry the material thus impregnated.
    [12" id="c-fr-0012]
    12. Method according to any one of the preceding claims, in which the impregnation treatment in supercritical CO2 is carried out at a temperature between 50 ° C and 150 ° C, in particular between 80 and 120 ° C and more particularly between 90 and 100 ° C.
    [13" id="c-fr-0013]
    13. Method according to any one of the preceding claims, in which the impregnation treatment in supercritical CO 2 is carried out at a pressure between 80 and 450 bar, in particular between 150 and 400 bar and more particularly between 200 and 350 bar. .
    [14" id="c-fr-0014]
    14. Method according to any one of the preceding claims, in which the duration of the supercritical CO 2 impregnation treatment is between 30 and 180 minutes, and in particular between 60 and 135 minutes.
    [15" id="c-fr-0015]
    15. Material based on polyamide (s) comprising fibers and / or silica fillers and impregnated with at least one hydrophobic additive, obtained by a process according to any one of claims 1 to 14.
    [16" id="c-fr-0016]
    16. Material according to the preceding claim, said material being impregnated with said hydrophobic additive (s) over a thickness extending from the surface of the material to a depth of at least 200 μm, in particular up to at least 300 μm deep and more particularly up to at least 400 μm deep.
    [17" id="c-fr-0017]
    17. Material according to claim 15 or 16, comprising a mass content of said hydrophobic additive (s) between 0.2 and 5%, in particular between 0.5 and 2% and more particularly between 0.8 and 1.2% , based on the total weight of the material.
    [18" id="c-fr-0018]
    18. Electrically insulating component formed in whole or in part of a material based on polyamide (s) comprising fibers and / or fillers of silica and impregnated with at least one hydrophobic additive, obtained by a process according to any one of claims 1 to 14.
    [19" id="c-fr-0019]
    19. Use of an electrically insulating component as defined in claim 18, in an electrical appliance, in particular in a circuit breaker.
    [20" id="c-fr-0020]
    20. An electrical appliance comprising at least one electrically insulating component as defined in claim 18.
    [21" id="c-fr-0021]
    21. An electrical device according to the preceding claim, said device comprising a sealed enclosure in which are located, in addition to said one or more electrically insulating components, electrical components and a gaseous medium ensuring electrical insulation and extinction of electric arcs liable to be forming within this sealed enclosure, said gaseous medium preferably comprising a mixture of fluoroketone and a carrier gas such as air.
    [22" id="c-fr-0022]
    22. An electrical appliance according to claim 20 or 21, said appliance being a medium or low voltage electrical appliance, such as a gas-insulated electrical transformer, a gas-insulated line or a busbar for transporting or distributing the electricity or an electrical connection / disconnection device, for example a circuit breaker.
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    同族专利:
    公开号 | 公开日
    WO2018078114A1|2018-05-03|
    EP3533071A1|2019-09-04|
    US10487186B2|2019-11-26|
    US20190248973A1|2019-08-15|
    CN109923620A|2019-06-21|
    EP3533071B1|2020-07-22|
    FR3058144B1|2019-03-29|
    CN109923620B|2020-10-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2003045448A1|2001-11-20|2003-06-05|The University Of Nottingham|Impregnation of polymeric substrates with antimicrobial substances using superficial fluids|
    WO2008055872A1|2006-11-10|2008-05-15|Rhodia Operations|Fireproof polyamide composition|
    WO2016128571A1|2015-02-13|2016-08-18|General Electric Technology Gmbh|Gas-insulated medium- or high-voltage electrical apparatus including heptafluoroisobutyronitrile and tetrafluoromethane|EP3817024A4|2018-06-26|2021-08-11|LS Electric Co., Ltd.|Arc extinguishing chamber base of molded case circuit breaker|JPH0422008A|1990-05-15|1992-01-27|Sumitomo Electric Ind Ltd|Wire|
    AT521660T|2001-11-05|2011-09-15|Alcatel Lucent|TRANSMISSION LINE CONTAINS A DIELECTRIC MICROCELLULAR FOAM|
    JP2012182116A|2011-02-03|2012-09-20|Nitto Denko Corp|Electric insulating resin sheet for motor, and method of manufacturing the same|
    FR2975836B1|2011-05-24|2014-07-04|Schneider Electric Ind Sas|ELECTRICAL GAS-INSULATING APPARATUS HAVING MEANS FOR CONTROLLING GAS PRESSURE|
    FR2975820B1|2011-05-24|2013-07-05|Schneider Electric Ind Sas|MIXTURE OF DECAFLUORO-2-METHYLBUTAN-3-ONE AND A VECTOR GAS AS A MEDIUM ELECTRICAL INSULATION AND / OR EXTINGUISHING ELECTRIC ARCS AT MEDIUM VOLTAGE|
    EP2629305B1|2012-02-20|2014-04-02|ABB Technology AG|Composite materials for use in high voltage devices|
    FR2988215B1|2012-03-16|2014-02-28|Schneider Electric Ind Sas|MIXTURE OF HYDROFLUOROOLEFIN AND HYDROFLUOROCARBIDE FOR IMPROVING INTERNAL ARC HOLDING IN MEDIUM AND HIGH VOLTAGE ELECTRIC APPLIANCES|
    FR3028678B1|2014-11-19|2016-12-30|Schneider Electric Ind Sas|ELECTRICAL INSULATION ELECTRICAL APPARATUS AND EXTINGUISHING ELECTRICAL ARCS AND METHOD THEREOF|
    JP6645237B2|2016-02-10|2020-02-14|富士ゼロックス株式会社|Resin particle composition|FR3105078A1|2019-12-20|2021-06-25|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Process for treating a material selected from a polyamide, a polyester and a polyacrylate|
    CN111534078A|2020-05-07|2020-08-14|北京宇航系统工程研究所|Temperature-resistant polyurethane-based rubber and preparation method thereof|
    法律状态:
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    2018-05-04| PLSC| Publication of the preliminary search report|Effective date: 20180504 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1660457A|FR3058144B1|2016-10-27|2016-10-27|PROCESS FOR TREATING POLYAMIDE CHARGED WITH SILICA BY IMPREGNATION IN SUPERCRITICAL CO2|
    FR1660457|2016-10-27|FR1660457A| FR3058144B1|2016-10-27|2016-10-27|PROCESS FOR TREATING POLYAMIDE CHARGED WITH SILICA BY IMPREGNATION IN SUPERCRITICAL CO2|
    US16/345,346| US10487186B2|2016-10-27|2017-10-27|Process for treating silica-filled polyamide by impregnation in supercritical CO2|
    PCT/EP2017/077636| WO2018078114A1|2016-10-27|2017-10-27|Method for treating a silica-filled polyamide by impregnating in supercritical co2|
    CN201780067200.0A| CN109923620B|2016-10-27|2017-10-27|Method for treating silica-filled polyamides by impregnation in supercritical CO2|
    EP17792031.1A| EP3533071B1|2016-10-27|2017-10-27|Method for treating a silica-filled polyamide by impregnating in supercritical co2|
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