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    • 专利摘要:
    Process for producing a piece of polymer material having fire-resistant properties, comprising at least the following steps: a) Providing a piece of polymer material, then b) Contacting the part with organometallic complexes of formula MmRn, with: - M a metal selected from aluminum, magnesium, zinc, manganese, cesium, and strontium; - m and n integers greater than 0; - R chosen from linear or branched C1-C4 alkyls, and the groups Si R 'where R' is a C1-C4 alkyl, linear or branched, and with a first fluid in the supercritical state, so as to incorporating the organometallic complexes in the part, then c) contacting the part with a second fluid in the supercritical state, the second fluid being carbon dioxide, so as to transform the organometallic complexes into metal carbonates of formula Mm ( CO3) n.
    公开号:FR3068700A1
    申请号:FR1756354
    申请日:2017-07-05
    公开日:2019-01-11
    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:

    PROCESS FOR PRODUCING A PART OF POLYMERIC MATERIAL HAVING
    FIRE-RESISTANT PROPERTIES
    DESCRIPTION
    TECHNICAL AREA AND PRIOR ART
    The present invention relates to a process for the production of a part made of polymer material having fire-fighting properties, and more particularly to a process for the production of a part made of flame-retardant and / or intumescent polymer material.
    To make a polymer flame retardant, it is possible to incorporate fillers having flame retardant properties such as, for example, fillers of aluminum hydroxides. During a fire, the charges are thermally degraded, according to an endothermic reaction which releases water by oxidation of the hydroxyl functions and forms aluminum oxides, in the case of aluminum hydroxide. The reaction cools the temperature of the hearth and the oxides formed can then act as a heat shield.
    A polymer containing metallic carbonates, such as magnesium carbonates for example, has intumescent properties. By decomposing, the carbonates will release gases and swell the polymer, giving it fire-resistant properties (thermal insulation) and thus slowing the supply of fire to fuel.
    It is known that it is possible to form polymer parts having fire-fighting properties by first producing a mixture comprising the polymer and the flame-retardant or intumescent fillers, then by forming the mixture, for example, by a classic plastics technique such as molding or injection. However, it is sometimes complicated to mix the fillers homogeneously with the polymer. In addition, the presence of these fillers has an impact on the shaping of the polymer parts, which can make it more difficult to implement.
    STATEMENT OF THE INVENTION
    It is therefore an object of the present invention to provide a process for the production of a part made of polymer material having fire-fighting charges distributed homogeneously, within the polymer, easy to implement and in which the incorporation of the fillers does not disturb the shaping of the polymer.
    By fire-fighting, we mean flame-retardant and / or intumescent properties.
    This object is achieved by a process for the production of a part made of polymer material having fire-fighting properties comprising at least the following steps:
    a) Supply of a part made of polymer material, and introduction of said part into a reaction chamber, then
    b) Bringing the part into contact with organometallic complexes of formula M m R n , with:
    - M a metal chosen from aluminum, magnesium, zinc, manganese, cesium, and strontium;
    - m an integer greater than 0;
    - n an integer greater than 0;
    - R chosen from C1-C4 alkyls, linear or branched, and Si R 'groups where R' is C1-C4 alkyl, linear or branched, and with a first fluid under pressure and temperature such as first fluid is in the supercritical state, so as to incorporate the organometallic complexes in the part, then
    c) Bringing the part into contact with a second fluid, the second fluid being carbon dioxide, under a pressure and a temperature such that the second fluid is in the supercritical state, so as to transform the organometallic complexes into metallic carbonates of formula M m (CO 3 ) n .
    By supercritical fluid is meant a fluid which is beyond its critical point, that is to say a fluid which is heated above its critical temperature and which is compressed above its critical pressure. It is also said that the fluid is in a supercritical state or in supercritical form. Typically, supercritical fluids are in the gaseous or liquid state at room temperature (20-25 ° C) and at room pressure (about 1 bar). When maintained beyond their critical point, superficial fluids have properties intermediate between those of a gas (for example, low surface tension) and those of a liquid (for example, high solvent power). A supercritical fluid can, like a gas, diffuse easily in materials, such as polymers. Due to its strong solvating power, it can entrain molecules and thus permeate, functionalize the part. The impregnation is carried out in a homogeneous manner. The critical temperature and the critical pressure depend on the fluid chosen, and will be selected accordingly by a person skilled in the art.
    In the process of the invention, the fillers having fire-retardant properties are incorporated into the piece of polymer material after it has been shaped. The incorporation of charges therefore has no impact on this stage. The parts can be of any shape: in the form of wires, thin films, tubes, fabrics or even in massive form. The piece of polymer material can, for example, be obtained by extrusion or by injection. The incorporation of fillers in the polymer material is carried out with fluids in the supercritical state and, as main reagent, organometallic complexes.
    Advantageously, when M = Mg or Al, the method comprises a step
    d) later in which the part is brought into contact with a solvent chosen from water, alcohols, or water / alcohol mixtures so as to transform the metal carbonates M m (CO 3 ) n into metal hydroxides of formula M m (OH) n . This step can be carried out at basic pH to promote the transition to the hydroxide form.
    The process can be carried out with any metal forming stable carbonates and / or hydroxides which decompose thermally at temperatures below 1000 ° C, for example between 200 ° C and 700 ° C, and preferably between 200 ° C and 500 ° C, which makes it possible to have a piece of polymer material having an anti-fire action at the appropriate time, ie when the hearth is not too advanced.
    Advantageously, during step d), the metal carbonates are in excess relative to the solvent so as to obtain a part comprising metal carbonates and metal hydroxides.
    According to a variant, in the two embodiments of the method, the solvent is introduced in excess with respect to the metal carbonates of the part so as to transform substantially all, and preferably all, the metal carbonates into metal hydroxides.
    Advantageously, during step b), the part is brought into contact with organometallic complexes of formula AIR 3 and MnR 2 . It is thus, for example, possible to obtain a part loaded with both AI (OH) 3 and / or AI (CO 3 ) 3 and Mn (CO 3 ) 2 and / or and Mn (OH) 2 .
    Advantageously, steps c) and d) are carried out simultaneously. Carbon dioxide in the supercritical state serves as a carrier fluid for the solvent which can penetrate the heart of the part made of polymer material.
    When steps c) and d) are dissociated, the solvent may not be carried by a fluid in the supercritical state. In this case, the solvent only penetrates into the surface layers of the piece of material to transform the carbonates into hydroxides. The solvent will preferably be basic so as to promote the formation of hydroxide. This embodiment is preferred in the case of magnesium because the carbonates at the heart of the part will not be transformed: the part will contain both carbonates (at the heart of the part) and hydroxides (at the surface of the part).
    According to a variant, when steps c) and d) are dissociated, the part can be brought into contact, firstly, with carbon dioxide in the supercritical state, then then with a solvent carried by a fluid at l supercritical state (of carbon dioxide or another fluid) so that it can reach the heart of the room.
    Advantageously, in the various embodiments of the production process, the first fluid is ethane, propane, ethylene or propylene.
    Advantageously, step b) is carried out in the presence of a co-solvent added to the first supercritical fluid. The co-solvent is not an element of the part made of polymer material, it is added to the reaction chamber, in addition to the first supercritical fluid. Advantageously, the co-solvent is chosen from ether, xylene or limonene.
    Advantageously, before step b), the complex M m R n is synthesized, by reacting a metal halide of formula M m X n with an organoalkali of formula AR, with X a halogen, preferably chosen from Cl, Br, and I; A = Li, Na, or K; R chosen from a C1-C4 alkyl, linear or branched, and SiR 'with R' a C1-C4 alkyl, linear or branched.
    Advantageously, X = CI or Br, and A = K.
    Advantageously, the complex M m R n is synthesized in the reaction chamber or in a secondary chamber connected to the reaction chamber.
    Advantageously, the polymeric material is a thermosetting polymer or a thermoplastic polymer.
    Advantageously, the polymer material is a thermoplastic polymer chosen from polyolefins such as polyethylene and polypropylene, or polyamides such as polyamide 11 or polyamide 12.
    Advantageously, between step b) and step c), the part is brought into contact with an alcohol of formula R'OH to form a metal alkoxide of formula M m (OR ') n . This step allows, if necessary, to remove the part from the enclosure between these two steps. Alcohol neutralizes organometallic complexes. Step c) can then be carried out to transform the alkoxides into carbonates.
    Advantageously, during the step during step c) or d), an oxidizer trap, such as an alkylphosphate or an alkylphosphinate, is added. It is possible to incorporate into the part made of polymer material, in the presence of a supercritical fluid such as carbon dioxide, other conventional fire-fighting agents and therefore to have a part protected by a water generator by oxidation, an intumescent agent and oxidizer traps for example.
    BRIEF DESCRIPTION OF THE DRAWINGS
    The present invention will be better understood on the basis of the description which follows and of the appended drawings in which:
    FIG. 1 is a curve obtained by Raman spectroscopy of a polyethylene sample into which charges of AI (OH) 3 have been incorporated, according to one embodiment of the method of the invention,
    FIG. 2 is a photograph obtained by scanning electron microscopy of a polymer sample into which particles of AI (OH) 3 have been incorporated.
    DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
    The part to be supplied in step a) is a part made of polymer material. The material may include a polymer or a co-polymer. The polymer is preferably a thermoplastic polymer or a thermosetting polymer.
    The thermoplastic polymer is advantageously a polyolefin such as polyethylene (PE), polypropylene (PP), or a polyamide (PA), preferably polyamide 11 or polyamide 12. It can also be a polymer LLDPE (“Linear Low Density PolyEthylene”) type, namely a linear low density polyethylene.
    Advantageously, a polymer having a low proportion of water, that is to say less than 5% by mass of water, and preferably less than 3% by mass of water, will be chosen to avoid reacting in situ. and highly reactive organometallic complexes. Avoid using a hygroscopic polymer. Preferably, the polymer is devoid of water.
    The part can be produced by any plastics processing technique suitable for shaping polymers, for example by injection, molding, thermoforming, calendering, induction or by rotational molding. The plastics processing operation gives the piece shape for its end use.
    The piece can be of any shape. It is, for example, a sheath of thermosetting electric wire or else a film of thermoplastic polymer.
    The part is introduced into a reaction chamber. It is a closed reactor, in particular an autoclave. The fluid can be introduced into the chamber at ambient pressure and at ambient temperature. The reaction chamber comprises means of regulation (in temperature and in pressure) to bring the fluid which is in the liquid or gaseous state, under normal conditions of temperature and pressure, in the supercritical state. The fluid can be introduced into the chamber in the supercritical state. Advantageously, a fluid will be chosen which may be in the supercritical state at a temperature below 400 ° C. and at a pressure below 100OObars. The reaction chamber can be connected to a so-called secondary chamber for storing and / or preparing the reagents. The reaction chamber may include means for introducing one or more compounds into the fluid. Advantageously, means for recycling and / or purifying the fluid can be provided.
    Incorporation of organometallic complexes in the polymer material:
    During step b), the part is brought into contact with a first fluid in the supercritical state and with organometallic complexes.
    By organometallic complex is meant a compound having at least one covalent bond between a carbon atom and a metal, for example, a bond, M-C, M'-C, M-Si-C or M'-Si-C.
    The organometallic complexes of general formula M m R n may be complexes of aluminum AIR 3 , complexes of magnesium MgR 2 , complexes of zinc ZnR 2 , complexes of manganese MnR 2 , complexes of strontium SrR 3 , or cesium complexes CsR, Cs 2 R 3 . The process could also be applied to complexes of calcium, barium, lead or even rare earths.
    The part can be impregnated with a single type of organometallic complexes, for example, only aluminum complexes, or with different complexes, for example aluminum complexes and magnesium complexes.
    The group R is a linear or branched C1-C4 alkyl radical. Preferably, it is not substituted. The group R can also be an SiR ' 3 group , with R' a linear or branched C1-C4 alkyl radical. The different groups R of the same metal complex can be chosen independently of each other.
    Advantageously, R is chosen from NiPr, nBu, tBu, and SiMe 3 .
    Advantageously, the synthesis of the complex will take place, before step b), in situ in the reaction chamber or in the secondary chamber, located upstream and connected to the reaction chamber.
    The synthesis reaction is carried out by reacting a metal halide of formula M m X n with an organoalkali. By organoalkaline is meant an organic compound comprising at least one covalent bond between a carbon atom and an alkali metal atom. The reaction is, in the case of the complex of formula M m X n : M m X n + nAR M m R n + nAX with
    X a halogen, preferably chosen from Cl, Br, or I,
    To an alkali metal, preferably chosen from Li, Na, or K, and
    - R a C1-C4 alkyl radical, linear or branched, or a SiR ' 3 group , with R' a C1-C4 alkyl radical, linear or branched.
    Preferably, and to simplify the handling of these pyrophoric products, which are very reactive with respect to oxygen and water, the synthesis is advantageously carried out in an adequate solvent (such as Et 2 O, THF , dimethyl ether (DME), iPr 2 O, hexane), and under a non-oxidizing atmosphere (such as, for example, N 2 , Ar, C 2 H 6 , C 3 H 8 , C 2 H 4 , C 3 H 6 ). The concentration of metal complex in the solvent can be increased by bubbling a neutral gas or by evaporation under low vacuum in the reactor.
    Advantageously, the salt AX formed is not soluble in the supercritical fluid. We will choose, for example, the KCI and KBr salts, and therefore, as reactants, the chlorides or bromides of magnesium or aluminum as well as the organoalkali AR with A = K.
    The reaction chamber containing the metal complex M m R n and the salt AX, and possibly traces of solvent, is advantageously filled with fluid after having synthesized and / or introduced the organometallic complexes.
    According to a variant, the fluid and the organometallic complexes can be introduced into the reactor, concomitantly.
    The fluid can be introduced into the reaction chamber in the supercritical state. The supercritical fluid is introduced, for example, in gaseous form or, preferably, in liquid form.
    The supercritical fluid can also be introduced in non-supercritical form, at room temperature and pressure. The reactor is then closed, pressurized and brought to the desired temperature, so that the fluid is in supercritical form in the reaction chamber. The temperature and the pressure are maintained for the time necessary to obtain the impregnation of the polymer by the metal complex.
    The contact time is, for example, between 30 minutes and 10 hours. The duration of the treatment will make it possible to control the depth of penetration of the metal complex into the polymer material. This duration also depends on the nature of the polymer. For example, for a polyamide 11 or 12, the fillers are incorporated into the polymer over a thickness ranging from 500 μm to 1 mm in 1 h, at 100 ° C. and 300 bars.
    By acting on both temperature and pressure, it is possible to control the concentration of metal complex M m R 3 in the fluid.
    The supercritical fluid is advantageously chemically inert with respect to the M-C and M-Si bonds, that is to say that the supercritical fluid will not react with the organometallic complexes. It will only have the role of transporting it.
    Preferably, the fluid has a technically reasonable supercritical domain start, that is to say that the supercritical domain begins at less than 400 bars and at less than 400 ° C. The temperature and pressure ranges depend on the nature of the supercritical fluid used. The temperature and pressure ranges during the incorporation process may vary, provided that the fluid always remains in a supercritical state. Generally, temperatures from 5 to 120 ° C and pressures from 30 to 300 bars are adequate. The fluid is advantageously chosen from ethane (critical point at 32.2 ° C and 48.8bar), propane (96.6 ° C and 42.5bar), ethylene (9.5 ° C and 50.76 ° bar) or propylene (91 ° C and 46, lbars).
    When the fluid is in the supercritical state, the organometallic complex is dissolved in the supercritical fluid, which makes it possible, thanks to the transport properties of the supercritical fluid, to incorporate charges in parts of very complex geometries. The incorporation is carried out not only on the surface, but also in volume, that is to say inside, in the heart of the room. The part is uniformly impregnated with the metal complex, in surface distribution and in thickness.
    The supercritical fluid can have its physico-chemical characteristics modified by the addition of one or more co-solvents. For example, it is possible to add a co-solvent to increase the concentration of complex in the supercritical fluid. The co-solvent is advantageously chemically inert with respect to the M-C or M-Si bonds. The co-solvent is advantageously chosen from ether, limonene or xylene (preferably, it is ortho-xylene). It will be possible, advantageously, to choose as co-solvent the solvent used during the synthesis of the organometallic complexes. The proportion of co-solvent in the fluid is, for example, from 0.1 to 5% by mass, preferably of the order of 1% by mass. The co-solvent is advantageously in liquid form when it is introduced into the reaction chamber. It is, for example, possible to place an open container containing the liquid cosolvent in the reaction chamber.
    The fluid and the co-solvent can be introduced simultaneously or concomitantly.
    Advantageously, after the polymer complex has been impregnated with the metal complex (step b)), the surface of the part is then swept by the supercritical fluid alone, that is to say without a metal complex, to remove from the surface of the part the molecules of complexes which have not been incorporated into the polymer.
    Advantageously, the fluid is evacuated from the reaction chamber before step c) and the pressure and the temperature have dropped to ambient pressure (lbar) and ambient temperature (20-25 ° C).
    Transformation of organometallic complexes into metallic carbonates:
    The parts obtained, at the end of step b), contain organometallic complexes M m R n . The part is then brought into contact with a second fluid in the supercritical state (step c)). The second fluid is carbon dioxide, which will diffuse in the room and react with the organometallic complexes M m R n to form metallic carbonates of formula M m (CO 3 ) n .
    Advantageously, the CO 2 is introduced in the liquid state into the reaction chamber. The pressure and the temperature are increased so as to have CO 2 in the supercritical state.
    Advantageously, during step c), the pressure and temperature ranges, to have CO 2 in the supercritical state, are from 50 to 350 bars and from 20 to 100 ° C., preferably from 250 bars to 350 bars and from 70 to 100 ° C. For example, we will place ourselves at a pressure of 300 bars and at a temperature of 90 ° C.
    The contact time between carbon dioxide in the supercritical state and the part ranges, for example, from 30 minutes to 3 hours, for example of the order of 1 hour.
    Advantageously, the polymer part containing the organometallic complexes M m R n will not be in contact with an oxidizing atmosphere between step b and step c), because the organometallic complexes are very reactive with air.
    According to a variant, it is possible, for practical reasons, to empty the reaction chamber, between step b) and step c). The organometallic complexes will be neutralized, before the opening of the reaction chamber, for example by injecting into the supercritical fluid, at the end of step b) or b), an alcohol of formula R'OH, with R 'an alkyl group. As an illustration, one can use methanol, ethanol, or isopropanol. The supercritical fluid will transport to the heart of the parts, the alcohol molecules which will react immediately with the organometallic complexes M m R n to form an alkoxide of formula M m (OR ') n . The alkanes generated will be eliminated in the supercritical fluid. The reactor can be opened and the parts stored or handled without risk. The part, containing the metal alkoxides, can also be brought into contact, thereafter, with the supercritical CO 2 , to form the metal carbonates (step c)).
    For example, when the organometallic complexes are zinc or magnesium complexes, at the end of step c) a polymer part is obtained containing fillers in the form of zinc carbonates or magnesium carbonates. These compounds have intumescent properties. The process can stop at step c).
    Magnesium has fire-fighting properties in the form of carbonate, but also in the form of hydroxide. In the case of magnesium, it is possible to carry out a subsequent step d) in which the carbonates are transformed into hydroxides, which have flame retardant properties.
    Aluminum carbonates have some instability and tend to naturally form hydrated carbonates. In the case of aluminum, a step d) is preferably carried out, after step c), to promote the formation of aluminum hydroxides having flame retardant properties.
    Transformation of metallic carbonates into metallic hydroxides:
    During step d), the part containing the metal carbonates is brought into contact with a solvent. The solvent is a source of protons for hydrolyzing carbonates. The solvent is chosen from water, alcohols, or water / alcohol mixtures so as to transform the metallic carbonates into metallic hydroxide M m (OH) n . Advantageously, the solvent is a polar compound, which cannot be dissolved in carbon dioxide in the supercritical state. Advantageously, an alcohol of formula ROH will be chosen, with R '' an alkyl group. The alcohol is, for example, ethanol (EtOH) or isopropanol (iPrOH). The hydrolysis, for example, of aluminum carbonate takes place according to the reaction:
    AI 2 (CO 3 ) 3 + 6ROH 2AI (OH) 3 + 3CO 2 + 3ROR
    Step d) can, for example, be carried out by dipping the part in the liquid solvent. The charges of metallic carbonates, placed in the surface layers of the part, will react with the solvent to form metallic hydroxides. This embodiment is advantageous in the case of magnesium. The part includes intumescent fillers Mg (CO 3 ) 2 and flame retardants Mg (OH) 2 .
    Step d) will preferably be carried out at high pH (greater than 10, for example, and preferably greater than 12).
    Advantageously, steps c) and d) can be carried out simultaneously, that is to say that the solvent and the supercritical CO 2 can be introduced simultaneously into the reaction chamber. Carbon dioxide in the supercritical state will carry the solvent to the heart of the part.
    According to one embodiment, the solvent is in excess to transform substantially all, and preferably all, of the carbonates into hydroxides.
    Alternatively, in the case of magnesium, the solvent may be the limiting reagent to have at the end of step d) magnesium carbonates, in addition to magnesium hydroxides.
    At the end of step c), or d), a polymer part is obtained, impregnated, homogeneously in surface and in volume, with fillers, having fire-fighting properties. The charges are dispersed homogeneously. The charges can be isolated from each other or in the form of aggregates, that is to say in the form of a cohesive set of charges.
    Advantageously, penetration of the charges into the heart of the part is as large as possible. The deep layers of charge can play the role of reservoir. Thus, when the surface layers of charges lose, under the effect of a fire, their fire-fighting characteristics, the underlying layers of charges still intact can be used, which prolongs the fire-fighting properties of the part in polymer material.
    Advantageously, the method will be carried out so as to incorporate at least 20% by mass of fire-fighting charges in order to have fire-protection only due to oxidation. It is possible to incorporate lower percentages (for example 5% to 10%), which will still slow the spread of fire. The percentage will be determined according to the use of the piece of polymer material.
    The incorporation of fire-fighting charges into the part made of polymer material does not modify, or very little, the shape and size of the part.
    During the last step of the process, for example during step c) or step d), an oxidizer trap can be added. The oxidizer trap can be a phosphine or a compound of the alkylphosphate, alkylphosphinate, alkylphosphonate, phosphic, halophosphinic, halogenoalkylphosphinic or arylphosphonate type.
    Illustrative and nonlimiting example of an embodiment:
    In this exemplary embodiment, even if steps a) and b) have not been implemented, steps c) and d) have been carried out.
    Polyethylene (PE) sold by the company Goodfellow was dissolved in xylene. An aluminum complex of formula AI (nBu) 3 was synthesized in this solution by reaction of nBuLi with AICI 3 in the presence of THF. The solution was then concentrated to polyethylene, under argon, keeping the medium hot to avoid recrystallization of the PE. After filtration to remove the insoluble residues of aluminum chloride and LiCI, the PE containing the metal complex AI (nBu) 3 was obtained.
    Steps c) and d) are then carried out in accordance with the method. The solid is transferred, under argon, to a one liter autoclave containing 1 ml of liquid ethanol in an open flask. Liquid CO 2 is introduced into the autoclave. A rise in temperature and pressure is carried out so as to reach a pressure of 300 bars and a temperature of 90 ° C. The fluid is in supercritical form. These temperatures and pressures are maintained for one hour. After one hour, the autoclave is cooled and brought to ambient pressure. The white solid recovered is not pyrophoric. From the sample, a tablet is prepared using a tablet press. An analysis by Raman spectroscopy, carried out on the pellet, confirms the presence of aluminum hydroxide. Note the characteristic bands of aluminum hydroxide around 1500cm 1 and 3300cm 1 (Figure 1). Thermogravimetric analysis confirms that the product contains sodium hydroxide (approximately
    7% by mass), also confirming that steps c) and d), which are essential steps of the process, have been successfully implemented. It is possible that the solid contains a little boehmite (AIO (OH)). Observation by scanning electron microscope also made it possible to confirm that charges had been incorporated at least on the surface of the polymer (FIG. 2).
    The polymer obtained, in which charges of aluminum hydroxide are incorporated, makes it possible, during a fire, to retard the flames and to trap the fumes.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. Process for the production of a part made of polymer material, having fire-fighting properties, comprising at least the following steps:
    a) Supply of a part made of polymer material, and introduction of said part into a reaction chamber, then
    b) Bringing the part into contact with organometallic complexes of formula M m R n , with:
    - M a metal chosen from aluminum, magnesium, zinc, manganese, cesium, and strontium;
    - m an integer greater than 0;
    - n an integer greater than 0;
    - R chosen from C1-C4 alkyls, linear or branched, and SiR 'groups where R' is C1-C4 alkyl, linear or branched, and with a first fluid under pressure and temperature such as the first fluid either in the supercritical state, so as to incorporate the organometallic complexes in the part, then
    c) Bringing the part into contact with a second fluid, the second fluid being carbon dioxide, under a pressure and a temperature such that the second fluid is in the supercritical state, so as to transform the organometallic complexes into metallic carbonates of formula M m (CO3) n ·
    [2" id="c-fr-0002]
    2. Method according to the preceding claim, characterized in that M is chosen from magnesium and aluminum and in that the method comprises a subsequent step d) in which the part is brought into contact with a solvent chosen from water , alcohols, or water / alcohol mixtures so as to transform the metal carbonates into metal hydroxides of formula M m (OH) n .
    [3" id="c-fr-0003]
    3. Method according to the preceding claim, characterized in that, during step d), the metal carbonates are in excess relative to the solvent so as to obtain a part comprising metal carbonates and metal hydroxides.
    [4" id="c-fr-0004]
    4. Method according to one of claims 2 and 3, characterized in that steps c) and d) are carried out simultaneously.
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, characterized in that during step b), the part is brought into contact with organometallic complexes of formula AIR3 and MnR2.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, characterized in that the first fluid is ethane, propane, ethylene or propylene.
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, characterized in that step b) is carried out in the presence of a co-solvent added to the first supercritical fluid.
    [8" id="c-fr-0008]
    8. Method according to the preceding claim, characterized in that the co-solvent is chosen from ether, xylene or limonene.
    [9" id="c-fr-0009]
    9. Method according to any one of the preceding claims, characterized in that, before step b), the complex M m R n is synthesized, by reacting a metal halide of formula MmXn with an organoalkali of formula AR, with X a halogen, preferably chosen from Cl, Br, and I; A = Li, Na, or K; R chosen from a C1-C4 alkyl, linear or branched, and SiR 'with R' a C1-C4 alkyl, linear or branched.
    [10" id="c-fr-0010]
    10. Method according to the preceding claim, characterized in that X = CI or Br, and A = K.
    [11" id="c-fr-0011]
    11. Method according to any one of the preceding claims, characterized in that the M m Rn complex is synthesized in the reaction chamber or in a secondary chamber connected to the reaction chamber.
    [12" id="c-fr-0012]
    12. Method according to any one of the preceding claims, characterized in that the polymer is a thermosetting polymer or a polymer
    10 thermoplastic.
    [13" id="c-fr-0013]
    13. Method according to the preceding claim, characterized in that the polymer is a thermoplastic polymer chosen from polyolefins such as polyethylene and polypropylene, or polyamides such as polyamide 11 or
    15 polyamide 12.
    [14" id="c-fr-0014]
    14. Method according to any one of the preceding claims, characterized in that during step c) or d), an oxidizer trap, such as an alkylphosphate or an alkylphosphinate, is added.
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    同族专利:
    公开号 | 公开日
    EP3649187B1|2021-08-04|
    WO2019008261A1|2019-01-10|
    FR3068700B1|2019-08-23|
    EP3649187A1|2020-05-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP3838570A1|2019-12-20|2021-06-23|Commissariat à l'énergie atomique et aux énergies alternatives|Method for treating a material chosen from a polyamide, a polyester and a polyacrylate|
    FR3107528A1|2020-02-26|2021-08-27|Commissariat A L'energie Atomique Et Aux Energies Alternatives|PROCESS FOR CHEMICAL MODIFICATION OF A POLYMERIC PART WITH A VIEW TO PROVIDING IT OR IMPROVING FIRE-RESISTANT PROPERTIES INVOLVING A COVALENT REACTION WITH AT LEAST ONE CARRIER COMPONENT OF AN ISOCYANATE GROUP|
    FR3107526A1|2020-02-26|2021-08-27|Commissariat A L'energie Atomique Et Aux Energies Alternatives|CHEMICAL MODIFICATION PROCESS OF A POLYMERIC PART|
    法律状态:
    2019-01-11| PLSC| Search report ready|Effective date: 20190111 |
    2019-07-31| PLFP| Fee payment|Year of fee payment: 3 |
    2020-07-31| PLFP| Fee payment|Year of fee payment: 4 |
    2021-07-29| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1756354A|FR3068700B1|2017-07-05|2017-07-05|PROCESS FOR PRODUCING A PIECE OF POLYMERIC MATERIAL HAVING ANTI-FIRE PROPERTIES|
    FR1756354|2017-07-05|FR1756354A| FR3068700B1|2017-07-05|2017-07-05|PROCESS FOR PRODUCING A PIECE OF POLYMERIC MATERIAL HAVING ANTI-FIRE PROPERTIES|
    EP18749021.4A| EP3649187B1|2017-07-05|2018-07-03|Method for producing a part made of polymer material having fireproof properties|
    PCT/FR2018/051642| WO2019008261A1|2017-07-05|2018-07-03|Method for producing a part made of polymer material having fireproof properties|
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