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    • 专利摘要:
    The present invention relates to a composite composition based on at least one aluminosilicate geopolymer composition and at least one low viscosity organic polymer or oligomer, its preparation process, a device comprising a cable and / or an accessory. cable, said cable and / or cable accessory comprising at least one composite layer obtained from said composite composition, and a method of manufacturing such a device.
    公开号:FR3049948A1
    申请号:FR1653074
    申请日:2016-04-07
    公开日:2017-10-13
    发明作者:Thierry Auvray；Franck Gyppaz；Anne-Gaelle Alexandre
    申请人:Nexans SA；
    IPC主号:
    专利说明:

    FIRE-RESISTANT COMPOSITE LAYER FOR CABLE OR ACCESSORY FOR CABLE
    The present invention relates to a composite composition based on at least one aluminosilicate geopolymer composition and at least one low viscosity organic polymer or oligomer, its preparation process, a device comprising a cable and / or an accessory. cable, said cable and / or cable accessory comprising at least one composite layer obtained from said composite composition, and a method of manufacturing such a device.
    It applies typically but not exclusively to electrical and / or optical cables intended for the transmission of energy and / or data transmission, in particular to electrical and / or optical safety cables resistant to fire, in particular halogen-free, susceptible to operate for a given period of time in fire conditions, without being a fire propagator or significant smoke generator; as well as their accessories such as junctions and / or terminations. These safety cables are in particular medium-voltage power transmission cables (in particular from 6 to 45-60 kV) or low-frequency transmission cables, such as control or signaling cables.
    An energy and / or telecommunication cable is a cable intended for the transport of electrical energy and / or the transmission of data. It conventionally comprises one or more insulated conductor elements, or in other words one or more elongated electrical and / or optical conductors surrounded by at least one electrically-layered layer. insulating. The electrically insulating layer may typically be an electrically insulating polymer layer in physical contact with the electrical (s) and / or optical (s) conductor (s). Said insulated conductor element or elements are surrounded by an outer protective sheath for mechanically protecting the isolated conductive element (s). In some cable constructions, there is only one layer that provides the two functions of electrical insulation and protective sheath.
    The materials generally used to form the electrically insulating layer and / or said protective sheath are composite materials based on polymers, for example silicone polymers, and various additives, especially reinforcing fillers such as silica, and flame retardant fillers (or flame retardants) for improving their fire resistance.
    Despite the presence of such charges, the fire resistance of these insulating layers does not always give complete satisfaction.
    In order to make one or more fire-resistant cables, it has also already been proposed, particularly in the patent application EP-A1-2,760,030, to cover said cables with an electrically insulating layer comprising a plurality of superimposed insulating strips comprising mica and glass fibers, and a polymeric binder (eg polyorganosiloxane) in contact with each of said insulating strips. However, the production cost of said electrically insulating layer is high (i.e. very long preparation time) and it has a large footprint. Other materials such as stone, brick, cement, lead, steel, concrete, rockwool, ceramics, geopolymers, etc. have fire resistance properties.
    In particular, the geopolymers are essentially inorganic chemical compounds or mixtures of compounds consisting of silico-oxide (-Si-O-Si-O-), silico-aluminate (-Si-O-Al-O-) type units. , ferro-silico-aluminate (-Fe-O-Si-O-AI-O-), or alumino-phosphate (-AI-O-P-O-), created by a process of geopolymerization (ie polycondensation). Geopolymers can be used alone or mixed with organic polymers, mineral, metallic or organic fibers (eg glass fibers, ceramic fibers, etc.), carbon, graphite, etc. depending on the type desired application. Geopolymers are generally capable of polymerizing and curing at room temperature (geopolymer cements). It is also possible to accelerate the polymerization rate and thus the hardening of the geopolymers by subjecting them to a heat treatment.
    The exact mechanism of geopolymerization is still unknown, particularly because of the rapidity of the reaction.
    The most common geopolymers are those based on aluminosilicates referred to as "poly (slalate)" [or "poly (silico-oxo-aluminate" or (-Si-O-AI-O-) n with n denoting the degree These aluminosilicate geopolymers result from the polycondensation of oligomers of the oligo (sialate) type generally formed from a mixture of at least one aluminosilicate, an alkaline reagent (eg sodium or potassium silicate) and The geopolymers based on aluminosilicates have been grouped into three families according to the Si / Al atomic ratio, which may be equal to 1, 2 or 3. We distinguish poly (slalates) corresponding to the formula Mn (- Si-O-Al-O-) n or (M) -PS, the poly (slalate-siloxos) corresponding to the formula Mn (-Si-O-Al-O-Si-O-) n or (M) - PPS, and poly (sialate-disiloxos) corresponding to the formula Mn (-Si-O-Al-O-Si-O-Si-O) n or (M) -PSDS, with M representing at least one alkaline cation or alkaline earth such as K, Na , U, Cs or Ca and n denoting the degree of polymerization.
    Geopolymers are used in many applications: designing new materials in the fields of civil engineering and construction, creating sculptures, making partitions and fire doors for fire protection, and most recently as a structure for the "black box" embedded in the planes. For example, US Patent Application 2012/0094028 A1 discloses a geopolymer-epoxy resin composite composition that can be used as a coating of a substrate, mortar, adhesive, or molding material. The composite composition is prepared by mixing a first composition comprising a crosslinking agent of the epoxy resin, amorphous silica and a source of an aluminosilicate, with a second composition comprising an epoxy resin and an alkali silicate solution; and crosslinking the mixture at room temperature.
    However, the geopolymers of the prior art are not optimized to allow their mixing with an organic polymer and form an inorganic organic polymer-geopolymer composite material. In particular, the geopolymer may exhibit excessive rigidity upon drying or consolidation and become brittle; or it can form a granular structure during the polycondensation, that is to say a heterogeneous structure having two phases: a homogeneous geopolymer matrix and inorganic micrometric grains induced by incomplete geopoiymerization, making it difficult to disperse a polymer organic within the inorganic geopolymer.
    Thus, the solutions described above are not suitable, especially in terms of flexibility, adhesion and thermal protection, to be able to serve as a fire-resistant layer in an electric cable and / or data transmission and / or in a cable accessory, especially during a fire. Moreover, they are not necessarily compatible with the preservation of the good mechanical and dielectric properties of the other constituents of a cable accessory or of a cable (electrical and / or optical conducting element, other layers, in particular electrically insulating layers, screens, etc ...).
    The object of the present invention is to overcome the drawbacks of the techniques of the prior art by providing a composite composition that can form a composite layer in a cable or in a cable accessory, said composite layer having good fire resistance, while guaranteeing good mechanical properties, especially in terms of flexibility, and an advantageous cost price.
    Another object of the invention is to provide a method for preparing a simple composite composition, economical, easy to implement, and to lead to a composite layer that can be used in a cable or in a cable accessory, which avoids the propagation of the flame, resists fire in order to function as long as possible, and limits its degradation in extreme thermal conditions such as a fire, while guaranteeing good mechanical properties, especially in terms of flexibility.
    The present invention firstly relates to a composite composition comprising at least one organic liquid at room temperature polymer or oligomer and at least one aluminosilicate geopolymer composition in the form of a gel comprising an alkali aluminate, an alkali silicate, water and optionally an alkaline base.
    The aluminosilicate geopolymer composition preferably comprises water, silicon (Si), aluminum (Al), oxygen (O), and at least one element selected from potassium (K), sodium ( Na), lithium (U), cesium (Cs) and calcium (Ca).
    In the present invention, the term "room temperature" means a temperature of from about 18 to about 25 ° C.
    In the present invention, the term "aluminosilicate geopolymer composition" means that the composition is capable of forming an aluminosilicate geopolymer. The ingredients of the aluminosilicate geopolymer composition can thus undergo polycondensation to form an aluminosilicate geopolymer. Indeed, the geopolymers result from a reaction of inorganic polycondensation by alkaline activation, called geosynthesis, as opposed to traditional hydraulic binders in which the hardening is the result of a hydration of calcium aluminates and calcium silicates.
    Consequently, the aluminosilicate geopolymer composition of the invention is different from a ceramic composition or powder or a composition comprising a conventional anhydrous cement (eg cements classified according to the EN-197-1-2000 standard, for example Portiand cement such as white cement or slag and ash cement) and water.
    Moreover, unlike aluminosilicate geopolymer compositions of the prior art, the aluminosilicate geopolymer composition of the invention has the advantage of being able to lead during the polycondensation to a uniform gel, that is to say without formation of micrometric grains during geopolymerization.
    The alkali silicate may be chosen from sodium silicates, potassium silicates and a mixture thereof. The alkali silicates sold by Silmaco and PQ Corporation are preferred. The alkali aluminate may be potassium or sodium aluminate.
    According to one embodiment of the invention, the aluminate is a sodium aluminate.
    When present, the alkaline base can be selected from KOH, NaOH and mixtures thereof.
    According to a particularly preferred embodiment of the invention, the aluminosilicate geopolymer composition comprises from 0.5 to 20% by weight of an alkaline aluminate, from 15 to 50% by weight of an alkali silicate, from 0 to About 3% by weight of an alkaline base and about 50 to about 90% by weight of water.
    According to a particularly preferred embodiment of the invention, the aluminosilicate geopolymer composition comprises from about 0.5 to about 15% by weight of an alkaline aluminate, from about 15 to about 40% by weight of an alkali silicate, from about 0 to about About 3% by weight of an alkaline base and about 55 to 85% by weight of water.
    In particular, the aluminosilicate geopolymer composition comprises from about 15 to about 50% by weight of solids (alkali aluminate, alkali silicate and alkaline base when present), and preferably about 15 to about 40% by weight, based on the total mass of said composition.
    The aluminosilicate geopolymer composition is in the form of a gel at room temperature. Indeed, the use of an alkali aluminate in place of an aluminosilicate generally used in the geopolymer compositions of the prior art, avoids the formation and the presence of micrometric grains within said geopolymers. Aluminosilicates [e.g. metakaolin or calcined kaolin, fly ash well known under the Anglicism "fly ash", blast furnace slag well known under the Anglicism "blast furnace slag", swelling clays such as bentonite, calcined clays, any type of compound comprising aluminum and silica fume, zeolites or one of their mixtures) in fact tend not to react completely during geopolymerization, inducing the formation of a heterogeneous structure.
    The composite composition further comprises a liquid organic polymer or oligomer at room temperature.
    Said organic polymer that is liquid at room temperature can have a molecular weight of at least about 10,000 g / mol.
    Said organic oligomer that is liquid at room temperature can have a molecular weight of at least about 1000 g / mol, and preferably at least about 2000 g / mol. The oligomer or the organic liquid polymer at room temperature may be chosen from polyorganosiloxanes, polyethylenes, copolymers of ethylene and vinyl acetate, polyethylene glycols, epoxy resins and acrylic resins.
    Polyorganosiloxanes, and in particular silicone oils with viscosity ranging from 5000 cP (or 6000 cP) to 50000 cP at about 25 ° C are preferred.
    The composite composition may further comprise a crosslinking agent. The crosslinking agent may be chosen from peroxides, especially organic peroxides.
    When used, the crosslinking agent is preferably from about 0.2 to about 5 weight percent, and preferably from about 0.2 to about 3 weight percent, based on the total weight of the composite composition.
    The composite composition may further comprise at least one cellulosic compound, in particular at a proportion of from 0.01 to 20% by weight, and more preferably from 0.1 to 10% by weight, relative to the total weight of the composite composition.
    The composite composition may further comprise at least one starch. The starch generally comprises amylose, amylopectin, and optionally phytoglycogen. By way of example (and depending on the source), the starch comprises from 15 to 30% by weight of amylose, from 70 to 85% by weight of amylopectin, and from 0 to 20% by weight of phytoglycogen, relative to the total mass of the starch. The starch may be a native starch or a modified starch, and preferably a native starch. Native starch can be cereal starch (eg wheat, corn, barley, triticale, sorghum or rice), tubers (eg potato or cassava), legumes (eg peas or soybeans), roots, bulbs , stems, fruit or a mixture thereof. The modified starch can be a physically, chemically or enzymatically modified starch. The modified starch may be chosen from oxidized starches, acid-hydrolysed, oxidizing or enzymatically-treated starches, modified starches (e.g. functionalized) by physico-chemical means, such as in particular esterified and / or etherified starches.
    The functionalization can be obtained by acetylation in aqueous phase with acetic anhydride, reactive extrusion of acid anhydrides, mixed anhydrides, fatty acid chlorides, oligomers of caprolactones or lactides, by hydroxypropylation in the glue phase, by cationization in dry phase or glue phase, by crosslinking, by anionization by phosphatation or by succinylation, by silylation, by butadiene telomerization, etc.
    Oxidized starches are preferred.
    According to the invention, the starch preferably represents from 0.01 to 20% by weight approximately, and more preferably from 0.1 to 10% by weight approximately, relative to the total mass of said composite composition.
    The composite composition may further comprise at least one plasticizer.
    The plasticizer may be intended to improve the dispersion of the starch within the composite layer or be used as an implementing agent (well known under the Anglicism "processing aid").
    The plasticizer may be a metal stearate, an ethylene glycol, a polyol such as glycerol, sorbitol, mannitol, maltitol, xylitol, a sucrose such as glucose or fructose, a plasticizer containing amide groups, any type of plasticizer based on modified polysaccharide (s) or a mixture thereof.
    The preferred plasticizer is a metal stearate such as zinc stearate.
    According to the invention, the plasticizer preferably represents from 0.01 to 20% by weight approximately, and more preferably from 0.1 to 10% by weight approximately, relative to the total mass of said composite composition.
    The composite composition may also comprise at least one inert filler, especially chosen from talc, phyllosilicates, hydrated hydroxides such as aluminum hydroxide (ATH) or magnesium hydroxide (MDH), silicas, borates, micas and kaolins.
    Talc is preferred.
    When used, the inert filler preferably represents about 0.01 to 18% by weight, and more preferably about 0.1 to 10% by weight, based on the total weight of the composite composition.
    The composite composition may further comprise at least one dye, in particular chosen from dyes that are liquid at room temperature.
    When used, the dye preferably represents about 0.5 to 1.5% by weight, based on the total weight of the composite composition.
    According to the invention, the aluminosilicate geopolymer composition preferably represents from 20 to 90% by weight approximately, and even more preferably from 50 to 85% by weight approximately, relative to the total mass of the composite composition.
    According to the invention, the organic polymer or oligomer preferably represents from 10 to 80% by weight approximately, and even more preferably from 15 to 50% by mass approximately, relative to the total mass of the composite composition. The subject of the invention is a process for the preparation of a composite composition according to the first subject, characterized in that it comprises at least the following stages: i) the preparation of an aluminosilicate geopolymer composition comprising an alkaline aluminate, a alkali silicate, water and optionally an alkaline base, said aluminosilicate geopolymer composition being as defined in the first subject of the invention, ii) mixing a liquid organic polymer or oligomer at ambient temperature such that defined in the first subject of the invention with the aluminosilicate geopolymer composition of step i), and iii) optionally the addition of a crosslinking agent to the mixture of step ii).
    When step iii) exists, a crosslinking agent as defined in the invention is used.
    The preparation of an aluminosilicate geopolymer composition according to step i) is generally carried out at a high pH, in particular ranging from 10 to 13. Step i) preferably comprises the following substeps: ia) the preparation of a aqueous solution of alkali silicate of molar ratio SiO 2 / M'2 O ranging from about 1.6 to about 35, and preferably from about 1.6 to about 4, where M 'is an alkali metal, the mass concentration of the alkali silicate in water ranging from about 30 to 60%, and preferably from about 40 to 60%. ib) the preparation of an aqueous solution of sodium aluminate, the mass concentration of sodium aluminate in water ranging from about 1.2 to 20%, and ic) the mixing of the aqueous solutions from the steps ia) and ib).
    The aqueous alkali silicate solution of the sub-step i-a) can be prepared by mixing silicon dioxide S102 or an alkali silicate with a base M'OH in which M 'is preferably K, Na or a mixture thereof.
    Si02 silicon dioxide may be selected from silica fume (i.e., fumed silica), quartz, and mixtures thereof.
    In particular, the alkaline base can be dissolved in water resulting in a release of heat (exothermic reaction), then silicon dioxide SiO 2 or alkali silicate can be added.
    The alkali silicate is preferably sodium silicate.
    The aqueous sodium aluminate solution of sub-step i-b) can be prepared by mixing sodium aluminate in the form of a powder and water. The combination of the aqueous alkali silicate solution and the sodium aluminate solution allows the formation of a low to high viscosity gel depending on the respective contents of sodium aluminate, water and alkali silicate.
    The aluminosilicate geopolymer composition at the end of the sub-step 1-c) is in the form of a gel.
    An inert filler and / or a dye and / or a starch and / or a plasticizer and / or a cellulosic compound as defined in the invention may be added to the aluminosilicate geopolymer composition during step II) or to the composite composition after step ii) and before step iii) if it exists.
    According to the invention, the composite composition according to the first subject of the invention may be prepared according to the following steps: a) the preparation of a first composition comprising an alkaline aluminate as defined in the invention and optionally a crosslinking agent as defined in the invention, b) the preparation of a second composition comprising a polymer or oligomer liquid at room temperature as defined in the invention and an alkali silicate solution as defined in the invention, and c) the mixture of the two previous compositions.
    An inert filler and / or a dye and / or a starch and / or a plasticizer and / or a cellulosic compound as defined in the invention may be added to the first composition of step a) or the second composition of the invention. step b), or the mixture of step c). The third object of the invention is a device comprising an energy and / or telecommunication cable and / or an accessory for an energy and / or telecommunication cable, characterized in that said cable and / or cable accessory comprises at least one composite layer obtained from a composite composition according to the first subject of the invention.
    The composite layer is preferably fire resistant.
    The liquid organic polymer at room temperature of the composite composition according to the first object makes it possible to ensure the cohesion of the composite layer and its adhesion on the layer of the cable with which it is intended to be in direct physical contact. The aluminosilicate geopolymer composition of the composite composition according to the first object, as for it, ensures the fire resistance of the composite layer.
    In other words, the composite layer of the device of the invention is a homogeneous organic / inorganic hybrid layer. In particular, this homogeneity is obtained thanks to the combination within the composite composition of an aluminosilicate geopolymer composition which is in the form of a gel and an organic polymer in liquid form at room temperature. The resulting composite layer is flexible.
    Advantageously, the device according to the invention satisfies at least one of the following fire resistance standards: EN50200, IEC60331-1, EN50399, IEC60331-11, IEC60331-21, IEC60331-23, IEC60331-25, DIN4102 , NBN713020 Addendum 3, EN50577, NFC32070 CRI, IEC600332-1 and BS6387CWZ.
    Advantageously, the composite layer defined above satisfies the IEC 60331-11 fire resistance standard, with electrical cables at a voltage of 10 kV exposed to a temperature of approximately 750 ° C. for 120 minutes.
    The composite layer preferably has a substantially constant thickness and in particular constitutes a continuous protective envelope.
    The composite layer preferably has a thickness of from about 0.5 to 4 mm, and more preferably from about 1.5 to 3 mm.
    When the thickness of the composite layer is less than 0.5 mm, the thermal protection of the device of the invention is not sufficient.
    The composite layer preferably comprises an aluminosilicate geopolymer having an Si / Al molar ratio of from 1 to 35, and preferably from 1.9 to 3.
    The aluminosilicate geopolymer of the composite layer may be chosen from poly (sialates) corresponding to the formula (I) Mn (-Si-O-Al-O-) n [(M) -PS], poly (sialate-siloxos) ) corresponding to the formula (II) Mn (-Si-O-Al-O-Si-O-) n [(M) -PPS], and the poly (sialate-disiloxos) corresponding to the formula (III) Mn ( -Si-O-Al-O-Si-O-Si-O) n [(M) -PSDS], wherein M is at least one alkaline cation K, Na, U, Cs or a mixture thereof, and n denoting the degree of polymerization. In the compound of formula (I), the molar ratio Si / Al is 1, in the compound of formula (II), the molar ratio Si / Al is 2, and in the compound of formula (III), the ratio molar Si / Al is 3.
    The composite layer of the invention is preferably non-porous.
    Due to the presence of the composite layer, the device according to the invention has excellent fire resistance while having good mechanical properties. In particular, the composite layer is sufficiently flexible to allow the handling of the cable (e.g. winding, folding, twisting) without causing unacceptable alteration of said layer which would have the effect of reducing its cohesion and fire resistance. Furthermore, the composite layer remains intact from ambient temperature to the operating temperature of the cable under charge (ie under tension) and has the advantage of forming an ordered porous structure as early as 450 ° C., thus making it possible to provide enhanced protection against the diffusion of heat for at temperatures greater than or equal to 1000 ° C for a duration of up to 120 min, especially reached during a fire. This porous and rigid structure contains air which by nature is an excellent thermal insulator.
    In other words, the composite layer is transformed under the effect of a high temperature, especially a temperature ranging from 450 ° C. to 1000 ° C., generally reached during a fire, to form a cohesive residual layer. and porous which protects the cable or cable accessory, and in particular the underlying layers and / or the elongate conductive element.
    An energy and / or telecommunication cable generally comprises at least one elongated conductive element and at least one outer protective sheath, in particular electrically insulating sheath.
    An accessory for a cable may be a junction or a termination that may comprise an assembly of several layers of materials generally of the silicone rubber type, one or more reinforcing layers, for example one or more metal layers, and an outer protective sheath. such as for example an elastomeric tape or a strip of mica.
    The composite layer is preferably an inner layer of said cable or cable accessory.
    According to the invention, the term "inner layer" means a layer which does not constitute the outermost layer of the cable or cable accessory, and more particularly: in the case of a cable, an interposed layer; between the elongated conductive element and an outer protective sheath, in particular electrically insulating, said layer being or not in direct contact with the elongated conductive element and - in the case of a junction or termination, a layer interposed between the outer protective sheath and one of the layers of silicone rubber material and / or one of the reinforcing layers, said layer being or not in direct contact with said outer sheath.
    The composite layer of the cable of the invention generally covers one or more elongated conductive elements or is positioned on an inner sheath or layer of the cable or cable accessory, it then acts as a stuffing.
    According to a preferred embodiment, the device is a cable.
    In this case, the cable comprises at least one elongated conductive element and the composite layer as defined in the invention surrounds said elongated conductive element.
    The composite layer is preferably in direct physical contact with the elongated conductive member.
    The cable may include a plurality of elongated conductive elements. The composite layer can then surround the plurality of elongated conductive elements of the cable.
    The composite layer of the invention is preferably in direct physical contact with the elongated conductive elements.
    The cable may comprise a plurality of composite layers as defined in the invention.
    According to a first variant of this embodiment, the cable comprises one or more elongated conductive elements and the plurality of composite layers surrounds the elongated conductive element or the plurality of elongated conductive elements. By way of example, the cable may comprise two composite layers as defined in the adjacent invention.
    According to a second variant of this embodiment, the cable comprises a plurality of elongated conductive elements and each of the composite layers individually surrounds each of the elongated conductive elements to form insulated elongated conductive elements.
    According to this second variant, each of the composite layers of the invention is preferably in direct physical contact with each of the elongate conductive elements which it surrounds.
    The elongated conductive element (s) of the cable of the invention are preferably elongated electrically conductive elements. The cable is therefore an electric cable.
    The cable of the invention may further comprise an outer protective sheath, in particular electrically insulating, surrounding the layer (s) composite (s).
    The outer protective sheath is preferably made of a halogen-free material. It can be carried out conventionally from materials which retard the propagation of the flame or resist the propagation of the flame. In particular, if they do not contain halogen, it is called cladding type HFFR (for the Anglicism "Halogen Free Flame Retardant").
    The sheath is the outermost layer of the cable (i.e. also known as the outer protective sheath).
    It comprises at least one organic or inorganic polymer.
    The choice of the organic or inorganic polymer is not limiting and these are well known to those skilled in the art.
    According to a preferred embodiment of the invention, the organic or inorganic polymer is chosen from crosslinked and non-crosslinked polymers.
    The organic or inorganic polymer may be a homo- or co-polymer having thermoplastic and / or elastomeric properties.
    The inorganic polymers may be polyorganosiloxanes.
    The organic polymers may be polyurethanes or polyolefins.
    The polyolefins may be chosen from ethylene and propylene polymers. By way of example of ethylene polymers, mention may be made of linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), copolymers of d ethylene and vinyl acetate (EVA), copolymers of ethylene and butyl acrylate (EBA), methyl acrylate (EMA), 2-hexylethyl acrylate (2HEA), ethylene copolymers and alpha-olefins such as for example polyethylene-octene (PEO), copolymers of ethylene and propylene (EPR), terpolymers of ethylene and propylene (EPT) such as for example terpolymers of ethylene propylene diene monomer (EPDM) or a mixture thereof.
    The sheath polymer is preferably an organic polymer, more preferably an ethylene polymer, and more preferably a copolymer of ethylene and vinyl acetate, linear low density polyethylene, or a mixture thereof.
    The outer protective sheath may further comprise a hydrated flame retardant mineral filler. This hydrated flame retardant mineral filler acts primarily physically by decomposing endothermically (e.g. water release), which results in lowering the sheath temperature and limiting the spread of flame along the cable. In particular, we speak of flame retardancy properties, well known under the Anglicism "f / ame retardant".
    The hydrated flame retardant inorganic filler may be a metal hydroxide such as magnesium hydroxide or aluminum trihydroxide.
    The outer protective sheath may further comprise an inert filler, especially chosen from talc, micas, dehydrated clays and a mixture thereof.
    The fourth subject of the present invention is a method for manufacturing a device comprising an energy and / or telecommunication cable and / or a cable accessory as defined according to the third subject of the invention, characterized in that it comprises at least the following steps: 1) the preparation of a composite composition according to the process according to the second subject of the invention; and 2) applying the composite composition of step 1): either around one or more elongated conductive elements and / or around an inner layer of an energy and / or telecommunication cable when the device is a cable, - or around at least one of the inner layers of a junction or termination when the device is a cable accessory, to form a composite layer as defined in the invention.
    The process according to the invention is fast, simple and economically advantageous. It allows to manufacture in a few steps a device with excellent fire resistance, while ensuring good mechanical properties, especially in terms of flexibility.
    Depending on the intended application, step 2) can be carried out by extrusion of said composite composition at room temperature or at a temperature, in particular at a temperature ranging from about 60 ° C. to 110 ° C., and preferably from 70 ° C. to About 95 ° C.
    The method may further comprise a step 3) of crosslinking the polymer or organic oligomer liquid at room temperature, when the composite composition of step 1) comprises a crosslinking agent.
    This step 3) can be performed by any means known to those skilled in the art.
    According to a particular embodiment of the invention, and when the device is an energy and / or transmission cable, the method may furthermore comprise, before, during or after step 2), a step 4) of application of an outer protective sheath, in particular electrically insulating, around the composite layer.
    The production of this outer protective sheath may in particular be carried out by extrusion. Step 4) is generally carried out at room temperature since the geopolymerization is carried out at ambient temperature. The invention will be better understood, and other objects, details, features and advantages thereof will appear more clearly in the following description of particular embodiments of the invention, given solely by way of illustration and not limitation, with reference to the appended figures.
    In these figures: - Figure 1 is a schematic sectional view of an electrical cable of the prior art not according to the invention; - Figure 2 is a schematic sectional view of an electric cable according to one embodiment of the present invention.
    For the sake of clarity, only the essential elements for understanding the invention have been shown schematically in these figures, and this without respect of the scale.
    The electric cable 10, illustrated in Figure 1, corresponds to a fire-resistant medium voltage electrical cable type SHXCHX for marine type applications.
    This electric cable 10 comprises: an elongated central electrically conductive element 1 and, successively and coaxially around this central conductive element 1, an internal semiconductor screen 1.1, an electrically insulating layer 2 (eg of ethylene and crosslinked propylene elastomer) EPR), an external semiconductor screen 2.1, a semiconducting banded layer 3, a metal braid 4 (eg consisting of tinned copper wire of circular section), an inner sheath comprising a polyester tape 5 and tinned copper 6, a polyester tape 7, and an outer sheath 8 (eg elastomer).
    The electric cable 11, illustrated in FIG. 2, corresponds to an electrical cable of structure similar to that of the cable of FIG. 1 but in which two composite layers as defined in the invention have been incorporated.
    This electric cable 11 comprises: an elongated central electrically conductive element 1 and, successively and coaxially around this central conductive element 1, an internal semiconductor screen 1.1, an electrically insulating layer 2 (eg of ethylene and crosslinked propylene elastomer) EPR), an external semiconductor screen 2.1, a semiconducting banded layer 3, a metal braid 4 (eg consisting of tinned copper wire of circular section), a composite layer 9 as defined in the invention, a inner sheath comprising a polyester ribbon 5 and tinned copper wires 6, a polyester ribbon 7, a composite layer 9 as defined in the invention, and an outer sheath 8 (eg of elastomer).
    The following examples illustrate the present invention. They do not have a limiting character on the overall scope of the invention as presented in the claims. The ratios between the oxides are molar ratios and the indicated percentages are in bulk.
    EXAMPLES
    The raw materials used in the examples are listed below: - about 50% by weight aqueous sodium silicate solution of "waterglass" type, Simalco, of formula Na 2 O 2 SiO 2 and with a SiO 2 / Na 2 O molar ratio of about 2, - sodium aluminate, Sigma-Alrich, - running water, - sodium hydroxide. Sigma Aldrich, purity> 85%.
    Unless otherwise indicated, all these raw materials have been used as received from the manufacturers.
    Example 1 Preparation of a Fire Resistant Device According to the Invention
    An aluminosilcate geopolymer composition was prepared in the following manner: An alkali silicate solution was prepared by dissolving mixing 900 g of sodium aluminate in 9 kg of H 2 O. To this solution are added 9 kg of an aqueous solution of sodium silicate.
    Said aluminosilcate geopolymer composition comprised about 28.6% by weight solids based on the total weight of said composition.
    The geopolymer composition was mixed with 5 kg of liquid EVA to form a composite composition. 300 g of talc was then added to the resulting composition.
    The composite composition was hot-extruded around an elongated 20 mm copper electrically conductive member with the aid of an extruder sold under the trade name FAIREX. The temperature within the extruder ranged from about 60 ° C to about 135 ° C.
    The composite layer was about 2.5 mm thick.
    权利要求:
    Claims (19)
    [1" id="c-fr-0001]
    A composite composition comprising at least one liquid organic polymer or oligomer at room temperature and at least one geopolymer-aluminosilicate composition in the form of a gel comprising an alkali aluminate, an alkali silicate, water and optionally a base alkaline.
    [2" id="c-fr-0002]
    2. Composition according to claim 1, characterized in that the alkali silicate is selected from sodium silicates, potassium silicates and a mixture thereof.
    [3" id="c-fr-0003]
    3. Composition according to claim 1 or 2, characterized in that the alkali aluminate is a sodium aluminate.
    [4" id="c-fr-0004]
    4. Composition according to any one of the preceding claims, characterized in that the alkaline base is chosen from KOH, NaOH and mixtures thereof.
    [5" id="c-fr-0005]
    5. Composition according to any one of the preceding claims, characterized in that the aluminosilicate geopolymer composition comprises from 0.5 to 20% by weight of an alkaline aluminate, from 15 to 50% by weight of an alkali silicate, from 0 to 3% by weight of an alkaline base and from 50 to 90% by weight of water.
    [6" id="c-fr-0006]
    6. Composition according to any one of the preceding claims, characterized in that the aluminosilicate geopolymer composition comprises from 15 to 50% by weight of solids, relative to the total weight of said composition.
    [7" id="c-fr-0007]
    7. Composition according to any one of the preceding claims, characterized in that the oligomer or the liquid organic polymer at room temperature is selected from polyorganosiloxanes, polyethylenes, copolymers of ethylene and vinyl acetate, polyethylenes. glycols, epoxy resins and acrylic resins.
    [8" id="c-fr-0008]
    8. Composition according to any one of the preceding claims, characterized in that the organic oligomer or liquid polymer at room temperature is a silicone oil with a viscosity ranging from 5000 to 50000 cP at 25®C.
    [9" id="c-fr-0009]
    9. Composition according to any one of the preceding claims, characterized in that the polymer or organic oligomer liquid at room temperature is from 15 to 50% by weight, relative to the total mass of the composite composition.
    [10" id="c-fr-0010]
    10. Composition according to any one of the preceding claims, characterized in that it further comprises a crosslinking agent.
    [11" id="c-fr-0011]
    11. Composition according to claim 10, characterized in that the crosslinking agent represents from 0.2 to 5% by weight, relative to the total mass of the composite composition.
    [12" id="c-fr-0012]
    12. Process for the preparation of a composite composition as defined in any one of the preceding claims, characterized in that it comprises at least the following steps: i) the preparation of an aluminosilicate geopolymer composition comprising an alkaline aluminate, an alkali silicate, water and optionally an alkaline base, said aluminosilicate geopolymer composition being as defined in any one of claims 1 to 6, and ii) adding a liquid organic polymer or oligomer at room temperature as defined in any one of claims 7 to 9, to the aluminosilicate geopolymer composition of step i), and iii) optionally adding a crosslinking agent as defined to any one of claims 10 or 11 to the mixture of step ii).
    [13" id="c-fr-0013]
    13. The method of claim 12, characterized in that step i) comprises the following substeps: ia) the preparation of an aqueous solution of alkali silicate of molar ratio SiO 2 / M'20 ranging from 1.6 to 35, M 'being an alkali metal, the mass concentration of the alkali silicate in water ranging from 30 to 60%, and ib) the preparation of an aqueous solution of sodium aluminate, the mass concentration of the aluminate of sodium in water ranging from 1.2 to 20%, and ic) the mixture of aqueous solutions from steps ia) and ib).
    [14" id="c-fr-0014]
    Device comprising an energy and / or telecommunication cable and / or an accessory for an energy and / or telecommunication cable, characterized in that said cable and / or cable accessory comprises at least one composite layer obtained from a composite composition as defined in any one of claims 1 to 11.
    [15" id="c-fr-0015]
    15. Device according to claim 14, characterized in that the composite layer has a thickness ranging from 0.5 to 4 mm.
    [16" id="c-fr-0016]
    16. Device according to claim 14 or 15, characterized in that the composite layer is an inner layer of said cable or said cable accessory.
    [17" id="c-fr-0017]
    17. A method of manufacturing a device comprising a power cable and / or telecommunications and / or a cable accessory as defined in any one of claims 14 to 16, characterized in that it comprises at least the following steps: 1) the preparation of a composite composition according to the process as defined in claim 12 or 13; and 2) applying the composite composition of step 1): either around one or more elongated conductive elements and / or around an inner layer of an energy and / or telecommunication cable when the device is a cable, - or around at least one of the inner layers of a junction or termination when the device is a cable accessory, to form a composite layer as defined in any of claims 14 to 16.
    [18" id="c-fr-0018]
    18. The method of claim 17, characterized in that step 2) is carried out by hot extrusion or at room temperature of said composite composition.
    [19" id="c-fr-0019]
    19. The method of claim 17 or 18, characterized in that it further comprises a step 3) of crosslinking the polymer or the organic oligomer liquid at room temperature, when the composite composition of step 1) comprises a crosslinking agent.
    类似技术:
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    同族专利:
    公开号 | 公开日
    WO2017174941A1|2017-10-12|
    US10919806B2|2021-02-16|
    KR20180127492A|2018-11-28|
    CN108883987A|2018-11-23|
    EP3440032A1|2019-02-13|
    FR3049948B1|2019-07-19|
    US20190112230A1|2019-04-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN101544484A|2009-04-20|2009-09-30|西安建筑科技大学|Method for preparing inorganic aluminosilicate polymer and inorganic macromolecule composite gelled material|
    EP2868637A1|2013-10-31|2015-05-06|Construction Research & Technology GmbH|Geopolymer foam formulation|
    CN105400131A|2015-12-12|2016-03-16|唐思钊|A composite material used for a special cable, a preparing method thereof and the special cable|FR3072496A1|2017-10-17|2019-04-19|Nexans|FIRE RESISTANT CABLE|
    EP3640956A1|2018-10-18|2020-04-22|Nexans|Filling layer for a low-voltage cable with improved fire protection|
    WO2021126759A1|2019-12-20|2021-06-24|Lubrizol Advanced Materials, Inc.|Hybrid coating system|JPH0680461A|1991-08-03|1994-03-22|Yasuo Yokoi|Heat-resistant heat-insulating composition and heat-resistant heat-insulating material|
    NL1033269C2|2007-01-23|2008-07-24|Ertecee B V|Aqueous gel-forming composition, e.g. as fire retardant coating to substrate, comprises aluminosilicate and organic liquid, where aluminosilicate comprises alkali metal aluminate and alkali metal silicate each having specified molar ratio|
    FR3001574B1|2013-01-28|2017-01-27|Nexans|ENERGY AND / OR TELECOMMUNICATION CABLE COMPRISING AT LEAST ONE ELECTRICALLY INSULATING LAYER|
    CN104327614B|2014-10-20|2016-09-28|芜湖县双宝建材有限公司|A kind of high-performance water-based expanding fire-proof paint|
    CN107001765A|2014-11-12|2017-08-01|Abb瑞士股份有限公司|Electrically insulating material and the method for preparing insulating material component|FR3098636A1|2019-07-12|2021-01-15|Nexans|Cable comprising a fire resistant layer|
    FR3103958A1|2019-11-29|2021-06-04|Nexans|cable comprising a fire resistant layer|
    FR3108913A1|2020-04-06|2021-10-08|Nexans|Fire resistant and / or retardant composition|
    CN112002476A|2020-08-28|2020-11-27|安徽瑞昊缆业有限公司|Stretch-proofing wear-resisting cable|
    法律状态:
    2017-04-19| PLFP| Fee payment|Year of fee payment: 2 |
    2017-10-13| PLSC| Search report ready|Effective date: 20171013 |
    2018-04-20| PLFP| Fee payment|Year of fee payment: 3 |
    2019-04-18| PLFP| Fee payment|Year of fee payment: 4 |
    2020-04-20| PLFP| Fee payment|Year of fee payment: 5 |
    2021-04-23| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1653074|2016-04-07|
    FR1653074A|FR3049948B1|2016-04-07|2016-04-07|FIRE RESISTANT COMPOSITE LAYER FOR CABLE OR ACCESSORY FOR CABLE|FR1653074A| FR3049948B1|2016-04-07|2016-04-07|FIRE RESISTANT COMPOSITE LAYER FOR CABLE OR ACCESSORY FOR CABLE|
    KR1020187032121A| KR20180127492A|2016-04-07|2017-04-06|A device comprising a cable or cable part comprising a refractory composite layer|
    US16/090,735| US10919806B2|2016-04-07|2017-04-06|Device comprising a cable or cable accessory containing a fire-resistant composite layer|
    CN201780022024.9A| CN108883987A|2016-04-07|2017-04-06|Equipment including cable or cable accessory with fire resisting composite layer|
    EP17719664.9A| EP3440032A1|2016-04-07|2017-04-06|Device comprising a cable or cable accessory containing a fire-resistant composite layer|
    PCT/FR2017/050821| WO2017174941A1|2016-04-07|2017-04-06|Device comprising a cable or cable accessory containing a fire-resistant composite layer|
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