Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/02—Inorganic materials
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
  • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
  • F16L58/04—Coatings characterised by the materials used
  • F16L58/10—Coatings characterised by the materials used by rubber or plastics
  • F16L58/1054—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe
  • F16L58/109—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe the coating being an extruded layer
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L9/00—Rigid pipes
  • F16L9/12—Rigid pipes of plastics with or without reinforcement
  • F16L9/133—Rigid pipes of plastics with or without reinforcement the walls consisting of two layers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B7/00—Insulated conductors or cables characterised by their form
  • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
  • H01B7/29—Protection against damage caused by extremes of temperature or by flame
  • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/12—Shape memory
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

• the invention relates to thermoplastic flame retardant compositions with high mechanical strength, more precisely with high mechanical strength whatever the relative humidity conditions, containing at least one particular combination of two coupling agents.
• the present invention also relates to the use of this composition as a coating layer (outer layer) in a cable, pipe or the like and as a constituent material (inner layer) of a protective sheath.
• compositions are useful in cabling for insulating and protecting electrical cables, optical fibers and for the manufacture of electrical parts such as electrical connectors, as well as in electrical engineering for molding objects such as housings.
• electrical parts such as electrical connectors
• electrical engineering for molding objects such as housings.
• the materials In applications such as covering electric cables, electrical and electrotechnical parts, automotive, in addition to their electrical insulating nature, the materials must above all possess a high level of fire resistance (fireproofing). Electrical installations can indeed cause short circuits and ignite, they can also be put in contact with a flame and thus ignite and spread the fire along the cable trays.
• Thermoplastic polymers such as polyethylenes, polyamides or their mixtures are good electrical insulators and are easy to implement. They are used to make enclosures and electrical connectors and also cable covers.
• the flame retardant qualities of a composition are conventionally measured by the Oxygen Limit Index or LOI test for "Limiting Oxygen Index".
• the measurement of the oxygen limit index makes it possible to determine the minimum oxygen concentration in an oxygen / nitrogen mixture which makes it possible to maintain the combustion of a plastic in a vertical position, with ignition at the top of the sample.
• the flammability of the materials is thus quantitatively characterized.
• LOI test results of between 21% and 30% the composition burns but extinguishes itself after a longer or shorter period of time.
• the result of the LOI test must not be less than 35% o, which corresponds to a spontaneous or immediate extinction of the combustion of the composition.
• halogenated derivatives has the great disadvantage of driving, during combustion, toxic and corrosive gases.
• the manufacturers and processors then moved towards the development of compositions containing oxides, hydroxides or inorganic salts of metals such as hydrates of aluminum and magnesia. .
• the addition of these materials confer fire-retardant properties but degrade the mechanical properties of the thermoplastic composition including them.
• thermoplastic compositions for thermoplastic compositions, the improvement of the fire resistance properties goes against the mechanical properties, there are currently no thermoplastic materials or compositions on the market with high performance characteristics for all of these properties combined (mechanical and fireproof properties) and especially that retain these properties regardless of the ambient humidity level and the duration of exposure to these conditions.
• thermoplastic materials or compositions on the market with high performance characteristics for all of these properties combined (mechanical and fireproof properties) and especially that retain these properties regardless of the ambient humidity level and the duration of exposure to these conditions.
• Document KR 20100113750 describes a flame-retarded thermoplastic composition consisting of 100 parts by weight of ethylene vinyl acetate, 1 to 5 parts by weight of an ethylene / acrylate / maleic anhydride terpolymer, 10 to 15 parts by weight of a low ethylene density grafted linear maleic anhydride copolymer, 90 to 150 parts by weight of magnesium hydroxide, 3 to 10 parts by weight of high molecular weight silicone compounds, and 1 to 5 parts by weight of a masterbatch including a resin and red phosphorus.
• This complex and difficult to implement composition seems to display good mechanical properties and allow to lower the density of smoke during a fire.
• compositions containing maleic anhydride grafted polyethylenes which have good mechanical properties and satisfactory results in the LOI test are also known, but a drastic drop in the mechanical properties under wet conditions or during aging.
• compositions containing terpolymers of ethylene, butyl acrylate and maleic anhydride which have a good fluidity and good resistance to changes in relative humidity and aging but lower mechanical properties.
• a composition associating, in particular proportions, on the one hand an ethylene-acrylate-maleic anhydride terpolymer and on the other hand a maleic anhydride grafted polyethylene exhibits an extremely synergistic effect. interesting to maintain the mechanical performance regardless of the surrounding humidity conditions (ie in high / high humidity conditions), while preserving the other properties of the composition.
• the present invention thus intends to remedy the catastrophic decline in the mechanical properties of the materials of the prior art, placed in a highly humid environment, by proposing a thermoplastic composition meeting all the specific requirements for electric cables, optical fibers and more generally insulating parts in the electrical and electrotechnical fields.
• thermoplastic flame retardant composition comprising a maleic anhydride grafted polyethylene having a melting point greater than 115 ° C. (Celsius), characterized in that this coupling agent further comprises an ethylene terpolymer. -acrylate-maleic anhydride, the proportion of said terpolymer representing from 33% to 99.5% by weight of the mixture forming the coupling agent.
• the coupling agent according to the invention consists (only) in these two components, namely the maleic anhydride grafted polyethylene and the ethylene-acrylate-maleic anhydride terpolymer.
• the aforesaid terpolymer is a terpolymer of ethylene, butyl acrylate and maleic anhydride.
• said coupling agent is present in the composition between
• the polar-functional ethylenic monomer comprises from 3 to 20 carbon atoms, preferably from 4 to 8 atoms.
• the polar-bearing ethylenic monomer is chosen from saturated carboxylic acid vinyl esters, unsaturated carboxylic acids or unsaturated carboxylic acid (meth) acrylic esters.
• the composition comprises up to 10% by weight of additives, namely antioxidants, UV stabilizers, lubricants, antistatic agents, mineral fillers, coloring pigments, anti-drip agents (products with silicone base (PDMS) or fluorinated products such as PTFE) and / or zeolites.
• additives namely antioxidants, UV stabilizers, lubricants, antistatic agents, mineral fillers, coloring pigments, anti-drip agents (products with silicone base (PDMS) or fluorinated products such as PTFE) and / or zeolites.
• the present invention relates more particularly to a cable or pipe having at least two layers of which at least one layer is formed by the aforesaid thermoplastic composition as stated above.
• FIG. 1 shows the results table, presented below, concerning the elongation test at rupture, in an environment at 50% relative humidity, for all the test pieces;
• - Figure 2 projects the table of results, presented below, concerning the maximum variation of elongation at break (in%) between a dry environment (relative humidity equal to or close to 0%), an environment at 50% d relative humidity and a saturated humidity environment (relative humidity equal to or close to 100%);
• polyethylene is understood to mean homo- or copolymers.
• alpha-olefins advantageously those having from 3 to 30 carbon atoms. Examples have been cited above. These alpha-olefins can be used alone or in a mixture of two or more.
• the polyethylene may comprise several of the foregoing comonomers.
• the polyethylene which may be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density may be between 0.910 and 0.96 g / cm.
• the MFI Melt Flow Index ", viscosity number measured at 190 ° C. under a load of 2.16 kg) is advantageously between 1 and 1000 g / 10 min.
• HDPE high density polyethylene
• MDPE medium density polyethylene
• LLDPE linear low density polyethylene
• the grafting of maleic anhydride onto polyethylene is an operation known per se by those skilled in the art.
• the degree of grafting of maleic anhydride that is to say the number of units of maleic anhydride monomer in the graft polymer, is variable according to the polyethylene considered and may vary from 0.1% to 4% by weight, preferably from 0.4% to 2% by weight of the graft polymer.
• the maleic anhydride grafted polyethylene has a "melting point greater than 115 ° C (Celsius)" is directly related to the choice of the polyethylene forming the long chain of this polymer. As a result, only certain polyethylenes can be chosen for the present invention.
• the ethylene-acrylate-maleic anhydride terpolymer is advantageously used, but an ethylene-vinyl acetate-maleic anhydride terpolymer may also be used.
• graft and terpolymers polyethylenes are sold by the Applicant under the trademarks ® and OREVAC LOTADER® ®.
• the coupling agent may be prepared by mixing the various constituents by the conventional means for using the thermoplastics, for example extrusion or kneading. It is possible to use internal mixers with blades or rotors, an external mixer, a co-kneader, single-screw extruders, co-rotating twin-screw or counter-rotating twin-screw extruders.
• the coupling agent is produced at a temperature greater than or equal to the melting temperature of the constituents.
• the coupling agent can be produced for example at a temperature in the range of from 100 to 260 ° C.
• ethylenic monomer is understood to mean a monomer comprising an unsaturation capable of reacting with ethylene in a radical process.
• polar function is meant a function having a dipole moment, such as amine, alcohol, urethane, acid or ester functions.
• the polar function is an acid function or an ester function.
• the polar-functional ethylenic monomer preferably comprises from 3 to 20 carbon atoms, preferentially from 4 to 8 carbon atoms.
• copolymers examples include copolymers of ethylene with a carboxylic acid vinyl ester, copolymers of ethylene with an unsaturated carboxylic acid or copolymers of ethylene and a acrylate and or alkyl methacrylates, grouped together in the present application under the term (meth) acrylate.
• the ethylenic monomer may be chosen from vinyl acetate and methyl, ethyl or butyl (meth) acrylates.
• the quantity by mass of ethylenic monomer relative to the total weight of the copolymer may be in the range of from 1 to 70%, advantageously from 10 to 60% and preferably from 20 to 45%.
• the amounts of the various monomers present in the copolymer can be measured by infrared spectroscopy using the standard IS08985 (1998).
• the softening temperature of the copolymer can be measured by ASTM Standard E 28-99 (2004).
• radical polymerization processes usually operating at pressures between 200 and 2500 bar, may be used. These processes are implemented industrially using two main types of reactors: an autoclave type reactor or a tubular type reactor. These polymerization processes known to those skilled in the art and can be used for example the methods described in documents FR2498609, FR2569411 and FR2569412. Those skilled in the art know in what proportions to use each of the monomers to obtain the copolymer (a) used in the invention.
• copolymers are marketed by the applicant under the EVATANE ® and LOTRYL ® brands.
• flameproofing agent in the context of the examples chosen to illustrate the invention, that is to say the carrying out of the tests of the compositions according to the invention with regard to those according to the prior art, it has has been chosen two conventionally used inorganic flame retardants (flame retardants), namely the trihydrate of aluminum (ATH) and, optionally as a replacement or supplement, magnesium hydroxide (MDH).
• flame retardants namely the trihydrate of aluminum (ATH) and, optionally as a replacement or supplement, magnesium hydroxide (MDH).
• Inorganic flame retardants are thus preferred in the composition according to the invention.
• the flame retardant meets the definition of compounds capable of forming at the time of combustion acids such as H3PO4 (orthophosphoric acid), (HP03) n (metaphosphoric acid) and H4P2O7 (pyrophosphoric acid).
• H3PO4 orthophosphoric acid
• HP03 metalphosphoric acid
• H4P2O7 pyrophosphoric acid
• ammonium phosphates, phosphinates, pyrophosphates and polyphosphates melamine phosphates, melamine phosphite, piperazine phosphite and diphosphite, guanazole phosphate, melamine pyrophosphate and piperazine pyrophosphate.
• ammonium polyphosphates which are single chain polymers of general formula (NH 4 ) n + 2 P n O 3 n + 1, in which n represents an integer greater than or equal to 2.
• the polyphosphate of ammonium can be encapsulated in a melamine-based resin. It would not depart from the scope of the invention using a mixture of the above flame retardants.
• the flame retardant can be functionalized, for example it can carry silane functions.
• the flame retardant of the composition according to the invention may also consist of a flame retardant containing nitrogen. It will then be chosen from pure melanin, melamine derivatives such as salts of organic or inorganic acids such as boric acid, cyanuric acid, phosphoric acid or pyro- / polyphosphoric acid, homologues of melamine like melam or melem.
• the flame retardant of the composition may consist of compounds containing boron (borates, mixtures of boric acids and borax, zinc borate, etc.), antimony trioxide, zinc compounds (zinc sulphides, hydroxystannate of zinc ...), intumescent mixtures (for example a mixture of ammonium polyphosphates, pentaerythritol, melanin derivatives), expandable graphite or nanocomposites (for example aluminum silicate clay such as montmorillonite).
• composition according to the invention optionally comprises red phosphorus, conventionally used in a mixture in polyolefins.
• the flame retardant of the composition according to the invention is one of the abovementioned products or a combination of these products.
• polyethylene is understood to mean all the polyethylenes that can be envisaged in the abovementioned definition of "polyethylene” in the context of maleic anhydride grafted polyethylene.
• compositions according to the invention can be prepared according to two different processes.
• the coupling agent in a first step, the coupling agent is first prepared by simply mixing the two compounds. Then, in a second step, the coupling agent previously prepared with the flame retardant additives, for example aluminum trihydrate and / or magnesium dihydroxide, the copolymer of ethylene and a polar functional ethylenic monomer as well as polyethylene.
• the aforesaid copolymer may be absent from the composition, as may polyethylene, but it is not possible not to have at least one of these two components in a composition according to the invention; the coupling agent having the particular function of bonding said copolymer and / or polyethylene with the flame retardant fillers.
• compositions according to the invention in a one-step process in which the ingredients are mixed to give a homogeneous composition and to carry out possible chemical reactions between components.
• These compositions can be prepared by mixing the various constituents by the conventional means of implementing the highly filled thermoplastics, for example extrusion or kneading. It is possible to use an internal mixer, a co-kneader or a co-rotating twin-screw extruder.
• the compositions are made at a temperature greater than or equal to the melting temperature of the constituents and less than the decomposition start temperature of the flame retardant agent. Fillers, in particular mineral fillers, can be added to improve the thermomechanical behavior of the composition.
• silica, alumina, talc or calcium carbonates or carbon nanotubes are exemplified.
• modified or unmodified clays are used which are mixed with the nano-metric order; this is to meet the requirements of certain flammability standards for plastics, such as the UL94-V0 (self-extinguishing in 10 seconds maximum, without inflamed drop).
• Plasticizers may be added to facilitate the implementation and improve the productivity of the method of making the composition and structures.
• Examples are aromatic paraffmic or naphthalenic mineral oils. Mention may also be made, as plasticizer, of phthalates, azelates, adipates and ticresyl phosphate.
• anti-drop agents such as silicone-based products (PDMS) or fluorinated products such as PTFE were added to the compositions.
• the formulations described below are prepared by extrusion using a BOSS PR46 co-kneader with a diameter of 46 millimeters, a length of 15 times its diameter and equipped with a single-screw diameter of 70 millimeters.
• the screw and the sheaths of the co-kneader are respectively heated at 100 ° C. and 110 ° C. while the rework mono-screw is heated to 150 ° C.
• the extrusion rate is 15 kg / h (kilograms per hour) for a speed of rotation of the co-kneader of 285 rpm (revolutions per minute).
• the different constituents (with the exception of the fire-retardant filler) are introduced into the first hopper (hopper 1), the fire-retardant filler is introduced in equal parts in the hoppers 1 and 2.
• the coupling agent is here defined as the core of the invention and is more particularly intended for use in an electrical cable coating composition.
• the coupling agent according to the invention find other applications where their characters of fire resistance and good mechanical properties are required.
• These coupling agents and compositions have the advantage of being convertible into industrial articles (sheets, plates, profiles, hollow bodies, pipes), having improved fire resistance, by conventional polyolefin processing techniques (extrusion, injection, rotational molding).
• Lotader® 3210 Terpolymer of ethylene, butyl acrylate (6% by weight) and maleic anhydride (3% by weight) produced by ARKEMA having an MFI (190 ° C, 2.16 kg measured according to ISO 1133) of 5 g / 10mn.
• ATH Aluminum trihydrate having a specific surface area of 4m 2 / g.
• Orevac® 18340 linear low density polyethylene grafted maleic anhydride, produced by ARKEMA having a MFI (190 ° C, 2.16kg measured according to ISO 1133) of 3 g / 10mn.
• Evatane® 28-03 Copolymer of ethylene and vinyl acetate (28% by weight) produced after ARKEMA having an MFI (190 ° C., 2.16 kg measured according to ISO 1133) of 3 g / 10 min.
• Polyethylene Linear low density polyethylene having an MFI (190 ° C, 2.16kg measured according to ISO 1133) of 1g / 10mn.
• Antioxidant Antioxidant for example phenolic type.
• compositions below contain exactly the same components in weight percentage relative to the total composition (Examples 1 to 6), namely 22.75% of Evatane 28-03 + 9% polyethylene + 63% ATH + 0.25 % Antioxidant + 5% coupling agent.
• the mass percentage or percentage of the coupling agent (whatever its intrinsic formulation) in the composition is identical so as not to distort the test results.
• the coupling agent according to the invention has presented satisfactory results, with regard to its primary function of improving the mixing of the components but also with regard to the advantageous properties that it confers on the composition, when present between 0, 1% and 10% by weight of the composition, and preferably between 2% and 7.5%.
• Example 1 The composition entitled “DM1” is a formulation within the scope of the present invention. It comprises, as a percentage by mass only of the coupling agent, 50% of Lotader 3210 and 50% of Orevac 18340.
• Example 2 The composition entitled “DM2” is a formulation within the scope of the present invention. It comprises, as a percentage by mass only of the coupling agent, 44% of Lotader 3210 and 56% of Orevac 18340.
• Example 3 The composition entitled “DM3” is a formulation within the scope of the present invention. It comprises, as a percentage by mass only of the coupling agent, 56% of Lotader 3210 and 44% of Orevac 18340.
• Example 4 The composition entitled "DM4" is a formulation within the scope of the present invention. It comprises, as a percentage by mass only of the coupling agent, 35% of Lotader 3210 and 65% of Orevac 18340.
• Example 5 The composition entitled "DM5" is a formulation within the scope of the present invention. It comprises, as a percentage by mass only of the coupling agent, 65% of Lotader 3210 and 35% of Orevac 18340.
• Example 6 The composition entitled “DM6” is a formulation within the scope of the present invention. It comprises, as a percentage by mass only of the coupling agent, 94% Lotader 3210 and 6% Orevac 18340.
• Example 7 The composition entitled “DM7” is a formulation comprising, as a percentage by weight only of the coupling agent, 30% of Lotader 3210 and 70% of Orevac 18340.
• Example 8 The composition entitled “DM8” is a formulation, in weight percent only of the coupling agent, comprising 100% Lotader 3210.
• Example 9 The composition entitled “DM9” is a formulation, in weight percent only of the coupling agent, comprising 100% Orevac 18340.
• the granules or components are shaped using a ThermoHaake Rheocord System 40 laboratory counter-rotating double screw extruder equipped with a flat die; the extruder being heated to 150 ° C to obtain strips from which will be cut the test pieces necessary to characterize or test the materials.
• the second test looks at the evolution of the elongation and the stress at break by performing a test, still according to ISO R527: 93-lBA, in the initial state then after having been immersed for 7 days in water at 70 ° C.
• melt index measured according to ASTM D1238, as well as the oxygen limit index (LOI), measured according to ASTM D2863 or BS ISO 4589-2.
• the elongation at break test at 50% humidity is absolutely not satisfactory since its value is much lower than 175% which constitutes a threshold of acceptability for this test (visible in bold type in Figure 1).

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• 2012
  • 2012-01-17 FR FR1250434A patent/FR2985731B1/fr active Active
• 2013
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  • 2013-01-14 EP EP13705208.0A patent/EP2804906B1/fr active Active
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