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WO2013030795A1 - Procédé pour la production d'une composition ignifuge - Google Patents

Procédé pour la production d'une composition ignifuge Download PDF

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Publication number
WO2013030795A1
WO2013030795A1 PCT/IB2012/054490 IB2012054490W WO2013030795A1 WO 2013030795 A1 WO2013030795 A1 WO 2013030795A1 IB 2012054490 W IB2012054490 W IB 2012054490W WO 2013030795 A1 WO2013030795 A1 WO 2013030795A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
weight
copolymers
process according
olefin
Prior art date
Application number
PCT/IB2012/054490
Other languages
English (en)
Inventor
Franco Peruzzotti
Original Assignee
R&D Innovaction S.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by R&D Innovaction S.R.L. filed Critical R&D Innovaction S.R.L.
Publication of WO2013030795A1 publication Critical patent/WO2013030795A1/fr

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    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/484—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with two shafts provided with screws, e.g. one screw being shorter than the other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/41—Intermeshing counter-rotating screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/793—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling upstream of the plasticising zone, e.g. heating in the hopper
    • B29C48/797—Cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • B29C48/84—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders by heating or cooling the feeding screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/405—Intermeshing co-rotating screws
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene

Definitions

  • the present invention relates to a process for the production of flame retardant compositions, particularly suited to the production of self- extinguishing cables.
  • Self-extinguishing cables can be produced by coating the cable itself with a sheath having flame- retardant properties, consisting of a polymeric material to which a product suitable to achieve flame-retardant properties (i.e. flame retardants) has been added, that has the capability of preventing the spread of the flame along the cable in case of fire.
  • a sheath having flame- retardant properties consisting of a polymeric material to which a product suitable to achieve flame-retardant properties (i.e. flame retardants) has been added, that has the capability of preventing the spread of the flame along the cable in case of fire.
  • flame retardant material is also used as a filler of the spaces present among said conductive elements.
  • a composition based on polyolefins for example polyethylene or ethylene/vinylacetate copolymers added with an organic halide combined with antimony trioxide, which work as flame retardants.
  • halogenated flame retardant additives has many drawbacks, for example during the production of the composition and/or of the cable they can partially decompose, forming halogenated gases that may be toxic or otherwise harmful to production workers and can corrode the metal components of the production plant.
  • their combustion when exposed to a flame action, their combustion generates large amounts of smoke also containing toxic halogenated gases.
  • PVC polyvinylchloride
  • flame retardant compositions free of halogenated components have been developed, using as flame retardant mineral fillers, particularly hydrated oxides or aluminum and/or magnesium hydroxides, for example, hydrated alumina or magnesium hydroxide, which, when exposed to high temperatures, decompose through endothermic reaction and release large quantities of water, so as to stop the flame propagation .
  • flame retardant mineral fillers particularly hydrated oxides or aluminum and/or magnesium hydroxides, for example, hydrated alumina or magnesium hydroxide, which, when exposed to high temperatures, decompose through endothermic reaction and release large quantities of water, so as to stop the flame propagation .
  • Patent US-5.707.732 refers to an electrical cable or for telecommunications coated with a flame- retardant composition comprising 100 parts by weight of a polymer mixture and 5 to 250 parts by weight of flame retardant filler.
  • This latter can be magnesium hydroxide or aluminum trihydrate
  • the polymer mixture consists of: (i) a polyethylene synthetized by using a metallocene single-site catalyst and having a M w /M n ratio not greater than 3; (ii) a polyethylene synthetized by using a transition metal catalyst other than a metallocene single-site catalyst and having a M w /M n ratio greater than 4, and optionally (iii) a copolymer of ethylene with an unsaturated ester or a very low density polyethylene having a density of not greater than 0.915 g/cm 3 wherein the polymers (i) or (ii) are modified with an unsaturated aliphatic diacid anhydride through grafting or copolymer
  • Patent application WO 99/05688 describes self- extinguishing cables and related flame retardant compositions, wherein these compositions comprise:
  • a copolymer of ethylene with at least one alpha- olefin, and optionally with a diene characterized by a composition distribution index (CDI) greater than 45%, said index being defined as the percentage by weight of the copolymer molecules having a content of alpha-olefin within 50% with respect to the average total mole content of alpha-olefin;
  • CDI composition distribution index
  • the crystalline propylene homopolymer or copolymer this generally has a melting enthalpy greater than 75 J/g, preferably greater than 85 J/g, and ensures the final composition sufficient resistance to thermopressure , an essential characteristic for the realization of a self- extinguishing cable to meet the market specifications.
  • the copolymer of. ethylene with at least one alpha-olefin (b) this is obtained by ethylene copolymerization with at least one alpha- olefin in the presence of a "single-site" catalyst, such as a metallocene catalyst, and it is characterized by a narrow distribution of molecular weights, in particular by a molecular weight distribution index (MWD) lower than 5.
  • MWD molecular weight distribution index
  • Patent application WO 00/19452 describes self- extinguishing cables coated with a flame-retardant composition which includes: (a) an ethylene homopolymer or copolymer having a density of from 0.905 to 0.970 g/cm 3 , selected from: ethylene homopolymers , copolymers of ethylene with an alpha- olefin, copolymers of ethylene with an ethylenically unsaturated ester, or mixtures thereof; (b) a copolymer of ethylene with an alpha-olefin, and optionally with a diene, said copolymer (b) having a density ranging from 0.860 to 0.904 g/cm 3 , and being characterized by a composition distribution index (CDI) higher than 45%; (c) natural magnesium hydroxide in a quantity sufficient to impart flame retardant properties; wherein at least one of the polymeric components (a) and (b) contains hydrolysable organic silane groups grafted
  • the Applicant has realized that, for the production on an industrial scale of HFFR compositions as those described above, it is generally necessary to use devices having a high mixing efficiency, such as co-rotating twin-screw extruders, characterized by high rotation speed of the screws (for example, for a cylinder with a diameter of about 90 mm, the rotation speed can also be higher than 1000 rpm) and by high length, both to ensure homogeneous mixing of the filler in the polymer base and also to carry out grafting reactions during the extrusion (the so-called "reactive extrusion"), in particular to modify the polymers through in-situ grafting of coupling agents such as silanes or maleic anhydride.
  • a high mixing efficiency such as co-rotating twin-screw extruders, characterized by high rotation speed of the screws (for example, for a cylinder with a diameter of about 90 mm, the rotation speed can also be higher than 1000 rpm) and by high length, both to ensure homogeneous
  • they are usually provided with different feeding zones, one or two degassing zones, and high power engines (for example: for a cylinder of about 90 mm diameter, powers also over 1000 kW) .
  • this machinery allows to obtain a good mixing both of dispersive and distributive type.
  • distributed mixing means the capability of the mixer to distribute homogeneously the filler particles evenly within the polymer matrix, thus avoiding the presence of filler aggregates in the finished product.
  • dispenser mixing means the capability of the mixer to disgregate up the particles having a size greater than a prefixed value.
  • mixing is carried out in the interpenetration area of the screw threads, while the flow channel of the material is longitudinally open, so reflux phenomena (back-flow) may occur, with consequent difficulties in temperature control and homogeneous flowing of the material.
  • Another kind of continuous mixing machines is based on single screw co-kneader extruders where, simultaneously with the rotational movement, the screw is making an alternative movement in the axial direction.
  • On the wall of the cylinder a series of pins are fitted: the interaction between these and the screw movement ensure a good level both of dispersive and distributive mixing, even for limited cylinder lengths (L/D between 8 and 30) and for low screw speeds (for example: for a cylinder having diameter of about 100 mm, the screw speed can reach 500 rpm) .
  • L/D between 8 and 30
  • low screw speeds for example: for a cylinder having diameter of about 100 mm, the screw speed can reach 500 rpm
  • a gentle mixing is also guaranteed, without application of high powers (for example: for a cylinder of about 100 mm diameter, generally the power does not exceed 300 kW) and a high control of the mixing temperature.
  • these machines are suitable to the processing of materials of very different nature (such as plastics or rubbers) and also of heat-sensitive materials (for example, the mixing of rubber in the presence of thermo-sensitive crosslinking agents such as peroxides or PVC, where often machines with a L/D ratio lower than 10 are used) .
  • less performing machines are widely used, such as counterrotating twin-screw extruders, characterized by relatively low screw rotation speed (for example: for a cylinder of 90 mm diameter, the rotation speed is generally lower than 100 rpm) and by limited length, with a L/D value not higher than 30, typically of 20-25 or, for upgraded machines, to L/D values up to 40. They are also equipped with a single feeder positioned in the initial part of the extruder and a single degassing zone; as these machines have simply to gel the composition, they are equipped with low power engines (for example: for a cylinder having a diameter equal to about 90 mm, the power is generally lower than 150 kW) .
  • the counter- rotating twin screw extruders have the advantage of allowing a good temeprature control and therefore the material to be extruded does not overheat, the energy transmitted by the engine being efficiently utilized for the transport of the material itself.
  • the flow channel is longitudinally closed, since at each step the thread of a screw is closed by the thread of the other screw: this prevent the material from reflowing (back flow) . Therefore, the counter-rotating twin-screw extruders are particularly used for the production of PVC-based compositions or other thermo- sensitive materials in which a high quantity of mixing energy is not required; all the ingredients are typically pre-mixed in the form of powders thus ensuring a substantially homogeneous feeding composition.
  • HFFR compositions low cost halogen- free flame retardant compositions
  • HFFR compositions flame-retardant inorganic filler
  • PVC-based compositions a flame-retardant inorganic filler
  • mixing equipment such as co- rotating twin screw extruders or single co-kneader extruders with high L/D, having characteristics as indicated above, as well as control systems for the continuous dosing of the required raw materials.
  • a polymeric matrix consisting of at least 10% by weight, with respect to the total weight of the polymeric matrix, of at least one polyolefin having a melting temperature (T f ) not greater than 100°C and a melting enthalpy ( ⁇ £ ) not greater than 110 J/g.
  • the present invention therefore relates to a process for the production of a flame-retardant composition including a polymeric matrix and at least one inorganic filler with flame retardant properties, said process comprising :
  • said polymeric matrix comprising at least 10% by weight,- with respect to the total weight of the polymeric matrix, of at least one polyolefin having a melting temperature (T f ) not higher than 100°C and a melting enthalpy ( ⁇ £ ) not higher than 110 J/g;
  • said extruder being selected from: counterrotating twin-screw extruders having a L/D value ( length/diameter of the extrusion cylinder) not higher than 40; single screw co-kneader extruders with a L/D value not higher than 16.
  • said polymeric matrix and said at least one inorganic filler are pre-mixed in a powder form in a mixer before being fed to the extruder .
  • said polymeric matrix in a powder form has an average particle size ranging from 50 i to 1500 ⁇ , preferably from 100 ⁇ to 500 ⁇ .
  • said at least one inorganic filler in a powder form has an average particle size ranging from 0.5 ⁇ to 20 ⁇ , preferably from 1.5 ⁇ to 5 ⁇ .
  • said at least one polyolefin having a melting temperature ( Tf ) not greater than 100°C and a melting enthalpy ( ⁇ £ ) not greater than 110 J/g is present in the polymeric matrix in an amount of at least 20% by weight. Preferably, this amount is lower or equal to 80% by weight.
  • said at least one polyolefin having a melting temperature ( T f ) not higher than 100°C and a melting enthalpy (AH f ) not higher than 110 J/g is selected from:
  • ethylene/propylene copolymers including 5 to 25% by weight of ethylene, 75 to 95% by weight of propylene, and optionally a quantity not exceeding 10% by weight of a diene, said copolymers having a molecular weight distribution index (MWDI) ranging from 1 to 5 ;
  • heterophasic propylene/ethylene copolymers comprising: a thermoplastic phase consisting of a propylene homopolymer or copolymer with ethylene and/or an alpha-olefin C 4 - Ci 2 , and an elastomeric phase consisting of a copolymer of ethylene with an alpha-olefin C 3 -C 12;
  • said at least one polyolefin has a melting temperature (T f ) ranging from 45° to 95 °C and a melting enthalpy ( ⁇ £ ) from 20 to 100 J/g.
  • T f melting temperature
  • ⁇ £ melting enthalpy
  • R is a linear or branched alkyl having from 1 to 10 carbon atoms.
  • the alpha-olefin is a C 4 -C 8 alpha-olefin.
  • the alpha-olefin is preferably selected from: 1- butene, 1-pentene, 4 -methyl - 1 -pentene , 1-hexene, 1- octene, 1-dodecene.
  • the melting temperature (T f ) and the melting enthalpy (AHf ) are determined by Differential Scanning Calorimetry (DSC) measurements, according to conventional methods.
  • the melting temperature is measured at the maximum peak of the DSC curve .
  • the molecular weight distribution index (MWDI) can be determined, according to conventional methods, by means of Gel Permeation Chromatography.
  • this preferably has the following monomer composition: 75-97% by mole, preferably 90-95% by mole, of ethylene; 3-25% by mole, preferably 5-10% by mole, of at least one alpha-olefin C 3 -C 12 ; 0-5% by mole, preferably 0-2% by moles, of at least one diene.
  • said at least one diene is selected from: conjugated or non-conjugated linear C 4 -C 2 o diolefins, (for example 1 , 3 -butadiene , 1 , -hexadiene , 1 , 6 -octadiene) ; monocyclic or polycyclic dienes (e.g. 1 , 4 -cyclohexadiene , 5-ethylidene-2-norbornene, 5- methylene-2 -norbornene) .
  • conjugated or non-conjugated linear C 4 -C 2 o diolefins for example 1 , 3 -butadiene , 1 , -hexadiene , 1 , 6 -octadiene
  • monocyclic or polycyclic dienes e.g. 1 , 4 -cyclohexadiene , 5-ethylidene-2-norbornene, 5- methylene-2 -
  • Said copolymer of ethylene with at least one alpha-olefin (a) can be produced by copolymerization of ethylene with at least one alpha-olefin, and optionally with a diene, in the presence of a single- site catalyst, in particular a metallocene catalyst as described, for example, in patents US-5,246,783 and US-5 , 272 , 236.
  • the metallocenes used as olefins catalysts are generally coordination complexes between a transition metal, usually of Group IV, in particular titanium, zirconium or hafnium, and two cyclopentadienylic ligands, which are optionally substituted, used in combination with a co-catalyst, for example an alumoxane, preferably a methylalumoxane , or a boron compound (see, for example, J. Organometallic Chemistry, 479 (1994), 1- 29, US-5, 414, 040, US- 5 , 229 , 478 , WO 93/19107, EP- 889,091, EP-632,065).
  • Other single-site catalysts usable for the production of component (c) are the so-called "Constrained Geometry Catalysts", described, for example, in patents EP-416,815, EP- 418,044, US-5, 703, 187.
  • ethylene copolymers (a) are the commercial products: EngageTM of Dow Chemical, ExactTM of ExxonMobil Chemical and TafmerTM of Mitsui Chemicals .
  • the ethylene copolymers with at least one ester having ethylenic instauration (b) they are generally copolymers of ethylene with at least one ester selected from: C x -C 3 (preferably Cx-Gj) alkyl acrylates, C x -C 8 (preferably Ci-C 4 ) alkyl methacrylates , and vinyl C 2 -C 8 (preferably C 2 -C 5 ) carboxylates .
  • the quantity of ester contained in the copolymer may generally vary from 5% to 50% by weight, preferably from 15% to 40% by weight.
  • Ci-C 8 acrylates and methacrylates are: ethyl acrylate, methyl acrylate, methyl methacrylate , tert-butyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, and the like.
  • vinyl C 2 -C 8 carboxylates are: vinylacetate , vinylpropionate , vinylbutanoate , and the like.
  • ethylene-n- butylacrylate copolymers preferably having a content of n-butylacrylate ranging from 15 to 20%, which, compared to other copolymers such as EVA (ethylene-vinylacetate) having an equivalent comonomer content, have a decomposition temperature higher than about 30-50°C, therefore they allow the use of higher processing temperatures.
  • EBA ethylene-n- butylacrylate copolymers
  • Ethylene copolymers (b) can be produced according to known processes, usually by high pressure copolymerization analogous to that used for LDPEs .
  • Examples of ethylene copolymers of the type (b) as described above are commercial products: LucofinTM of Lucobit, EscoreneTM of ExxonMobil Chemical and LotrylTM of Arkema .
  • ethylene/propylene copolymers (c) these preferably include from 5 to 15% by weight of ethylene, from 85 to 95% by weight of propylene, and optionally a diene quantity not exceeding 5% by weight.
  • Dienes suitable as possible termonomers can be preferably selected from: 1 , 4 -hexadiene , 1,6- octadiene, 5-methyl-l, 4-hexadiene, 3 , 7-dimethyl-l , 6- octadiene, dicyclopentadiene (DCPD) , ethylidene norbornene (ENB) , or mixtures thereof. Particularly preferred is ethylidene norbornene (ENB) .
  • the ethylene/propylene copolymers (c) have a triad tacticity value measured by 13 C-NMR spectroscopy, of at least 75%, more preferably at least 85%.
  • the ethylene/propylene copolymers (c) have a melting enthalpy (AH f ) of from 0.5 to 70 J/g, more preferably from 1 to 35 J/g.
  • AH f melting enthalpy
  • T f melting temperature
  • the melting temperature (T f ) of the copolymer (c) is preferably from 25° C to 100°C, more preferably from 30°C to 80°C.
  • Copolymers (c) as indicated above are available on the market under the brand names VistamaxxTM (ExxonMobil Chemical Co.) and VersifyTM (The Dow Chemical Co . ) . Further details about these products can be found, for example, in the text of the patent application U.S. 2007/0134506.
  • heterophase propylene/ethylene copolymers (d) these are usually produced by sequential copolymerization of: (a) propylene, optionally containing small quantities of at least one olefin comonomer selected from ethylene and alpha-olefin C 4 -C 12 , and subsequently of (b) a mixture of ethylene with an alpha-olefin C 3 - Ci 2 , preferably propylene, and optionally with small quantities of a diene.
  • the so obtained copolymers are also known as "reactor thermoplastic elastomers".
  • the production of said heterophasic copolymers is usually made with Ziegler-Natta catalysts based on halogenated titanium compounds supported on magnesium chloride. Processes of this type are described, for example, in patents EP 0 400 333 Al , EP 0 373 660 Al , US 5,286,564.
  • thermoplastic phase of said heterophasic copolymers is essentially formed by a propylene homopolymer or a propylene copolymer with an olefin comonomer selected from ethylene and alpha-olefin C 4 - Ci2 (preferably ethylene) .
  • the quantity of comonomer is preferably not higher than 10% by mole with respect to the total moles of monomers forming the thermoplastic phase.
  • the elastomeric phase is preferably equal to at least 40% by weight, more preferably at least 50% by weight, with respect to the total weight of the heterophasic copolymer. It is essentially formed by an ethylene elastomeric copolymer with an alpha- olefin, preferably propylene, and optionally a diene.
  • the composition of the elastomeric phase is the following: from 15 to 50% by weight, more preferably from 20 to 40% by weight, of ethylene; from 50 to 85% by weight, more preferably from 60 to 80% by weight, of propylene, with respect to the total weight of the elastomeric phase.
  • Heterophase copolymers (d) as defined above are available on the market under the brand names AdflexTM, HifaxTM and SoftellTM (Lyondell Basell) .
  • said at least one polyolefin is mixed with at least another polyolefin having a melting temperature (T f ) greater than 100°C and/or a melting enthalpy ( ⁇ £ ) greater than 110 J/g, more preferably a melting temperature (T f ) greater than 110° C and/or a melting enthalpy (AH f ) greater than 115 J/g.
  • T f melting temperature
  • ⁇ £ melting enthalpy
  • Said at least another polyolefin is preferably selected from:
  • ethylene homopolymers or copolymers with at least one alpha-olefin C 3 - Ci 2 said homopolymers or copolymers having a density of from 0.910 to 0.940 g/cm 3 , preferably from 0.915 to 0.930 g/cm 3 ;
  • copolymers of ethylene with at least one alpha-olefin C 3 - Ci 2 said copolymers having a density of from 0.870 to 0.909 g/cm 3 preferably from 0.880 to 0.905 g/cm 3 , and a molecular weight distribution index ( DI) greater than 4, preferably greater than 5.
  • ethylene homopolymer or copolymer (e) this is preferably selected from: medium density polyethylene (MDPE) having a density of from 0.926 to 0.970 g/cm 3 ; low density polyethylene (LDPE) , linear low density polyethylene (LLDPE) , having a density of from 0.910 to 0.926 g/cm 3 and linear high density polyethylene (HDPE) having a density greater than 0.940 g/cm 3 .
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • HDPE linear high density polyethylene
  • the component (e) generally has a molecular weight distribution index (MWDI) higher than 4, preferably higher than 5.
  • MWDI molecular weight distribution index
  • This type of polymers is available on the market under different brand names (for example FlexireneTM of Polimeri Europa, ExxonMobil LLDPE LL of ExxonMobil Chemical) and they can be produced according to processes well known in the art.
  • MDPE is generally produced by homopolymerization of ethylene at medium-low pressure in the presence of a Ziegler-Natta catalyst, with formation of a homopolymer having a very low branching degree.
  • LDPE is generally produced by a high-pressure process wherein ethylene is homopolymerized in the presence of oxygen or a peroxide as initiator with formation of polyethylene chains having long branching (long branched PE) .
  • LLDPE is a copolymer with short branchings, resulting from copolymerization of ethylene with an alpha-olefin C3-C12, preferably 1- butene, 1-hexene or 1-octene, and it is usually produced by means of low-pressure processes in the presence of a Ziegler-Natta catalyst or a chromium catalyst.
  • the alpha-olefin C 3 -Ci 2 is preferably contained in the copolymer in a quantity ranging from 1 to 15% by mole.
  • this is preferably a very low density polyethylene (VLDPE) having a density of from 0.870 to 0.909 g/cm 3 , preferably from 0.880 to 0.905 g/cm 3 .
  • VLDPE very low density polyethylene
  • ethylene typically obtained by copolymerization of ethylene with an alpha-olefin C 3 -C 12 , such as 1-butene, 1-hexene, 1- octene, in the presence of: (i) a catalyst based on chromium and titanium; or (ii) a catalyst based on magnesium, titanium, a halogen and an electron donor; or (iii) a catalyst based on vanadium, an electron donor, an aluminum halide and a halogenated hydrocarbon as promoter.
  • the process according to the present invention is used for the production of a flame-retardant composition including:
  • T f melting temperature
  • ⁇ £ melting enthalpy
  • this is generally selected from hydroxides, hydrated oxides, metal salts or hydrated salts, in particular of calcium, aluminum or magnesium, such as: magnesium hydroxide, alumina trihydrate, magnesium carbonate hydrate, magnesium carbonate, calcium and magnesium carbonate hydrate, calcium and magnesium carbonate, or mixtures thereof.
  • the flame-retardant inorganic filler is typically used in the form of particles having a granulometry ranging within wide limits, which may be untreated or surface-treated with saturated or unsaturated fatty acids containing from 8 to 24 carbon atoms, or salts thereof, such as for example: oleic acid, palmitic acid, stearic acid, isostearic acid, lauric acid, magnesium or zinc oleate or stearate, and mixtures thereof.
  • the flame- retardant inorganic filler can also be treated with a coupling agent selected, for example, from silanes or organic titanates such as vinyltriethoxysilane , vinyltriacetylsilane , tetra- isopropyltitanate , tetra-n-butyl titanate, and the like.
  • a coupling agent selected, for example, from silanes or organic titanates such as vinyltriethoxysilane , vinyltriacetylsilane , tetra- isopropyltitanate , tetra-n-butyl titanate, and the like.
  • the flame retardant inorganic filler is present in the composition according to the present invention in an amount ranging preferably from 70% to 280% by weight, more preferably from 100% to 220% by weight, with respect to the total weight of the polymeric components .
  • said at least one coupling agent is typically a compound having an ethylenic unsaturation and at least one functional group able to interact with the hydroxyl groups present on the flame retardant filler.
  • said coupling agent instead of an ethylenic unsaturation, may contain a polar functional group able to interact with the groups of the polar ethylene copolymer of type (b) .
  • the coupling agent may be selected in particular from :
  • Silane compounds (i) are preferably selected from compounds of formula RR'SiY 2 , wherein R is a hydrocarbon group containing an ethylenic unsaturation, Y is a hydrolyzable organic group, and R' is a saturated hydrocarbon group or is equal to Y.
  • Y is a C1-C12 alkoxide, for example: methoxy, ethoxy, propoxy, hexoxy, dodecoxy, methoxyethoxy, and the like; R is vinyl, allyl, acryl, methacryl, acryloxyalkyl or metacryloxyalkyl .
  • Examples of silane compounds (i) are:
  • Silane compounds (ii) are of the same type as described in (i) wherein the group R is a polar functional group, preferably amino, both of primary, secondary or tertiary type.
  • An example of silane compounds (ii) is aminosilane.
  • epoxy compounds (iii) are: glycidyl acrylate, glycidyl methacrylate , monoglycidyl ester of itaconic acid, maleic acid glycidyl ester, vinyl glycidyl ether, allyl glycidyl ether, or mixtures thereof .
  • Examples of monocarboxylic or dicarboxylic compounds or derivatives thereof are: maleic acid, maleic anhydride, fumaric acid, citaconic acid, itaconic acid, acrylic acid, methacrylic acid, and anhydrides or esters derived therefrom, or mixtures thereof. Particularly preferred is maleic anhydride.
  • Said at least one coupling agent can be added to the composition related to the present invention, according to at least three different methods.
  • the coupling agent is pre-grafted on at least one ethylene homopolymer or ethylene copolymer with at least one alpha-olefin C 3 -C 12 , which is added to the composition as an additional component.
  • the quantity of pre-grafted coupling agent is preferably between 0.5 and 10% by weight, preferably from 1 to 5% by weight, with respect to the total weight of said at least one ethylene homopolymer or copolymer.
  • Pre-grafted polyolefins with maleic anhydride are commercially available, for example, under the trademarks FusabondTM (Du Pont) , OrevacTM (Arkema, ExxelorTM (ExxonMobil Chemical) , YparexTM (DSM) , TecnobondTM (Tecnofilm) .
  • the coupling agent is grafted on at least one of the polymer components through a so-called "reactive extrusion", i.e. by means of a grafting reaction carried out inside the extruder by adding said at least one coupling agent and at least one radical initiator.
  • the quantity of said at least one radical initiator, for example an organic peroxide, added to achieve the reactive extrusion is generally from 0.01 to 1% by weight, preferably from 0.1 to 0.5% by weight, with respect to the total weight of the polymeric matrix.
  • the latter is added to the HFFR composition as any other ingredient, without special treatments as described above.
  • compositions according to the present invention may include other components known in the art, such as antioxidants, light stabilizers, processing aids, lubricants, pigments, other fillers.
  • suitable antioxidants are: polymerized trimethyldihydroquinoline , 4,4' -thiobis (3-methyl-6- tertbutyl) phenol, pentaerythrityl tetra- [3- (3 , 5- ditertbutyl -4 -hydroxyphenyl ) ropionate] , 2,2- thiodiethylene bis [3- (3 , 5 -ditertbutyl -4 -hydroxyphenyl propionate], and the like, or mixtures thereof.
  • fillers usable in the compositions according to the present invention can be selected for example from: glass particles or fibers (short or long), kaolin (calcined or not calcined), talc, calcium carbonate or mixtures thereof.
  • processing aids may be used, for example: calcium stearate, zinc stearate, stearic acid, paraffin wax, silicone rubbers, polyalkyleneglycols or mixtures thereof.
  • the composition according to the present invention may further include at least one dehydrating agent, according to what described in patent application WO 00/39810, which is able to absorb moisture trapped in the flame retardant filler and released during extrusion.
  • dehydrating agents suitable for the purpose are, for example: calcium oxide, calcium chloride, anhydrous alumina, zeolites, magnesium sulfate, magnesium oxide, barium oxide, or mixtures thereof .
  • compositions according to the present invention are preferably used in uncrosslinked form, in order to obtain coatings having thermoplastic properties and thus recyclable.
  • the components forming the composition are fed to the extruder in a powder form, possibly pre-mixed in a mixer (for example a turbomixer or a "dries" helix stirrer) before the feed hopper, in order to ensure a pre-dispersion of the components making the subsequent homogenization inside the extruder easier.
  • a mixer for example a turbomixer or a "dries" helix stirrer
  • the flame retardant filler but also the polymeric components are previously reduced in a powder form, for example by means of disc or blade pulverizers, optionally by pre-cooling the granules of the less crystalline polymeric components in order to facilitate their pulverization and increase the process yield.
  • Fig. 1 is a sectional view of a self- extinguishing low voltage unipolar electrical cable according to a first embodiment
  • Fig. 2 is a sectional view of a self- extinguishing low voltage unipolar electrical cable according to a second embodiment
  • Fig 3 is a sectional view of a self-extinguishing low voltage three-polar electrical cable.
  • a self-extinguishing cable (11) includes a metallic or bimetal conductor (e.g. copper/aluminum, Copper Clad Aluminum (CCA), copper/steel, Copper Clad Steel CCS) (12), an internal electrically insulating layer (13) and an external layer (14) (sheath) consisting of the composition according to the present invention.
  • a metallic or bimetal conductor e.g. copper/aluminum, Copper Clad Aluminum (CCA), copper/steel, Copper Clad Steel CCS
  • CCA Copper Clad Aluminum
  • CCS Copper Clad Steel CCS
  • the internal layer (13) can be constituted by a polymeric composition known in the art, crosslinked or uncrosslinked, preferably halogen- free , which can for example include: polyolefins (particularly polyethylene, polypropylene, ethylene/propylene thermoplastic copolymers, ethylene/propylene (EPR) or ethylene/propylene/diene (EPDM) elastomers, ethylene/ ethylenically unsaturated ester copolymers (for example EVA, EBA, EMA, EEA) , ethylene/alpha-olefin copolymers, or mixtures thereof.
  • polyolefins particularly polyethylene, polypropylene, ethylene/propylene thermoplastic copolymers, ethylene/propylene (EPR) or ethylene/propylene/diene (EPDM) elastomers, ethylene/ ethylenically unsaturated ester copolymers (for example EVA, EBA, EMA, EEA)
  • a self -extinguishing cable (21) includes a metallic or bimetallic conductor (22) as described above directly coated with an external layer (23) consisting of a composition according to the present invention, without interposition of an electrically insulating layer.
  • the external layer (23) also acts as electrical insulation.
  • a thin layer (not shown on Fig 2) acting as anti-abrasive coating, can also be externally applied to the external layer (23) .
  • (31) includes three metallic or bimetallic conductors
  • the insulating layers (33) can be constituted by an electrically insulating polymeric material as described above for Fig 1, or by a flame- retardant composition, in particular according to the present invention.
  • the so insulated conductors (32) are stranded together and the interstices present among them are usually filled with a filling material (35) in order to form a continuous structure having a substantially cylindrical shape.
  • the filler material (35) is preferably a material having flame retardant properties, usually a low viscosity and low cost material containing a flame retardant filler as described above, or even a composition according to the present invention.
  • an external sheath (36) is applied, formed by the composition according to the present invention.
  • the different layers of the above described cables are usually produced by means of an extrusion process.
  • compositions shown on the following Table 1 were produced using a counterrotating twin-screw extruder having a cylinder of 115 mm diameter, a L/D value (length/diameter of the extrusion cylinder) equal to 25, the cylinder being electrically thermostated into 6 separate zones (temperature setup increasing from 160 to 185°C) , thermostatization of the screw with oil (temperature set-up at 80°C) . All components in a powder form were dosed and fed into a dries mixer to be premixed and then pneumatically transferred to the forced hopper, the only feeding zone of the extruder.
  • the outlet of the extruder there was a filter-holding head (to which a filter mesh with a width size of 300 ⁇ was applied) and cutting in air; the so produced granules were cooled by means of a fluidized bed system by means of air cooling and then collected in bags of 25 kgs .
  • the screw was set at 17 rpm and 180 bar pressure on the head and 130 A of current absorption of the extruder motor were reached.
  • the composition temperature when discharged from the head was of 210 °C.
  • the quantities of the single components in Table 1 are indicated as % by weight with respect to the total weight of the polymeric components .
  • thermoplastic flame- retardant layer having average thickness of about 0.7 mm.
  • PolyplastolTM 51 0.5 0.5 0.5 0.5 0.5 0.5 ⁇ TM 20 0.5 0.5 0.5 0.5 0.5 0.5 0.5
  • DynasylanTM 6498 coupling agent, concentrated vinylsilane (oligomeric siloxane) containing vinyl and epoxy groups, density about 1 g/cm 3 , boiling point 242°C, flash point 75°C (Evonik) ;
  • PeroximonTM DC40 radical initiator, cumyl peroxide in 40% calcium carbonate (Arkema) ;
  • PolyplastolTM 51 processing aid based on amide derivatives (Eigenmann & Veronelli);
  • Anox 20TM antioxidant, penthaerytrityl tetra-[3- (3 , 5-diterbutyl-4 hydroxyphenyl ) propyonate]
  • the flame-retardant coatings so obtained were evaluated according to their tensile properties, in accordance with standards CEI 20-34, ⁇ 5.1. or CEI EN 60811-1-1 (2001) .
  • compositions according to the present invention allow obtaining flame- retardant coatings having high flexibility (elongation at break greater than 100%) without compromising tensile strength and flame-retardant properties .
  • compositions reported in the following Table 2 were produced, using the same equipment and the same conditions as described above for Examples 1-5.
  • the quantities of the single components in Table 2 are expressed as % by weight with respect to the total weight of the polymeric components.
  • Each composition was used to produce a unipolar cable according to Fig 1, as indicated above for Examples 1-5.
  • the so obtained flame-retardant coatings were evaluated according to their tensile properties, in accordance with standards CEI 20-34, ⁇ 5.1. or CEI EN 60811-1-1 (2001).
  • the self- extinguishing properties of the compositions were evaluated by measuring the Limited Oxygen Index (LOI) , determined according to ASTM D 2863 as described above for Examples 1-5. The results are reported in Table 2.
  • LOI Limited Oxygen Index
  • compositions according to the present invention allow obtaining flame-retardant coatings having high flexibility (elongation at break greater than 100%) without compromising tensile strength and flame- retardant properties.
  • IrganoxTM 1010 antioxidant - penthaerytrytol tetrakis (3- (3 , 5 -di-tert-butyl -4 -hydroxyphenyl)

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Abstract

L'invention porte sur un procédé pour la production d'une composition ignifuge comprenant une matrice polymère et au moins une charge inorganique dotée de propriétés ignifuges, la matrice polymère sous forme de poudre et la charge inorganique sous forme de poudre étant introduites dans une extrudeuse choisie parmi : les extrudeuses à double vis contrarotatives ayant une valeur de L/D (rapport longueur/diamètre du cylindre d'extrusion) inférieure ou égale à 40 ; et les extrudeuses associées à un malaxeur à une seule vis présentant une valeur de L/D inférieure ou égale à 16. La matrice polymère comprend au moins 10 % en poids, par rapport au poids total de la matrice polymère, d'au moins une polyoléfine ayant une température de fusion (Tf) inférieure ou égale à 100 °C et une enthalpie de fusion (ΔΗf) inférieure ou égale à 110 J/g.
PCT/IB2012/054490 2011-09-01 2012-08-31 Procédé pour la production d'une composition ignifuge WO2013030795A1 (fr)

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CN105161201A (zh) * 2015-08-06 2015-12-16 台州携康电子有限公司 阻燃电缆
US20160189829A1 (en) * 2014-12-30 2016-06-30 General Cable Technologies Corporation Multi-layer cables
EP3050937A1 (fr) * 2015-01-27 2016-08-03 Borealis AG Composition de polypropylène ignifuge
EP3264425A1 (fr) * 2016-06-17 2018-01-03 Hitachi Metals, Ltd. Fil et câble isolés
EP3264424A1 (fr) * 2016-06-17 2018-01-03 Hitachi Metals, Ltd. Fil isolé
WO2018046097A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Composition polymère à souplesse et propriété ignifuge élevées
WO2018046098A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Article allongé présentant une bonne souplesse et une ininflammabilité élevée
WO2018046096A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Dispositif de conjonction de type câble et sa composition polymère de préparation
WO2018046099A1 (fr) * 2016-09-09 2018-03-15 Leoni Kabel Gmbh Éléments en forme de brin et composition polymère pour leur préparation
EP3480829A1 (fr) * 2017-11-07 2019-05-08 Hitachi Metals, Ltd. Fil électrique isolé
CN110198982A (zh) * 2017-01-27 2019-09-03 伊奎斯塔化学有限公司 过氧化物改性的聚乙烯、组合物和应用
IT201900004127A1 (it) * 2019-03-21 2020-09-21 Prysmian Spa Cavo elettrico ritardante di fiamma
US11248111B2 (en) 2016-09-09 2022-02-15 Leoni Kabel Gmbh Conjunction device such as a cable and polymer composition for preparing same

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US10923246B2 (en) 2019-03-21 2021-02-16 Prysmian S.P.A. Flame retardant electrical cable
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