WO2002100942A1 - Fluorinated polymer composition with improved fire resistance - Google Patents

Fluorinated polymer composition with improved fire resistance Download PDF

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Publication number
WO2002100942A1
WO2002100942A1 PCT/FR2002/001859 FR0201859W WO02100942A1 WO 2002100942 A1 WO2002100942 A1 WO 2002100942A1 FR 0201859 W FR0201859 W FR 0201859W WO 02100942 A1 WO02100942 A1 WO 02100942A1
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Prior art keywords
composition
fire resistance
composition according
fluoropolymer
fluorinated polymer
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PCT/FR2002/001859
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French (fr)
Inventor
Anthony Bonnet
Thomas Fine
James Mason
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Atofina
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Publication of WO2002100942A1 publication Critical patent/WO2002100942A1/en

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    • 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
    • H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445—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 vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the invention relates to a fluoropolymer composition with improved fire resistance.
  • PVDF polyvinylidene fluoride
  • the American standard UL 910 to which electrical cladding must meet is the most restrictive on a global level and PVDF is one of the few polymers that can meet it.
  • This standard corresponds to a flame propagation test along the sheath, the flame must not propagate along the sheath beyond a certain value.
  • a measurement of the opacity of the fumes is carried out. This criterion is just as important as flame spread.
  • One of the methods making it possible to improve the fire resistance of a fluoropolymer consists in incorporating fillers therein, this incorporation of fillers is done by mixing them with the fluoropolymer in the molten state. However, during this incorporation, reactions can take place between the fillers and the fluoropolymer which can lead to the rapid release of a large quantity of hydrofluoric acid.
  • the present invention relates to a composition comprising a fluoropolymer and fillers and which does not have these drawbacks during its preparation. In addition, it has very good fire resistance.
  • This formulation is based on kaolin up to 0.2 to 1.2% by weight and ZnO (color reducer) up to 5%. The same results are obtained with hydrated or calcined kaolin. The preparation of this composition is carried out in a molten medium with shearing, but using only small quantities of fillers.
  • Patent EP 0709429 relates to the production of PVDF / PVC mixtures and describes more particularly the use of a vinyl chloride polymer as a filler, highlighting its dielectric properties which are more advantageous than PVDF and, in particular a dielectric constant and lower high frequency dielectric losses (> 1 MHz).
  • these polymers do not have a good resistance to fire (higher flammability, significant smoke generation) and it is necessary to incorporate plasticizers therein, but this further decreases the fire resistance and increases the fumigancy.
  • PVDF and PVC are not compatible, the inventors describe the use of a third compatibilizing body.
  • the PVDF used is a copolymer containing 5 to 25% of CTFE or HFP.
  • the compatibilizer used is a methacrylic polymer chosen from homopolymers of methyl methacrylate and its copolymers with a preponderant content of methyl methacrylate with C2 to C6 alkyl acrylates and / or methacrylates. It contains between 55% and 90% by weight of methyl methacrylate.
  • Patent FR 2608165 describes flame-retarded storage stabilized compositions based on vinylidene fluoride comprising a metal molybdate, characterized in that they additionally contain as stabilizing an alkaline earth metal.
  • the mass ratio between the metal molybdate and the alkaline earth metal carbonate is 5 to 30 parts of alkaline earth per 100 parts of metal molybdate and the metal molybdate is used in an amount of 0.05 to 2 parts by weight , expressed as metallic molybdenum, per 100 parts of PVDF.
  • Patent FR 1591996 describes PVDF containing (i) carbon black or chromic oxide and (ii) Zinc oxide.
  • the mixture can contain from 65 to 78% by weight of PVDF, from 20 to 30% by weight of (i) and from 2 to 5% by weight of ZnO.
  • a plasticizer from the polyester family is used. It is taught in this patent that silica, titanium dioxide, magnesia, antimony oxide, mica accelerate the degradation of PVDF. This patent is therefore limited to the aforementioned charges (carbon black and chromic oxide) as well as to a stabilizer for zinc oxide and more particularly to their synergy.
  • the patent FR 1577758 describes PVDF thermally stabilized by the oxides of a metal from the second group of the periodic system until the fourth period.
  • the level of stabilizers varies from 0.3 to 0.5% by weight.
  • the present invention relates to a fluoropolymer composition with improved fire resistance comprising by weight, the total being 100%:
  • the complement being at least one inorganic filler based on silicate.
  • This composition can be prepared by introducing the polyether and the inorganic filler into the fluorinated polymer in the molten state.
  • the usual devices for mixing or kneading (compounding) of thermoplastics can be used. These are for example an extruder, a BUSS® mixer.
  • This composition has good stability during the compounding step as well as good behavior during fire resistance tests. It is useful for making objects that have to resist fire, in particular sheathing and insulation for electric or telecommunication cables. The invention also relates to these cables. [Detailed description of the invention]
  • any polymer having in its chain at least one monomer chosen from compounds containing a vinyl group capable of opening up to polymerize and which contains, directly attached to this vinyl group, at least one atom is thus designated. of fluorine, a fluoroalkyl group or a fluoroalkoxy group.
  • the fluoropolymer can comprise a homopolymer or a copolymer, it can also comprise non-fluorinated monomers such as ethylene.
  • the fluoropolymer is PVDF homopolymer or copolymer containing at least 60% by weight of VF2, the optional comonomer is chosen from the fluorinated monomers mentioned above and is advantageously HFP.
  • the fluoropolymer can contain plasticizers or additives, such as for example a well-known plasticizer, dibutyl sebacate. It would not be departing from the scope of the invention to use a mixture of two or more fluoropolymers.
  • polyether oligomers or polymers are thus designated having alkylene oxide units.
  • poly (oxyethyene) glycol commonly known as polyethylene glycol (PEG), advantageously the mass Mn is between 400 and 15,000 g / mol and the melting temperature between 50 and 80 ° C.
  • PEG polyethylene glycol
  • PLURIOL E® from the company BASF
  • POLYGLYKOL® 1500 from the company CLARIANT. It would not be departing from the scope of the invention to use a mixture of two or more polyethers.
  • inorganic filler based on silicate there may be mentioned alumino-silicate, or magnesium silicates.
  • alumino-silicate mention will be made of kaolin and mica
  • magnesium silicates mention may be made of talc. It would not be departing from the scope of the invention to use a mixture of two or more inorganic fillers.
  • part of this silicate-based filler can be replaced by antimony trioxide, the proportion of antimony trioxide can be from 5 to 30% by weight of the total mass of the filler inorganic.
  • the proportions of fluoropolymer are from 75 to 85%.
  • the proportions of polyether are from 0.5 to 2%.
  • the extruder used is a DSK 42/5 double screw. This extruder is of the counter-rotating type and has a length of 105 mm. The maximum speed is 90 rpm and the maximum torque is 200 N.m. The various mixtures were carried out at a temperature of 200 ° C., at 40 rpm.
  • the Brabender plastograph consists of a dynamometric motor and a gearbox.
  • the mixing chamber has a volume of 60 cm 3 .
  • Two rotors rotating in opposite directions ensure the mixing of the material in the molten state.
  • the mixtures were carried out at 230 ° C, at 80 rpm for 5 minutes.
  • the measurements are carried out according to standard ASTM E 1354.
  • the calorimeter cone consists of 5 main elements.
  • the values reported in the table are:
  • the specific extinction area which is obtained by measuring the extinction of a laser beam projected through the gas stream is a measure of the "obscuring power" of the fumes generated by the combustion of the sample. This measurement is expressed in m 2 per mass of product remaining at time t. This value must be as low as possible (the lower it is the less the fumes are opaque).
  • the effective heat of combustion represents the total calorific energy per unit of mass which can be released by the complete combustion of the material (lower calorific value). This value is expressed in kJ / g of sample. This value must be as low as possible (the lower it is the better the fire resistance). All the samples tested have two combustion phases.
  • a first phase corresponding to the most rapid rate of mass loss and the generation of practically all the quantity of smoke and energy and the second phase which produces almost no smoke and releases practically no energy.
  • the values given in the following table are the values of the first phase.
  • FIG. 1 is presented a typical curve of the Kynar® 2950-05 giving the evolution of the loss of mass during a measurement with a cone calorimeter according to the standard ASTM E 1354.
  • Kynar® 2950-05 is used, which is a VF2 / HFP copolymer containing 17% by weight of HFP.
  • This polymer from the company ATOFINA has an MFI at 230 ° C. under 5 kg of 10 gr / 10 minutes.
  • the polyether used is a PEG with a molar mass of 1500 gr / mole, with a melting temperature of approximately 55 ° C., in the form of flaking This PEG is marketed under the name POLYGLYKOL® 1500 from the company CLARIANT

Abstract

The invention concerns a fluorinated polymer composition with improved fire resistance comprising by weight, the total being 100 %: 60 to 90 % of at least a fluorinated polymer; 0.1 to 5 % of a polyether; the complement being at least an inorganic silicate filler. Said composition can be prepared by introducing polyether and the inorganic filler in the molten fluorinated polymer. The usual devices for mixing or compounding thermoplastics can be used including, for example, an extruder, a BUSS® kneader. Said composition exhibits good stability during the compounding step as well as good performance during fire resistance tests. Said composition is useful for making objects which have to be fire resistant, in particular claddings and insulants for electric or telecommunication cables. The invention also concerns said cables.

Description

COMPOSITION DE POLYMERE FLUORE A TENUE AU FEU AMELIOREE IMPROVED FIRE-RESISTANT FLUORINATED POLYMER COMPOSITION
[Domaine de l'invention][Field of the invention]
L'invention concerne une composition de polymère fluoré à tenue au feu améliorée. Par exemple le polyfluorure de vinylidène (PVDF) possède d'exceptionnelles propriétés de stabilité thermique et de tenue au feu, ce qui explique son utilisation dans le marché du bâtiment pour réaliser du gainage électrique. La norme américaine UL 910 à laquelle doivent répondre les gainages électriques est la plus contraignante au niveau mondial et le PVDF fait partie des quelques polymères à pouvoir y répondre. Cette norme correspond à un test de propagation de flamme le long de la gaine, la flamme ne doit pas se propager le long de la gaine au-delà d'une certaine valeur. De plus lors de la combustion de la gaine, une mesure d'opacité des fumées est réalisée. Ce critère est tout aussi important que la propagation de flamme. L'une des méthodes permettant d'améliorer la tenue au feu d'un polymère fluoré consiste à y incorporer des charges, cette incorporation de charges se fait en les mélangeant avec le polymère fluoré à l'état fondu. Cependant au cours de cette incorporation il peut se produire des réactions entre les charges et le polymère fluoré pouvant conduire à la libération de façon rapide d'une grande quantité d'acide fluorhydrique. La présente invention concerne une composition comprenant un polymère fluoré et des charges et qui ne présente pas ces inconvénients lors de sa préparation. De plus elle a une très bonne tenue au feu.The invention relates to a fluoropolymer composition with improved fire resistance. For example, polyvinylidene fluoride (PVDF) has exceptional thermal stability and fire resistance properties, which explains its use in the building market to produce electrical sheathing. The American standard UL 910 to which electrical cladding must meet is the most restrictive on a global level and PVDF is one of the few polymers that can meet it. This standard corresponds to a flame propagation test along the sheath, the flame must not propagate along the sheath beyond a certain value. In addition, during combustion of the sheath, a measurement of the opacity of the fumes is carried out. This criterion is just as important as flame spread. One of the methods making it possible to improve the fire resistance of a fluoropolymer consists in incorporating fillers therein, this incorporation of fillers is done by mixing them with the fluoropolymer in the molten state. However, during this incorporation, reactions can take place between the fillers and the fluoropolymer which can lead to the rapid release of a large quantity of hydrofluoric acid. The present invention relates to a composition comprising a fluoropolymer and fillers and which does not have these drawbacks during its preparation. In addition, it has very good fire resistance.
[L'art antérieur et le problème technique][The prior art and the technical problem]
l'art antérieur a déjà décrit des compositions devant résister au feu. Le brevet US 4804702 décrit une formulation de PVDF permettant de constater une chute de l'indice de fumée et une augmentation du LOI (Limitingthe prior art has already described compositions having to resist fire. US Patent 4804702 describes a formulation of PVDF making it possible to note a fall in the smoke index and an increase in LOI (Limiting
Oxygen Index ou indice limite d'oxygène). Cette formulation est à base de kaolin à hauteur de 0,2 à 1 ,2 % en poids et de ZnO (réducteur de couleur) jusqu'à 5%. Les même résultats sont obtenus avec du kaolin hydraté ou calciné. La préparation de cette composition se fait en milieu fondu avec cisaillement mais en ne faisant intervenir que de faibles quantités de charges.Oxygen Index). This formulation is based on kaolin up to 0.2 to 1.2% by weight and ZnO (color reducer) up to 5%. The same results are obtained with hydrated or calcined kaolin. The preparation of this composition is carried out in a molten medium with shearing, but using only small quantities of fillers.
Le brevet EP 0709429 concerne la réalisation de mélanges PVDF/PVC et décrit plus particulièrement l'emploi d'un polymère du chlorure de vinyle comme charge en mettant en avant ses propriétés diélectriques plus intéressantes que le PVDF et, en particulier une constante diélectrique et des pertes diélectriques à haute fréquence(> à 1 MHz) moins élevées. Cependant ces polymères n'ont pas une bonne tenue au feu (inflammabilité plus élevée, dégagement de fumée important) et il est nécessaire d'y d'incorporer des plastifiants mais ceci diminue encore la résistance au feu et augmente la fumigénicité. Le PVDF et le PVC n'étant pas compatibles, les inventeurs décrivent l'utilisation d'un tiers corps compatibilisant. Le PVDF utilisé est un copolymère contenant 5 à 25% de CTFE ou d'HFP. Le compatibilisant utilisé est un polymère méthacrylique choisi parmi les homopolymères du méthacrylate de méthyle et ses copolymères à teneur prépondérante en méthacrylate de méthyle avec des acrylates et /ou des méthacrylates d'alkyles en C2 à C6. Il contient entre 55% et 90% en poids de méthacrylate de méthyle.Patent EP 0709429 relates to the production of PVDF / PVC mixtures and describes more particularly the use of a vinyl chloride polymer as a filler, highlighting its dielectric properties which are more advantageous than PVDF and, in particular a dielectric constant and lower high frequency dielectric losses (> 1 MHz). However, these polymers do not have a good resistance to fire (higher flammability, significant smoke generation) and it is necessary to incorporate plasticizers therein, but this further decreases the fire resistance and increases the fumigancy. Since PVDF and PVC are not compatible, the inventors describe the use of a third compatibilizing body. The PVDF used is a copolymer containing 5 to 25% of CTFE or HFP. The compatibilizer used is a methacrylic polymer chosen from homopolymers of methyl methacrylate and its copolymers with a preponderant content of methyl methacrylate with C2 to C6 alkyl acrylates and / or methacrylates. It contains between 55% and 90% by weight of methyl methacrylate.
Le brevet FR 2608165 décrit des compositions ignifugées stabilisées au stockage à base de fluorure de vinylidène comprenant un molybdate de métal, caractérisées en ce qu'elles contiennent en outre comme stabilisant un alcalino- terreux. Le rapport massique entre le molybdate de métal et le carbonate de métal alcalino-terreux est de 5 à 30 parties d'alcalino-terreux pour 100 parties de molybdate de métal et le molybdate de métal est utilisé à raison de 0.05 à 2 parties en poids, exprimées en molybdène métallique, pour 100 parties de PVDF.Patent FR 2608165 describes flame-retarded storage stabilized compositions based on vinylidene fluoride comprising a metal molybdate, characterized in that they additionally contain as stabilizing an alkaline earth metal. The mass ratio between the metal molybdate and the alkaline earth metal carbonate is 5 to 30 parts of alkaline earth per 100 parts of metal molybdate and the metal molybdate is used in an amount of 0.05 to 2 parts by weight , expressed as metallic molybdenum, per 100 parts of PVDF.
Ces compositions ne sont pas complètement satisfaisantes de plus elles ne sont pas faciles à préparer parce qu'au cours de l'incorporation des charges dans le polymère fluoré il peut y avoir une dégradation du polymère fluoré. Dans les deux arts antérieurs suivants on a proposé des solutions à ce problème de l'incorporation des charges. Le brevet FR 1591996 décrit du PVDF contenant (i) du noir de carbone ou de l'oxyde chromique et (ii) de l'oxyde de Zinc. Le mélange peut contenir de 65 à78 % en poids de PVDF, de 20 à30 % en poids de (i) et de 2 à 5% en poids de ZnO. Parfois, un plastifiant de la famille des polyesters est utilisé. Il est enseigné dans ce brevet que la silice, le dioxyde de titane, la magnésie, l'oxyde d'antimoine, le mica accélèrent la dégradation du PVDF. Ce brevet se limite donc aux charges précitées (noir de carbone et oxyde chromique) ainsi qu'à un stabilisant l'oxyde de zinc et plus particulièrement à leur synergie.These compositions are not completely satisfactory, moreover they are not easy to prepare because during the incorporation of the fillers in the fluoropolymer there may be a degradation of the fluoropolymer. In the following two prior arts solutions have been proposed to this problem of incorporating fillers. Patent FR 1591996 describes PVDF containing (i) carbon black or chromic oxide and (ii) Zinc oxide. The mixture can contain from 65 to 78% by weight of PVDF, from 20 to 30% by weight of (i) and from 2 to 5% by weight of ZnO. Sometimes a plasticizer from the polyester family is used. It is taught in this patent that silica, titanium dioxide, magnesia, antimony oxide, mica accelerate the degradation of PVDF. This patent is therefore limited to the aforementioned charges (carbon black and chromic oxide) as well as to a stabilizer for zinc oxide and more particularly to their synergy.
Le brevet FR 1577758 décrit du PVDF stabilisé thermiquement par les oxydes d'un métal du deuxième groupe du système périodique jusqu'à la quatrième période. Dans cet enseignement le taux de stabilisants varie de 0,3 à 0,5% en poids.The patent FR 1577758 describes PVDF thermally stabilized by the oxides of a metal from the second group of the periodic system until the fourth period. In this teaching the level of stabilizers varies from 0.3 to 0.5% by weight.
On a maintenant trouvé qu'un polymère fluoré comprenant des charges à base de silicates et des polyethers avait une très bonne tenue au feu et était facile à préparer. L'art antérieur n'a jamais décrit de telles formulations.It has now been found that a fluoropolymer comprising fillers based on silicates and polyethers has very good fire resistance and is easy to prepare. The prior art has never described such formulations.
[Brève description de l'invention][Brief description of the invention]
La présente invention concerne une composition de polymère fluoré à tenue au feu améliorée comprenant en poids, le total étant 100% :The present invention relates to a fluoropolymer composition with improved fire resistance comprising by weight, the total being 100%:
• 60 à 90 % d'au moins un polymère fluoré,• 60 to 90% of at least one fluoropolymer,
• 0,1 à 5 % d'un polyether,• 0.1 to 5% of a polyether,
• le complément étant au moins une charge inorganique à base de silicate.• the complement being at least one inorganic filler based on silicate.
Cette composition peut être préparée par introduction du polyether et de la charge inorganique dans le polymère fluoré à l'état fondu. On peut utiliser les dispositifs habituels de mélange ou de malaxage (compoundage) des thermoplastiques. Ce sont par exemple une extrudeuse, un malaxeur BUSS®. Cette composition présente une bonne stabilité lors de l'étape de compoundage ainsi qu'un bon comportement lors des tests en résistance au feu. Elle est utile pour faire des objets devant résister au feu, en particulier des gainages et des isolants de câbles électriques ou de télécommunication. L'invention concerne aussi ces câbles. [Description détaillée de l'invention]This composition can be prepared by introducing the polyether and the inorganic filler into the fluorinated polymer in the molten state. The usual devices for mixing or kneading (compounding) of thermoplastics can be used. These are for example an extruder, a BUSS® mixer. This composition has good stability during the compounding step as well as good behavior during fire resistance tests. It is useful for making objects that have to resist fire, in particular sheathing and insulation for electric or telecommunication cables. The invention also relates to these cables. [Detailed description of the invention]
S'agissant du polymère fluoré on désigne ainsi tout polymère ayant dans sa chaîne au moins un monomère choisi parmi les composés contenant un groupe vinyle capable de s'ouvrir pour se polymériser et qui contient, directement attaché à ce groupe vinyle, au moins un atome de fluor, un groupe fluoroalkyle ou un groupe fluoroalkoxy.As regards the fluoropolymer, any polymer having in its chain at least one monomer chosen from compounds containing a vinyl group capable of opening up to polymerize and which contains, directly attached to this vinyl group, at least one atom is thus designated. of fluorine, a fluoroalkyl group or a fluoroalkoxy group.
A titre d'exemple de monomère on peut citer le fluorure de vinyle; le fluorure de vinylidene (VF2); le trifluoroethylene (VF3); le chlorotrifluoroethylene (CTFE); le 1 ,2-difluoroethylene; le tetrafluoroethylene (TFE); l'hexafluoropropylene (HFP); les perfluoro(alkyl vinyl) ethers tels que le perfluoro(methyl vinyl)ether (PMVE), le perfluoro(ethyl vinyl) ether (PEVE) et le perfluoro ropyl vinyl) ether (PPVE); le perfluoro( 1 ,3 -dioxole); le perfluoro(2,2- dimethyl- 1 ,3 -dioxole) (PDD); le produit de formule CF2=CFOCF2CF(CF3)OCF2CF2X dans laquelle X est SO2F, CO2H, CH2OH, CH20CN ou CH20PO3H; le produit de formule CF2=CFOCF2CF2S02F; le produit de formule F(CF2)nCH20CF=CF2 dans laquelle n est 1 , 2, 3, 4 or 5; le produit de formule R1CH2OCF=CF2 dans laquelle R1 est l'hydrogène ou F(CF2)z et z vaut 1 , 2, 3 ou 4; le produit de formule R3OCF=CH2 dans laquelle R3 est F(CF2)z- et z est 1 , 2, 3 or 4; le perfluorobutyl ethylene (PFBE); le 3,3,3- trifluoropropene et le 2-trifluoromethyl-3 ,3 ,3 -trifluoro- 1 -propene.By way of example of a monomer, mention may be made of vinyl fluoride; vinylidene fluoride (VF2); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro (alkyl vinyl) ethers such as perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE) and perfluoro ropyl vinyl) ether (PPVE); perfluoro (1, 3 -dioxole); perfluoro (2,2-dimethyl-1, 3 -dioxole) (PDD); the product of formula CF2 = CFOCF2CF (CF3) OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH20CN or CH20PO3H; the product of formula CF2 = CFOCF2CF2S02F; the product of formula F (CF2) nCH20CF = CF2 in which n is 1, 2, 3, 4 or 5; the product of formula R1CH2OCF = CF2 in which R1 is hydrogen or F (CF2) z and z is 1, 2, 3 or 4; the product of formula R3OCF = CH2 in which R3 is F (CF2) z- and z is 1, 2, 3 or 4; perfluorobutyl ethylene (PFBE); 3,3,3-trifluoropropene and 2-trifluoromethyl-3, 3, 3 -trifluoro- 1 -propene.
Le fluoropolymere peut comprendre un homopolymere ou un copolymère, il peut aussi comprendre des monomères non fluorés tels que l'éthylène. Avantageusement le fluoropolymere est du PVDF homopolymere ou copolymère contenant au moins 60% en poids de VF2, le comonomère éventuel est choisi parmi les monomères fluorés cités plus hauts et est avantageusement le HFP. Le fluoropolymere peut contenir des plastifiants ou des additifs, comme par exemple un plastifiant bien connu le dibutyle sébaçate. On ne sortirait pas du cadre de l'invention en utilisant un mélange de deux ou plusieurs polymères fluorés. S'agissant du polyether on désigne ainsi des oligomères ou des polymères ayant des motifs oxyde d'alkylène. On peut citer à titre d'exemple le poly(oxyethy!ène)glycol appelé communément polyéthylène glycol (PEG), avantageusement la masse Mn est comprise entre 400 et 15000 g/mole et la température de fusion comprise entre 50 et 80°C. A titre d'exemple de PEG on peut citer le PLURIOL E® de la société BASF ou le POLYGLYKOL® 1500 de la société CLARIANT. On ne sortirait pas du cadre de l'invention en utilisant un mélange de deux ou plusieurs polyethers.The fluoropolymer can comprise a homopolymer or a copolymer, it can also comprise non-fluorinated monomers such as ethylene. Advantageously, the fluoropolymer is PVDF homopolymer or copolymer containing at least 60% by weight of VF2, the optional comonomer is chosen from the fluorinated monomers mentioned above and is advantageously HFP. The fluoropolymer can contain plasticizers or additives, such as for example a well-known plasticizer, dibutyl sebacate. It would not be departing from the scope of the invention to use a mixture of two or more fluoropolymers. As regards polyether, oligomers or polymers are thus designated having alkylene oxide units. By way of example, mention may be made of poly (oxyethyene) glycol commonly known as polyethylene glycol (PEG), advantageously the mass Mn is between 400 and 15,000 g / mol and the melting temperature between 50 and 80 ° C. By way of example of PEG, mention may be made of PLURIOL E® from the company BASF or POLYGLYKOL® 1500 from the company CLARIANT. It would not be departing from the scope of the invention to use a mixture of two or more polyethers.
S'agissant de la charge inorganique à base de silicate on peut citer les alumino-silicate, ou les silicates de magnésium. Parmi les alumino-silicate on citera le kaolin et le mica, parmi les silicates de magnésium on peut citer le talc. On ne sortirait pas du cadre de l'invention en utilisant un mélange de deux ou plusieurs charges inorganiques.As regards the inorganic filler based on silicate, there may be mentioned alumino-silicate, or magnesium silicates. Among the alumino-silicate mention will be made of kaolin and mica, among the magnesium silicates mention may be made of talc. It would not be departing from the scope of the invention to use a mixture of two or more inorganic fillers.
Selon une forme avantageuse de l'invention une partie de cette charge à base de silicate peut être remplacée par du trioxyde d'antimoine, la proportion de trioxyde d'antimoine peut être de 5 à 30% en poids de la masse totale de la charge inorganique.According to an advantageous form of the invention, part of this silicate-based filler can be replaced by antimony trioxide, the proportion of antimony trioxide can be from 5 to 30% by weight of the total mass of the filler inorganic.
Avantageusement les proportions de polymère fluoré sont de 75 à 85 %. Avantageusement les proportions de polyether sont de 0,5 à 2 %.Advantageously, the proportions of fluoropolymer are from 75 to 85%. Advantageously, the proportions of polyether are from 0.5 to 2%.
[Exemples][Examples]
Tous les exemples sont regroupés sur le tableau 1 afin de faciliter la lecture et l'analyse des résultats. Trois paramètres sont importants à retenir, i) la couleur et l'aspect du produit après un cisaillement à l'état fondu, avec un changement possible de couleur et d'aspect et la présence de bulles significatives d'une libération de volatiles, ii) l'aire spécifique d'extinction, iii) la chaleur de combustion.All the examples are grouped in Table 1 in order to facilitate reading and analysis of the results. Three parameters are important to remember, i) the color and appearance of the product after a shear in the molten state, with a possible change in color and appearance and the presence of significant bubbles of a release of volatiles, ii ) the specific extinction area, iii) the heat of combustion.
Préparation des compositions: Préparation des compositons sur extrudeuse bi-vis Brabender® DSK :Preparation of the compositions: Preparation of compositons on Brabender® DSK twin-screw extruder:
L'extrudeuse utilisée est une double vis DSK 42/5. Cette extrudeuse est de type contra-rotative et présentent une longueur de 105 mm. La vitesse maximum est de 90 tr/min et le couple maximum est de 200 N.m. Les différents mélanges ont été réalisés à une température de 200°C, à 40 tr/min.The extruder used is a DSK 42/5 double screw. This extruder is of the counter-rotating type and has a length of 105 mm. The maximum speed is 90 rpm and the maximum torque is 200 N.m. The various mixtures were carried out at a temperature of 200 ° C., at 40 rpm.
Préparation des compositions sur Malaxeur Brabender® : Le plastographe Brabender est constitué d'un moteur dynamométrique et d'une boite de vitesse. La chambre de malaxage présente un volume de 60 cm3. Deux rotors tournant en sens inverse assurent le malaxage du matériau à l'état fondu. Les mélanges ont été réalisés à 230°C, à 80 tr/min pendant 5 minutes.Preparation of compositions on Brabender® mixer: The Brabender plastograph consists of a dynamometric motor and a gearbox. The mixing chamber has a volume of 60 cm 3 . Two rotors rotating in opposite directions ensure the mixing of the material in the molten state. The mixtures were carried out at 230 ° C, at 80 rpm for 5 minutes.
Mesures au cône calorimètre : Les mesures sont réalisées suivant la norme ASTM E 1354. Le cône calorimètre se compose de 5 éléments principaux. Un four tronconique et son circuit de régulation, un support d'échantillon monté sur une cellule de pesée, une hotte munie d'un ventilateur pour capter les produits de combustion, un banc d'analyse de gaz et un laser pour mesurer l'opacité des fumées. Les valeurs reportées dans le tableau sont :Measurements with the calorimeter cone: The measurements are carried out according to standard ASTM E 1354. The calorimeter cone consists of 5 main elements. A frustoconical oven and its regulation circuit, a sample support mounted on a load cell, a hood fitted with a fan to capture the combustion products, a gas analysis bench and a laser to measure the opacity fumes. The values reported in the table are:
L'aire spécifique d'extinction qui est obtenue en mesurant l'extinction d'un faisceau laser projeté à travers la veine gazeuse est une mesure du « pouvoir obscurissant » des fumées générées par la combustion de l'échantillon. Cette mesure s'exprime en m2 par masse de produit restant à l'instant t. Cette valeur doit être la plus faible possible (plus elle est faible moins les fumées sont opaques). La chaleur de combustion efficace représente l'énergie calorifique totale par unité de masse qui peut être dégagée par la combustion complète du matériau (pouvoir calorifique inférieur). Cette valeur s'exprime en kJ/g d'échantillon. Cette valeur doit être la plus faible possible (plus elle est faible meilleure est la résistance au feu). Tous les échantillons testés présentent deux phases de combustion. Une première phase correspondant à la vitesse de perte de masse la plus importante et à la génération de pratiquement toute la quantité de fumée et d'énergie et la deuxième phase qui ne produit quasiment aucune fumée et ne libère pratiquement pas d'énergie. Les valeurs données dans le tableau suivant sont les valeurs de la première phase. Sur la figure 1 est présentée une courbe typique du Kynar® 2950-05 donnant l'évolution de la perte de masse au cours d'une mesure au cône calorimètre suivant la norme ASTM E 1354.The specific extinction area which is obtained by measuring the extinction of a laser beam projected through the gas stream is a measure of the "obscuring power" of the fumes generated by the combustion of the sample. This measurement is expressed in m 2 per mass of product remaining at time t. This value must be as low as possible (the lower it is the less the fumes are opaque). The effective heat of combustion represents the total calorific energy per unit of mass which can be released by the complete combustion of the material (lower calorific value). This value is expressed in kJ / g of sample. This value must be as low as possible (the lower it is the better the fire resistance). All the samples tested have two combustion phases. A first phase corresponding to the most rapid rate of mass loss and the generation of practically all the quantity of smoke and energy and the second phase which produces almost no smoke and releases practically no energy. The values given in the following table are the values of the first phase. In FIG. 1 is presented a typical curve of the Kynar® 2950-05 giving the evolution of the loss of mass during a measurement with a cone calorimeter according to the standard ASTM E 1354.
Dans tous les exemples on utilise Le Kynar® 2950-05 qui est un copolymère VF2/ HFP à 17 % en poids de HFP. Ce polymère de la société ATOFINA présente un MFI à 230°C sous 5 kg de 10 gr/10 minutes. Le polyether utilisé est un PEG de masse molaire 1500 gr/mole, de température de fusion environ 55°C se présentant sous forme d'écaillé Ce PEG est commercialisé sous le nom POLYGLYKOL® 1500 de la société CLARIANT In all the examples, Kynar® 2950-05 is used, which is a VF2 / HFP copolymer containing 17% by weight of HFP. This polymer from the company ATOFINA has an MFI at 230 ° C. under 5 kg of 10 gr / 10 minutes. The polyether used is a PEG with a molar mass of 1500 gr / mole, with a melting temperature of approximately 55 ° C., in the form of flaking This PEG is marketed under the name POLYGLYKOL® 1500 from the company CLARIANT
Tableau 1Table 1
Figure imgf000010_0001
Figure imgf000010_0001

Claims

REVENDICATIONS
1 Composition de polymère fluoré à tenue au feu améliorée comprenant en poids, le total étant 100% : • 60 à 90 % d'au moins un polymère fluoré,1 composition of fluoropolymer with improved fire resistance comprising by weight, the total being 100%: • 60 to 90% of at least one fluoropolymer,
• 0,1 à 5 % d'un polyether,• 0.1 to 5% of a polyether,
• le complément étant au moins une charge inorganique à base de silicate.• the complement being at least one inorganic filler based on silicate.
2 Composition selon la revendication 1 dans laquelle le polymère fluoré est un PVDF homopolymere ou copolymère.2 Composition according to claim 1 in which the fluoropolymer is a homopolymer or copolymer PVDF.
3 Composition selon l'une quelconque des revendications précédentes dans laquelle le polyether est un PEG de masse Mn comprise entre 400 et 15000 g/mole.3 Composition according to any one of the preceding claims in which the polyether is a PEG with a mass Mn of between 400 and 15,000 g / mole.
4 Composition selon l'une quelconque de revendications précédentes dans laquelle la charge inorganique est choisie parmi les alumino- silicate et les silicates de magnésium.4 Composition according to any one of the preceding claims in which the inorganic filler is chosen from aluminosilicate and magnesium silicates.
5 Composition selon la revendication 4 dans laquelle la charge inorganique est choisie parmi le kaolin, le talc et le mica.5 Composition according to claim 4 in which the inorganic filler is chosen from kaolin, talc and mica.
6 Composition selon l'une quelconque des revendications précédentes dans laquelle une partie de la charge inorganique est remplacée par du trioxyde d'antimoine.6 Composition according to any one of the preceding claims in which part of the inorganic filler is replaced by antimony trioxide.
7 Composition selon la revendication 6 dans laquelle la proportion de trioxyde d'antimoine peut être de 5 à 30% en poids de la masse totale de la charge inorganique. 8 Composition selon l'une quelconque de revendications précédentes dans laquelle les proportions de polymère fluoré sont de 75 à 857 Composition according to claim 6 in which the proportion of antimony trioxide can be from 5 to 30% by weight of the total mass of the inorganic filler. 8 Composition according to any one of the preceding claims in which the proportions of fluoropolymer are from 75 to 85
%.%.
9 Composition selon l'une quelconque de revendications précédentes dans laquelle les proportions de polyether sont de 0,5 à 2 %.9 Composition according to any one of the preceding claims, in which the proportions of polyether are from 0.5 to 2%.
10 Câbles électriques ou de télécommunication ayant un isolant et/ou une gaine constituée d'une composition selon l'une quelconque des revendications précédentes. 10 Electric or telecommunication cables having an insulator and / or a sheath consisting of a composition according to any one of the preceding claims.
PCT/FR2002/001859 2001-06-08 2002-06-03 Fluorinated polymer composition with improved fire resistance WO2002100942A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4804702A (en) * 1986-04-02 1989-02-14 Pennwalt Corporation Low smoke and reduced flame fluorinated polymer compositions and cable constructions
US5552199A (en) * 1994-09-02 1996-09-03 Minnesota Mining And Manufacturing Company Melt-processable electroconductive fluoroplastic

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4804702A (en) * 1986-04-02 1989-02-14 Pennwalt Corporation Low smoke and reduced flame fluorinated polymer compositions and cable constructions
US5552199A (en) * 1994-09-02 1996-09-03 Minnesota Mining And Manufacturing Company Melt-processable electroconductive fluoroplastic

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