EP0010586B2 - Flame retardant insulating material for an electrical cable and electrical cable made with such a material - Google Patents

Flame retardant insulating material for an electrical cable and electrical cable made with such a material Download PDF

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Publication number
EP0010586B2
EP0010586B2 EP79103159A EP79103159A EP0010586B2 EP 0010586 B2 EP0010586 B2 EP 0010586B2 EP 79103159 A EP79103159 A EP 79103159A EP 79103159 A EP79103159 A EP 79103159A EP 0010586 B2 EP0010586 B2 EP 0010586B2
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EP
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Prior art keywords
matrix
agent
material according
fire
diphosphaspiro
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EP79103159A
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German (de)
French (fr)
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EP0010586B1 (en
EP0010586A1 (en
Inventor
Jean-Pierre Bonicel
Christian Cottevieille
Michel Maucolot
Madeleine Prigent
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Cables de Lyon SA
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Cables de Lyon SA
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Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/907—Nonurethane flameproofed cellular product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating

Definitions

  • the present invention relates to a fireproof insulating material for an electric cable, as well as an electric cable obtained using this material.
  • Such materials are used in particular for the insulation of electrical conductors providing static connections in a telephone exchange. They must meet many conditions of dielectric strength and mechanical strength, especially when hot, and in addition, in the event of a fire in the central, they must on the one hand burn with difficulty, that is to say have an index of high oxygen, and on the other hand, if they burn, do not generate excessively corrosive vapors.
  • IOL limiting oxygen index
  • the insulating material consists of a matrix formed by an organic polymer and optional additives, in particular flame retardants.
  • Crosslinked polyethylene can also be used, but crosslinking requires significant investment if the material is to be extruded at high speed.
  • Copolymers of propylene and ethylene, high density polyethylene and thermoplastic polyesters can also be satisfactory as regards mechanical properties and hot aging, but this type of material like the previous one requires effective flame retardancy to be used.
  • the original IOL of propylene and ethylene copolymers with a low ethylene content is indeed close to 18, whereas an IOL of 27 should be obtained.
  • alumina trihydrate and organic materials containing chlorine or bromine have been used, for example exabromocyclododecane, tetrabromoethane or halogenated aromatic compounds.
  • US-A-3 997 505 describes flame retardant polymer compositions comprising in particular as flame retardant 3,9-bis (2,3-dibromopropoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro (5 , 5) undecane-3.9-dioxide or 3.9 bis (2,2 [dibromomethyl] -3-chloropropoxy) -2,4,8,10-tetraoxa 3,9-diphosphaspiro (5,5) undecane-3, 9-dioxide, as well as antimony oxide and a free radical generator formed by an organic peroxide.
  • the object of the present invention is to produce a fire-retardant insulating material for an electric cable which has both a high oxygen index, a low chemical aggressiveness of the vapors released in the event of combustion, good mechanical and electrical qualities, in particular for hot and cold (winding), good resistance to thermal aging and low cost price.
  • the invention further extends to an electric cable comprising at least one sheath made of a material as defined above, and preferably an internal sheath and an external sheath made of said material, separated by an envelope of glass silk or of mica.
  • flame retardant A 3-9-bis (2,2-dibromomethyl-3-chloropropoxy) -2,4,8,10- tetraoxa-3,9-diphosphaspiro (5,5) undecane-3,9-dioxide, which will be designated hereinafter flame retardant A.
  • flame retardant A 3-9-bis (2,2-dibromomethyl-3-chloropropoxy) -2,4,8,10- tetraoxa-3,9-diphosphaspiro (5,5) undecane-3,9-dioxide.
  • this compound contains phosphorus in its molecule. The role of phosphorus appears to be to slow the propagation of the flame, whether it is incorporated into the molecule of the organic flame retardant or added to it in the form of red phosphorus.
  • thermoplastic polyester forming the matrix it is possible in particular to use polybutane-1,4-diol and teramethylene glycol terephthalate marketed under the trade name Hytrel by the company DU PONT DE NEMOURS or that marketed under the name 1010-5 by KOPPERS Company.
  • polybutane-1,4-diol and teramethylene glycol terephthalate marketed under the trade name Hytrel by the company DU PONT DE NEMOURS or that marketed under the name 1010-5 by KOPPERS Company.
  • a mixture of polypropylene and 12.5% by weight of the flame retardant A intimately mixed in a kneader and then subjected to an injection molding, gives an oxygen index I.O.L. 25.5 in the test according to the American standard ASTMD-2863 of 1970. After adding 0.5 part by weight of 2,3-dimethyl-2,3-diphenylbutane (free radical generator), an index d is obtained oxygen of 30.
  • An oxygen index of 27 is generally considered to be very satisfactory.
  • a mineral antimony compound such as antimony oxide, should be added to the mixture to fix the bromine, chlorine, hydrobromic acid or hydrochloric acid released by the decomposition of the flame retardant.
  • a matrix consisting of a copolymer of propylene and ethylene, in which the proportion of ethylene is preferably less than 10% by weight, it will preferably be used as flame retardant 3,9-bis ( 2,3-dibromopropoxy) 2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undécane-3,9-dioxide, which will be designated hereinafter flame retardant B, or hexabromocyclododecane of formula which will be designated below the flame retardant C.
  • a mixture of 100 parts of a copolymer of propylene and ethylene with 2.8% of ethylene, of 15 parts of the flame retardant B or C and 10 parts of antimony oxide, added with the known antioxidants and anti-brass necessary for the processing and good aging of the material for example the phenolic derivatives marketed under the names Irganox 10-10 or 10-76 by the company CIBA GEIGY
  • the known antioxidants and anti-brass necessary for the processing and good aging of the material for example the phenolic derivatives marketed under the names Irganox 10-10 or 10-76 by the company CIBA GEIGY
  • Oxygen indices of 24.5 are obtained with the flame retardant B and 29 with the flame retardant C.
  • Drip resistance when required, can be improved by adding carbon black.
  • the material can be made cellular by the addition of very fine grains of a chemical compound which decomposes at its extrusion temperature with the release of a gas, in particular azodicarbonamide, and possibly of a nucleating agent.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)

Description

La présente invention concerne un matériau isolant ignifugé pour câble électrique, ainsi qu'un câble électrique obtenu à l'aide de ce matériau.The present invention relates to a fireproof insulating material for an electric cable, as well as an electric cable obtained using this material.

De tels matériaux sont notamment utilisés pour l'isolation des conducteurs électriques assurant les connexions statiques dans un central téléphonique. Ils doivent satisfaire à de nombreuses conditions de rigidité diélectrique et de tenue mécanique, notamment à chaud, et en outre, en cas d'incendie du central, ils doivent d'une part brûler difficilement, c'est-à-dire présenter un indice d'oxygène élevé, et d'autre part, s'ils brûlent, ne pas engendrer de vapeurs excessivement corrosives. On sait que l'indice d'oxygène limite (I.O.L.) (en anglais « limiting oxygen index ») est la teneur en oxygène minimale, dans un mélange oxygène-azote, pour entretenir la combustion d'un matériau disposé verticalement dans ce mélange et allumé à sa partie supérieure.Such materials are used in particular for the insulation of electrical conductors providing static connections in a telephone exchange. They must meet many conditions of dielectric strength and mechanical strength, especially when hot, and in addition, in the event of a fire in the central, they must on the one hand burn with difficulty, that is to say have an index of high oxygen, and on the other hand, if they burn, do not generate excessively corrosive vapors. We know that the limiting oxygen index (IOL) is the minimum oxygen content, in an oxygen-nitrogen mixture, to maintain the combustion of a material placed vertically in this mixture and lit at its top.

Le matériau isolant est constitué d'une matrice formée par un polymère organique et d'additifs éventuels, notamment des agents ignifugeants.The insulating material consists of a matrix formed by an organic polymer and optional additives, in particular flame retardants.

Les corps les plus couramment utilisés dans les centraux téléphoniques étaient jusqu'ici les polychlorures de vinyle qui ont déjà de par leur structure un indice d'oxygène élevé mais présentent l'inconvénient de dégager des vapeurs corrosives d'acide chlorhydrique très gênantes. D'autres matériaux sont susceptibles d'être utilisés - polyamides, silicones, dérivés fluorés - mais leur prix élevé limite leur utilisation.The bodies most commonly used in telephone exchanges have so far been polyvinyl chloride which already has a high oxygen index by structure but has the disadvantage of giving off very troublesome corrosive hydrochloric acid vapors. Other materials are likely to be used - polyamides, silicones, fluorinated derivatives - but their high price limits their use.

Le polyéthylène réticulé (PRC) peut également être utilisé, mais la réticulation nécessite des investissements importants si on veut extruder le matériau à grande vitesse. Les copolymères de propylène et d'éthylène, le polyéthylène à haute densité et les polyesters thermoplastiques peuvent également être satisfaisants quant aux propriétés mécaniques et au vieillissement à chaud, mais ce type de matériau comme le précédent nécessite une ignifugation efficace pour être utilisé. L'IOL d'origine des copolymères de propylène et d'éthylène à faible teneur en éthylène est en effet voisin de 18 alors qu'il convient d'obtenir un IOL de 27.Crosslinked polyethylene (PRC) can also be used, but crosslinking requires significant investment if the material is to be extruded at high speed. Copolymers of propylene and ethylene, high density polyethylene and thermoplastic polyesters can also be satisfactory as regards mechanical properties and hot aging, but this type of material like the previous one requires effective flame retardancy to be used. The original IOL of propylene and ethylene copolymers with a low ethylene content is indeed close to 18, whereas an IOL of 27 should be obtained.

On connaît de nombreux agents ignifugeants, mais le problème de la résistance au feu est rendu complexe par le fait que des conditions très diverses doivent être satisfaites en même temps et que l'action d'un même agent ignifugeant varie en fonction de la matrice et des autres additifs.Many flame retardants are known, but the problem of fire resistance is made complex by the fact that very diverse conditions must be satisfied at the same time and that the action of the same flame retardant varies according to the matrix and other additives.

On a notamment utilisé l'alumine trihydratée et des matériaux organiques contenant du chlore ou du brome, par exemple l'exabromocyclododécane, le tétrabromoéthane ou des composés aromatiques halogénés.In particular, alumina trihydrate and organic materials containing chlorine or bromine have been used, for example exabromocyclododecane, tetrabromoethane or halogenated aromatic compounds.

On sait par ailleurs que l'addition de petites quantités d'un générateur de radicaux libres peut augmenter l'efficacité de l'agent ignifugeant.It is also known that the addition of small amounts of a free radical generator can increase the effectiveness of the flame retardant.

Un article de Eichhorn (Amer. Chem. Soc. Div. Org. Coatings Plastics Chem. Preprints, 23 (1), 37 (1964) et J. Appl. Polymer Sci., 8,2497 (1964)) mentionne l'utilisation de peroxyde de dicumyle avec un agent ignifugeant bromé aliphatique qui est le tétrabromoéthane, dans une matrice de polystyrène.An article by Eichhorn (Amer. Chem. Soc. Div. Org. Coatings Plastics Chem. Preprints, 23 (1), 37 (1964) and J. Appl. Polymer Sci., 8.2497 (1964)) mentions the use of dicumyl peroxide with an aliphatic brominated flame retardant which is tetrabromoethane, in a polystyrene matrix.

Le brevet américain n° 3 850 882 (Underwood et autres) mentionne l'utilisation d'un générateur de radicaux libres carbone-carbone, c'est-à-dire dont la molécule se rompt entre deux atomes de carbone, avec des agents ignifugeants bromés nombreux et divers, mais qui contiennent tous au moins un noyau aromatique.US Patent No. 3,850,882 (Underwood and others) mentions the use of a carbon-carbon free radical generator, that is to say the molecule of which breaks between two carbon atoms, with flame retardants numerous and diverse bromines, but all of which contain at least one aromatic nucleus.

Le brevet US-A-3 997 505 décrit des compositions polymères ignifugées comprenant notamment comme agent ignifugeant le 3,9-bis (2,3-dibromopropoxy)-2,4,8,10-tétraoxa-3,9-diphosphaspiro (5,5) undécane-3.9-dioxyde ou le 3,9 bis(2,2[dibromométhyl]-3-chloropropoxy)-2,4,8,10-tétraoxa 3,9-diphosphaspiro (5,5) undécane-3,9-dioxyde, ainsi que de l'oxyde d'antimoine et un générateur de radicaux libres formé par un peroxyde organique.US-A-3 997 505 describes flame retardant polymer compositions comprising in particular as flame retardant 3,9-bis (2,3-dibromopropoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro (5 , 5) undecane-3.9-dioxide or 3.9 bis (2,2 [dibromomethyl] -3-chloropropoxy) -2,4,8,10-tetraoxa 3,9-diphosphaspiro (5,5) undecane-3, 9-dioxide, as well as antimony oxide and a free radical generator formed by an organic peroxide.

Le brevet US-A-3 655 589 décrit des compositions polymères ignifugées comprenant notamment comme agent ignifugeant l'hexabromocyclododécane, ainsi qu'un copolymère organique halogéné, un dérivé de l'antimoine et un générateur de radicaux libres tel qu'un peroxyde organique ou un dérivé azo organique.US-A-3,655,589 describes flame retardant polymer compositions comprising in particular as flame retardant hexabromocyclododecane, as well as a halogenated organic copolymer, an antimony derivative and a free radical generator such as an organic peroxide or an organic azo derivative.

Des essais de laboratoire ont montré que l'utilisation d'un générateur de radicaux libres carbone-carbone avec divers composés aromatiques connus comme agents ignifugeants tels que le décabromodi- phényloxyde et le 1-2 bis (2,4,6-tribromophénoxyéthane) a également donné des résultats mauvais. On entend ici par résultat mauvais l'obtention d'un indice d'oxygène inférieur à 22 malgré l'adjonction d'une proportion optimale d'oxyde d'antimoine SbZ03.Laboratory tests have shown that the use of a carbon-carbon free radical generator with various aromatic compounds known as flame retardants such as decabromodiphenyloxide and 1-2 bis (2,4,6-tribromophenoxyethane) has also gave bad results. The term poor result is understood here to mean obtaining an oxygen index of less than 22 despite the addition of an optimal proportion of antimony oxide Sb Z 0 3 .

La présente invention a pour but la réalisation d'un matériau isolant ignifugé pour câble électrique qui présente à la fois un indice d'oxygène élevé, une faible agressivité chimique des vapeurs dégagées en cas de combustion, de bonnes qualités mécaniques et électriques, notamment à chaud et à froid (enroulement), une bonne résistance au vieillissement thermique et un faible prix de revient.The object of the present invention is to produce a fire-retardant insulating material for an electric cable which has both a high oxygen index, a low chemical aggressiveness of the vapors released in the event of combustion, good mechanical and electrical qualities, in particular for hot and cold (winding), good resistance to thermal aging and low cost price.

Elle a pour objet un matériau isolant ignifugé pour câble électrique comportant :

  • a) une matrice formée par un polymère synthétique,
  • b) un agent ignifugeant constitué par un dérivé halogéné stable à la température d'extrusion de la matrice, et se décomposant à une température supérieure, et dans lequel au moins la majorité des substituants halogènes sont des atomes de brome,
  • c) un composé d'antimoine susceptible de réagir avec le brome de l'agent ignifugeant lors d'une combustion, et
  • d) un générateur de radicaux libres, ce générateur ne se décomposant qu'à une température supérieure à la température d'extrusion de la matrice, et étant susceptible de se couper de façon homolytique entre deux atomes de carbone à ladite température supérieure, caractérisé en ce que l'agent ignifugeant comprend un membre de groupe constitué par le 3,9-bis(2,3-dibromopropoxy)-2,4,8,10-tétraoxa 3,9-diphosphaspiro (5,5) undécane-3,9-dioxyde, le 3,9-bis-(2,2)[-dibromométhyl]-3-chloropro- poxy)-2,4,8,10-tétraoxa-3,9-diphosphaspiro (5,5) undécane-3,9-dioxyde et l'hexabromocyclododécane, ce dernier étant additionné d'environ 2% en poids de phosphore rouge par rapport au matériau.
It relates to a fireproof insulating material for electric cable comprising:
  • a) a matrix formed by a synthetic polymer,
  • b) a flame retardant agent consisting of a halogenated derivative stable at the extrusion temperature of the matrix, and decomposing at a higher temperature, and in which at least the majority of the halogen substituents are bromine atoms,
  • c) an antimony compound capable of reacting with the bromine of the flame retardant during combustion, and
  • d) a free radical generator, this generator decomposing only at a temperature higher than the extrusion temperature of the matrix, and being capable of cutting homolytically between two carbon atoms at said higher temperature, characterized in that the flame-retardant agent comprises a group member consisting of 3,9-bis (2,3-dibromopropoxy) -2,4,8,10-tetraoxa 3,9-diphosphaspiro (5,5) undecane-3, 9-dioxide, 3,9-bis- (2,2) [- dibromomethyl] -3-chloroproxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undecane- 3,9-dioxide and hexabromocyclododecane, the latter being added with about 2% by weight of red phosphorus relative to the material.

Il répond en outre de préférence à au moins l'une des caractéristiques suivantes :

  • - le polymère synthétique est un membre du groupe constitué par le polyéthylène à haute densité et les polyesters thermoplastiques
  • - sa matrice est le polypropylène ou un polyester thermoplastique et son agent ignifugeant le 3,9- bis (2,2-[dibromométhyl]-3-chloropropoxy)-2,4,8,10-tétraoxa-3,9 diphosphaspiro (5,5) undécane-3,9 dioxyde
  • - sa matrice est un copolymère de propylène et d'éthylène contenant moins de 10% en poids d'éthylène, et son agent ignifugeant le 3,9-bis (2,3-dibromopropoxy) 2,4,8,10-tétraoxa-3,9-diphosphaspiro (5,5) undécane-3,9-dioxyde ou l'hexabromocyclododécane additionné de phosphore rouge
  • - la proportion d'agent ignifugeant est comprise entre 2 % et 30 % du poids de la matrice
  • - il contient en outre du noir de carbone
  • - il présente une structure cellulaire obtenue par décomposition d'un agent poroforme se décomposant à la température d'extrusion de la matrice, de préférence l'azodicarbonamide.
It also preferably meets at least one of the following characteristics:
  • - the synthetic polymer is a member of the group consisting of high density polyethylene and thermoplastic polyesters
  • - its matrix is polypropylene or a thermoplastic polyester and its flame retardant agent 3,9- bis (2,2- [dibromomethyl] -3-chloropropoxy) -2,4,8,10-tétraoxa-3,9 diphosphaspiro (5 , 5) undecane-3.9 dioxide
  • - Its matrix is a copolymer of propylene and ethylene containing less than 10% by weight of ethylene, and its flame retardant agent 3,9-bis (2,3-dibromopropoxy) 2,4,8,10-tetraoxa- 3,9-diphosphaspiro (5,5) undecane-3,9-dioxide or hexabromocyclododecane supplemented with red phosphorus
  • - the proportion of flame retardant is between 2% and 30% of the weight of the matrix
  • - it also contains carbon black
  • - It has a cellular structure obtained by decomposition of a poroform agent decomposing at the extrusion temperature of the matrix, preferably azodicarbonamide.

L'invention s'étend en outre à un câble électrique comprenant au moins une gaine en un matériau tel que défini ci-dessus, et de préférence une gaine interne et une gaine externe en ledit matériau, séparées par une enveloppe de soie de verre ou de mica.The invention further extends to an electric cable comprising at least one sheath made of a material as defined above, and preferably an internal sheath and an external sheath made of said material, separated by an envelope of glass silk or of mica.

Dans le cas d'une matrice constituée de polypropylène ou d'un polyester thermoplastique, on utilisera de préférence comme agent ignifugeant le 3,9-bis (2,2-dibromométhyl-3-chloropropoxy)-2,4,8,10-tétraoxa-3,9-diphosphaspiro (5,5) undécane-3,9-dioxyde, qui sera désigné ci-après l'agent ignifugeant A. On notera que ce composé contient du phosphore dans sa molécule. Le rôle du phosphore paraît être de ralentir la propagation de la flamme, qu'il soit incorporé à la molécule de l'agent ignifugeant organique ou ajouté à celui-ci sous forme de phosphore rouge. Comme polyester thermoplastique formant la matrice, on peut utiliser notamment le polytéréphtalate de butane-1,4-diol et de téraméthylène- glycol commercialisé sous la désignation commerciale Hytrel par la Société DU PONT DE NEMOURS ou celui commercialisé sous la désignation 1010-5 par la Société KOPPERS. A titre d'exemple, un mélange de polypropylène et de 12,5 % en poids de l'agent ignifugeant A, intimement mélangés dans un malaxeur puis soumis à un moulage par injection, donne un indice d'oxygène I.O.L. de 25,5 à l'essai selon la norme américaine ASTMD-2863 de 1970. Après addition de 0,5 partie en poids de 2,3-diméthyl-2,3-diphénylbutane (générateur de radicaux libres) on obtient un indice d'oxygène de 30. Un indice d'oxygène de 27 est généralement considéré comme très satisfaisant. Il convient en pratique d'ajouter au mélange un composé minéral d'antimoine, tel que de l'oxyde d'antimoine, pour fixer le brome, le chlore, l'acide bromhydrique ou l'acide chlorhydrique dégagés par la décomposition de l'agent ignifugeant.In the case of a matrix consisting of polypropylene or of a thermoplastic polyester, it will preferably be used as flame retardant 3,9-bis (2,2-dibromomethyl-3-chloropropoxy) -2,4,8,10- tetraoxa-3,9-diphosphaspiro (5,5) undecane-3,9-dioxide, which will be designated hereinafter flame retardant A. It will be noted that this compound contains phosphorus in its molecule. The role of phosphorus appears to be to slow the propagation of the flame, whether it is incorporated into the molecule of the organic flame retardant or added to it in the form of red phosphorus. As thermoplastic polyester forming the matrix, it is possible in particular to use polybutane-1,4-diol and teramethylene glycol terephthalate marketed under the trade name Hytrel by the company DU PONT DE NEMOURS or that marketed under the name 1010-5 by KOPPERS Company. For example, a mixture of polypropylene and 12.5% by weight of the flame retardant A, intimately mixed in a kneader and then subjected to an injection molding, gives an oxygen index I.O.L. 25.5 in the test according to the American standard ASTMD-2863 of 1970. After adding 0.5 part by weight of 2,3-dimethyl-2,3-diphenylbutane (free radical generator), an index d is obtained oxygen of 30. An oxygen index of 27 is generally considered to be very satisfactory. In practice, a mineral antimony compound, such as antimony oxide, should be added to the mixture to fix the bromine, chlorine, hydrobromic acid or hydrochloric acid released by the decomposition of the flame retardant.

Dans le cas d'une matrice constituée d'un copolymère de propylène et d'éthylène, dans lequel la proportion d'éthylène est de préférence inférieure à 10 % en poids, on utilisera de préférence comme agent ignifugeant le 3,9-bis (2,3-dibromopropoxy) 2,4,8,10-tétraoxa-3,9-diphosphaspiro (5,5) undécane-3,9-dioxyde, qui sera désigné ci-après l'agent ignifugeant B, ou l'hexabromocyclododécane de formule

Figure imgb0001
qui sera désigné ci-après l'agent ignifugeant C. A titre d'exemple, un mélange de 100 parties d'un copolymère de propylène et d'éthylène à 2,8 % d'éthylène, de 15 parties de l'agent ignifugeant B ou C et de 10 parties d'oxyde d'antimoine, additionnés des antioxydants et anticuivres connus nécessaires à la mise en oeuvre et au bon vieillissement du matériau (par exemple les dérivés phénoliques commercialisés sous les désignations Irganox 10-10 ou 10-76 par la société CIBA GEIGY) est intimement malaxé vers 160 °C pendant quelques minutes, puis granulé et extrudé autour d'un fil conducteur. On obtient des indices d'oxygène de 24,5 avec l'agent ignifugeant B et de 29 avec l'agent ignifugeant C. En répétant l'essai avec addition au mélange comme générateur de radicaux libres de 0,4 % en poids de 2,3-diméthyl 2,3-diphénylbutane avec l'agent ignifugeant B et de 0,5 % en poids du même composé avec l'agent ignifugeant C, on obtient respectivement des indices d'oxygène de 29,5 et 32. Avec un mélange de 100 parties d'un copolymère de propylène et d'éthylène à 2,8 % d'éthylène, de 6 parties de l'agent ignifugeant C et de 6 parties d'oxyde d'antimoine, additionné des mêmes antioxydants et anti-cuivres, extrudé autour d'un fil conducteur de la même manière, on obtient des indices d'oxygène de 25 lorsque le mélange ne comporte pas de générateur de radiaux libres, et de 31 lorsqu'il est additionné de 0,4 % en poids de 2.3-diméthyl-2.3 diphénylbutane. Seules les compositions mettant en oeuvre les agents ignifugeants A et B sont illustratives de l'invention.In the case of a matrix consisting of a copolymer of propylene and ethylene, in which the proportion of ethylene is preferably less than 10% by weight, it will preferably be used as flame retardant 3,9-bis ( 2,3-dibromopropoxy) 2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undécane-3,9-dioxide, which will be designated hereinafter flame retardant B, or hexabromocyclododecane of formula
Figure imgb0001
 which will be designated below the flame retardant C. For example, a mixture of 100 parts of a copolymer of propylene and ethylene with 2.8% of ethylene, of 15 parts of the flame retardant B or C and 10 parts of antimony oxide, added with the known antioxidants and anti-brass necessary for the processing and good aging of the material (for example the phenolic derivatives marketed under the names Irganox 10-10 or 10-76 by the company CIBA GEIGY) is intimately kneaded at around 160 ° C. for a few minutes, then granulated and extruded around a conducting wire. Oxygen indices of 24.5 are obtained with the flame retardant B and 29 with the flame retardant C. By repeating the test with addition to the mixture as a free radical generator of 0.4% by weight of 2 , 3-dimethyl 2,3-diphenylbutane with the flame retardant B and 0.5% by weight of the same compound with the flame retardant C, we obtain oxygen indices of 29.5 and 32 respectively. mixture of 100 parts of a copolymer of propylene and ethylene with 2.8% of ethylene, of 6 parts of the flame retardant C and of 6 parts of antimony oxide, added with the same antioxidants and anti brass, extruded around a conducting wire in the same way, we obtain oxygen indices of 25 when the mixture does not include a free radical generator, and of 31 when it is added with 0.4% by weight of 2.3-dimethyl-2.3 diphenylbutane. Only the compositions using the flame retardants A and B are illustrative of the invention.

Les fils gainés à l'aide des matériaux ci-dessus répondent par ailleurs aux qualités chimiques, électriques et mécaniques requises par les câbles utilisés dans les centraux téléphoniques, notamment

  • - un point éclair supérieur à 350 °C
  • - une agressivité chimique après combustion faible
  • - une bonne rigidité diélectrique
  • - un maintien satisfaisant des propriétés mécaniques après vieillissement de 5 jours à 100 °C
  • - une bonne résistance mécanique à -10°C
  • - un enroulement sans fissure ni déformation d'un fil de diamètre 1 mm sur un mandrin de diamètre 20 mm pendant une heure à 135 °C
  • - une bonne résistance aux solvants, aux acides et aux bases.
The wires sheathed using the above materials also meet the chemical qualities, electrical and mechanical requirements for cables used in telephone exchanges, in particular
  • - a flash point higher than 350 ° C
  • - chemical aggressiveness after weak combustion
  • - good dielectric strength
  • - satisfactory maintenance of the mechanical properties after aging for 5 days at 100 ° C.
  • - good mechanical resistance at -10 ° C
  • - a winding without cracking or deformation of a wire of diameter 1 mm on a mandrel of diameter 20 mm for one hour at 135 ° C
  • - good resistance to solvents, acids and bases.

La résistance au gouttage, quand elle est requise, peut être améliorée par addition de noir de carbone.Drip resistance, when required, can be improved by adding carbon black.

Le matériau peut être rendu alvéolaire par addition de grains très fins d'un composé chimique se décomposant à sa température d'extrusion avec dégagement d'un gaz, notamment l'azodicarbonamide, et éventuellement d'un agent de nucléation.The material can be made cellular by the addition of very fine grains of a chemical compound which decomposes at its extrusion temperature with the release of a gas, in particular azodicarbonamide, and possibly of a nucleating agent.

On peut enfin améliorer encore la résistance à la flamme des câbles gainés avec le matériau ci-dessus en les munissant de deux gaines coaxiales en ce matériau séparées par une enveloppe en soie de verre ou de mica, formée par exemple par un ruban enroulé autour de la gaine intérieure.Finally, it is possible to further improve the flame resistance of the cables sheathed with the above material by providing them with two coaxial sheaths in this material separated by a glass or mica silk envelope, formed for example by a ribbon wound around the inner sheath.

On comprendra que diverses modifications peuvent être apportées au matériau et au câble qui viennent d'être décrits sans sortir du cadre de l'invention, notamment par incorporation au matériau d'additifs destinés à lui conférer des propriétés particulières.It will be understood that various modifications can be made to the material and to the cable which have just been described without departing from the scope of the invention, in particular by incorporating into the material additives intended to give it particular properties.

Claims (8)

1. A fire-proof insulating material for an electric cable, said material including :
a) a matrix made of a synthetic polymer,
b) a fire-proofing agent comprising a halogenated derivative which is stable at the extrusion temperature of the matrix, and decomposes at a higher temperature, and wherein at least the majority of the halogen substituents are bromine atoms,
c) an antimony compound which is capable of reacting with the bromine of the fire-proofing agent during combustion, and
d) a free radicals forming agent, this agent decomposing only at a temperature higher than the extrusion temperature of the matrix, and being able to split in a homolytic way between two carbon atoms at said higher temperature,

characterized in that the fire-proofing agent is a member of the group consisting of 3,9-di(2,3-dibromopropoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undecane-3,9-dioxyde, 3,9-di (2,2-[dibromomethyl]-3-chloropropoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undecane-3,9-dioxide and hexabromocyclododecane, the latter being added with about 2 % by weight of red phosphoros with respect to the material.
2. A material according to claim 1, characterized in that the synthetic polymer is selected from the group consisting of high density polyethylene and thermoplastic polyesters.
3. A material according to claims 1 or 2, characterized in that its matrix is polypropylene or a thermoplastic polyester and its fire-proofing agent is 3,9-di(2,2-[dibromomethyl]-3-chloropropoxy)-2,4,8,10-tetraoxa-3,9 diphosphaspiro (5,5) undecane-3,9 dioxide.
4. A material according to claims 1 or 2, characterized in that its matrix is a copolymer of propylene and ethylene containing less than 10 % by weight of ethylene, and its fireproofing agent is the 3,9-di(2,3-dibromopropoxy) 2,4-8,10-tetra-oxa-3,9-diphosphaspiro (5,5) undecane-3,9-dioxide or hexabromo-cyclododecane, the latter being added with red phosphoros.
5. A material according to one of claims 1 to 4, characterized in that the proportion of the fire- proofing agent ranges between 2 % and 30 % by weight of the matrix.
6. A material according to one of claims 1 to 5, characterized in that it contains carbon black.
7. A material according to one of claims 1 to 6, characterized in that it has a cellular structure obtained by decomposing a poreforming agent, preferably azodicarbonamide, which decomposes at the extrusion temperature of the matrix.
8. An electric cable comprising at least one sheath of a material according to one of claims 1 to 7, and preferably an inner sheath and an outer sheath of said material, separated by an envelope of glass silk or mica.
EP79103159A 1978-11-07 1979-08-27 Flame retardant insulating material for an electrical cable and electrical cable made with such a material Expired EP0010586B2 (en)

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FR7831467 1978-11-07
FR7831467 1978-11-07

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EP0224281B1 (en) * 1982-10-01 1990-12-27 Raychem Limited Flame retarded cladding
NO153511C (en) * 1983-08-25 1986-04-02 Standard Tel Kabelfab As FIRE AND OIL RESISTANT CABLE.
EP3397672A1 (en) 2015-12-31 2018-11-07 SABIC Global Technologies B.V. Polyetherimide compositions, methods of manufacture, and articles prepared therefrom

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DE1260136B (en) * 1965-07-21 1968-02-01 Basf Ag Molding compounds for the production of self-extinguishing moldings
GB1221950A (en) * 1967-03-03 1971-02-10 Bostik Ltd Improvements in or relating to sound-deadening material
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DE2966496D1 (en) 1984-01-26
EP0010586A1 (en) 1980-05-14
JPS6234783B2 (en) 1987-07-29
JPS5565244A (en) 1980-05-16
US4324863A (en) 1982-04-13
CA1129636A (en) 1982-08-17

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