EP0010586B2 - Feuerhemmendes isolierendes Material für elektrisches Kabel und mit diesem Material erhaltenes elektrisches Kabel - Google Patents

Feuerhemmendes isolierendes Material für elektrisches Kabel und mit diesem Material erhaltenes elektrisches Kabel 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
Authority
EP
European Patent Office
Prior art keywords
matrix
agent
material according
fire
diphosphaspiro
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
EP79103159A
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English (en)
French (fr)
Other versions
EP0010586A1 (de
EP0010586B1 (de
Inventor
Jean-Pierre Bonicel
Christian Cottevieille
Michel Maucolot
Madeleine Prigent
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cables de Lyon SA
Original Assignee
Cables de Lyon SA
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Publication date
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Application filed by Cables de Lyon SA filed Critical Cables de Lyon SA
Publication of EP0010586A1 publication Critical patent/EP0010586A1/de
Application granted granted Critical
Publication of EP0010586B1 publication Critical patent/EP0010586B1/de
Publication of EP0010586B2 publication Critical patent/EP0010586B2/de
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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.

Landscapes

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

Claims (8)

1. Feuerhemmendes Isoliermaterial für elektrische Kabel, mit
a) einer aus einem synthetischen Polymer gebildeten Matrix,
b) einem feuerhemmend machenden Mittel mit einem bei der Extrusionstemperatur der Matrix stabilen halogenierten Derivat, das sich bei einer höheren Temperatur zersetzt und in dem mindestens die Mehrheit der Halogensubstituenten Bromatome sind,
c) einer Antimon-Verbindung, die bei einer Verbrennung mit dem Brom des feuerhemmend machenden Mittels reagieren kann, und
d) einem Freiradikal-Bildner, der sich erst bei einer Temperatur zersetzt, die höher ist als die Extrusionstemperatur der Matrix, und der sich auf homolytische Weise zwischen zwei Kohlenstoffatomen bei der genannten höheren Temperatur spalten kann,

dadurch gekennzeichnet, daß das feuerhemmend machende Mittel ein Vertreter aus der Gruppe 3,9-Bis(2,3-dibromopropoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undecan-3,9-Dioxid, 3,9-Bis(2,2-[dibromomethy)]-3-ch)oropropoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undecan-3,9-Dioxid und Hexabromocylcododecan ist, wobei letzterem ungefähr 2 Gew.% roter Phosphor, bezogen auf das Material, zugesetzt ist.
2. Material nach Anspruch 1, dadurch gekennzeichnet, daß das synthetische Polymer ein Vertreter der Gruppe Polyäthylen hoher Dichte und thermoplastisches Polyester ist.
3. Material nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß seine Matrix Polypropylen oder ein thermoplastisches Polyester ist, und daß sein feuerhemmend machendes Mittel das 3,9-Bis(2,2-[dibromomethyl]-3-chloropropoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undecan-3,9-Dioxid ist.
4. Material nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß seine Matrix ein Copolymer von Propylen und Äthylen ist, das weniger als 10 Gew.% Äthylen enthält, und daß sein feuerhemmend machendes Mittel das 3,9-Bis(2,3-dibromopropoxy) 2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5) undecan-3,9-dioxid oder das Hexabromocyclododecan ist, wobei letzterem roter Phosphor zugesetzt ist.
5. Material nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Anteil des feuerhemmend machenden Mittels zwischen 2 und 30 % des Gewichtes der Matrix beträgt.
6. Material nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es außerdem Ruß enthält.
7. Material nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es eine Zellstruktur aufweist, die durch Zersetzung eines Porenbildners, vorzugsweise Azodicarbonamid, der sich bei der Extrusionstemperatur der Matrix zersetzt, entsteht.
8. Elektrisches Kabel, das mindestens eine Hülle aus einem Material gemäß einem der Ansprüche 1 bis 7, und vorzugsweise eine innere Hülle und eine äußere Hülle aus diesem Material, die durch eine Schicht aus Glasseide oder Glimmer getrennt sind, aufweist.
EP79103159A 1978-11-07 1979-08-27 Feuerhemmendes isolierendes Material für elektrisches Kabel und mit diesem Material erhaltenes elektrisches Kabel Expired EP0010586B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7831467 1978-11-07
FR7831467 1978-11-07

Publications (3)

Publication Number Publication Date
EP0010586A1 EP0010586A1 (de) 1980-05-14
EP0010586B1 EP0010586B1 (de) 1983-12-21
EP0010586B2 true EP0010586B2 (de) 1987-04-15

Family

ID=9214565

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79103159A Expired EP0010586B2 (de) 1978-11-07 1979-08-27 Feuerhemmendes isolierendes Material für elektrisches Kabel und mit diesem Material erhaltenes elektrisches Kabel

Country Status (5)

Country Link
US (1) US4324863A (de)
EP (1) EP0010586B2 (de)
JP (1) JPS5565244A (de)
CA (1) CA1129636A (de)
DE (1) DE2966496D1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3373039D1 (en) * 1982-10-01 1987-09-17 Raychem Ltd Electric wire with flame retarded cladding
NO153511C (no) * 1983-08-25 1986-04-02 Standard Tel Kabelfab As Brann-og oljeresistent kabel.
US10995180B2 (en) 2015-12-31 2021-05-04 Shpp Global Technologies B.V. Polyetherimide compositions, methods of manufacture, and articles prepared therefrom

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3189513A (en) * 1960-11-14 1965-06-15 Westinghouse Electric Corp Track resistant self-extinguishing composition
FR1486273A (de) * 1965-07-09 1967-10-05
DE1260136B (de) * 1965-07-21 1968-02-01 Basf Ag Formmassen zur Herstellung selbstverloeschender Formkoerper
GB1221950A (en) * 1967-03-03 1971-02-10 Bostik Ltd Improvements in or relating to sound-deadening material
GB1221949A (en) * 1967-03-22 1971-02-10 Bostik Ltd Improvements in or relating to sound-deadening material
US3914513A (en) * 1967-06-15 1975-10-21 Ici Ltd Substrates coated with fire resistant compositions
US3639304A (en) * 1968-06-27 1972-02-01 Dow Chemical Co Self-extinguishing polyethylene foams comprising an antimony compound a halogen-containing aliphatic or cyclo-aliphatic compound and a bromine-containing aromatic or acyclic compound
US3655589A (en) * 1969-03-27 1972-04-11 Bayer Ag Flameproofed organic synthetic resins
US3660346A (en) * 1970-08-14 1972-05-02 Phillips Petroleum Co Flame-retarded compositions and additive systems therefor
US3826766A (en) * 1972-10-10 1974-07-30 Koppers Co Inc Self-extinguishing polymer compositions containing brominated aryl butanes
US4022945A (en) * 1973-09-26 1977-05-10 General Electric Company Electric conductor product having a flame resistant insulation
US3997505A (en) * 1974-01-02 1976-12-14 Michigan Chemical Corporation Flame retardant polymeric compositions containing pentaerythritol cyclic diphosphates or diphosphoramidates
US3908067A (en) * 1974-09-12 1975-09-23 Gen Electric Flame resistant polyolefin, method of producing same, and insulated product
ES444945A1 (es) * 1975-03-03 1977-08-16 Gen Electric Procedimiento para preparar un compuesto de poliolefina cu- rado por reticulacion.
US4131690A (en) * 1975-05-05 1978-12-26 Northern Electric Company Limited Method of powder coating an insulated electrical conductor
FR2314239A1 (fr) * 1975-06-09 1977-01-07 Gen Electric Ignifugeant pour compositions polymeriques polyolefiniques et compositions ainsi obtenues
US4151366A (en) * 1977-06-30 1979-04-24 General Electric Company Flame resistant, insulated multi-conductor electric cable
FR2411475A1 (fr) * 1977-12-06 1979-07-06 Thomson Brandt Cable electrique resistant a la propagation de l'incendie, et procede de fabrication d'un tel cable

Also Published As

Publication number Publication date
JPS5565244A (en) 1980-05-16
EP0010586A1 (de) 1980-05-14
CA1129636A (fr) 1982-08-17
JPS6234783B2 (de) 1987-07-29
DE2966496D1 (en) 1984-01-26
EP0010586B1 (de) 1983-12-21
US4324863A (en) 1982-04-13

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