EP0010586A1 - 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 PDFInfo
- Publication number
- EP0010586A1 EP0010586A1 EP79103159A EP79103159A EP0010586A1 EP 0010586 A1 EP0010586 A1 EP 0010586A1 EP 79103159 A EP79103159 A EP 79103159A EP 79103159 A EP79103159 A EP 79103159A EP 0010586 A1 EP0010586 A1 EP 0010586A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- flame retardant
- material according
- matrix
- bromine
- bis
- 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.)
- Granted
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 35
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011810 insulating material Substances 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 title claims description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 239000012757 flame retardant agent Substances 0.000 claims abstract description 9
- 229920000728 polyester Polymers 0.000 claims abstract description 9
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 8
- 229920001155 polypropylene Polymers 0.000 claims abstract description 7
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 4
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 4
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- -1 polypropylene Polymers 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000004156 Azodicarbonamide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 4
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- WQJUBZMZVKITBU-UHFFFAOYSA-N (3,4-dimethyl-4-phenylhexan-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(CC)C(C)(CC)C1=CC=CC=C1 WQJUBZMZVKITBU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 2
- 210000003850 cellular structure Anatomy 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- IHACONBWUMNMLD-UHFFFAOYSA-N 3,9-bis[2,2-bis(bromomethyl)-3-chloropropoxy]-2,4,8,10-tetraoxa-3$l^{5},9$l^{5}-diphosphaspiro[5.5]undecane 3,9-dioxide Chemical compound C1OP(OCC(CBr)(CBr)CCl)(=O)OCC21COP(=O)(OCC(CCl)(CBr)CBr)OC2 IHACONBWUMNMLD-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- KWGRBVOPPLSCSI-WPRPVWTQSA-N (-)-ephedrine Chemical compound CN[C@@H](C)[C@H](O)C1=CC=CC=C1 KWGRBVOPPLSCSI-WPRPVWTQSA-N 0.000 description 1
- LERFHXCLIVRDIK-UHFFFAOYSA-N 1,3,5-tribromo-2-ethoxybenzene Chemical compound CCOC1=C(Br)C=C(Br)C=C1Br LERFHXCLIVRDIK-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 208000031968 Cadaver Diseases 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- PCVVBHUFWPHCAL-UHFFFAOYSA-N butane-1,4-diol;terephthalic acid Chemical compound OCCCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 PCVVBHUFWPHCAL-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
Classifications
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- 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 satisfy 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 in terms of mechanical properties and hot aging, but this type of material like the previous one requires effective fireproofing 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 hexabromocyclododecane, tetrabromoethane or halogenated aromatic compounds.
- 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 given off during combustion, good mechanical and electrical qualities, hot and cold (winding), good resistance to thermal aging and low cost price.
- the flame retardant insulating material according to the invention is characterized in that the synthetic matrix polymer is a member of the group consisting of copolymers of propylene and ethylene, high density polyethylene and thermoplastic polyesters, and in that the flame retardant is a cyclic derivative of pentaerythritol, an aliphatic derivative or a cycloaliphatic derivative, halogenated and stable at the extrusion temperature of the matrix, and decomposing at a higher temperature, and in which at least the majority of the halogenated substituents are bromine atoms.
- the synthetic matrix polymer is a member of the group consisting of copolymers of propylene and ethylene, high density polyethylene and thermoplastic polyesters
- the flame retardant is a cyclic derivative of pentaerythritol, an aliphatic derivative or a cycloaliphatic derivative, halogenated and stable at the extrusion temperature of the matrix, and decomposing at a higher temperature, and in which at least the
- 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 a glass fiber envelope or of mica.
- flame retardant A 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 - dibromcmethyl-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 spread 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 tetramethylene glycol terephthalate marketed under the trade designation Hytrel by the company DU PONT DE NEMOURS or that marketed under the designation 1010-5 by the 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 IOL of 25.5 to the test according to the American standard ASTMD-2863 of 1970. After adding 0.5 part by weight of 2,3-2,3-dimethyl-diphenylbutane (free radical generator) an oxygen index of 30 is obtained.
- 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, preferably used as flame retardant 3.9 - bis ( 2,2 - dibromomethyl) - 3 chloro-propoxy) 2,4,8,10 - tetroxa - 3,9 - diphosphaspiro (5,5) undécane-3,9 - dioxide, which will be designated below the flame retardant B, or the 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 anticoppers 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 anticoppers 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.
- oxygen indices of 25 are obtained when the mixture does not include a free radical generator, and of 31 when 0.4% by weight of 2 is added , 3 - 2,3 - dimethyl - diphenylbutane.
- 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)
Abstract
Matériau isolant ignifugé pour câble électrique, comprenant une matrice en copolymère de propylène et d'éthylène, en polyéthylène à haute densité ou en polyester thermoplastique, un agent ignifugeant formé par un dérivé cyclique du pentaérythritol, un dérivé aliphatique ou cycloaliphatique, halogéné, stable à la température d'extrusion de la matrice et se décomposant à une température supérieure, et un composé minéral d'antimoine susceptible de réagir avec le brome de l'agent ignifugeant lors d'une combustion.Flame retardant insulating material for electric cable, comprising a matrix of propylene and ethylene copolymer, of high density polyethylene or of thermoplastic polyester, a flame retardant agent formed by a cyclic derivative of pentaerythritol, an aliphatic or cycloaliphatic derivative, stable at the extrusion temperature of the matrix and decomposing at a higher temperature, and an inorganic antimony compound capable of reacting with the bromine of the flame retardant during combustion.
Description
La présent 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 satisfy 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 annoying 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 in terms of mechanical properties and hot aging, but this type of material like the previous one requires effective fireproofing 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'hexabromocyclododécane, le tétrabromoéthane ou des composés aromatiques halogénés.In particular, alumina trihydrate and organic materials containing chlorine or bromine have been used, for example hexabromocyclododecane, 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 Soi., 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 Soi., 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 many and diverse bromines, but all of which contain at least one aromatic nucleus.
Il est à remarquer que l'utilisation d'un générateur de radicaux libres carbone-carbone avec divers composés aromatiques connus comme agents ignifugeants tels que le décabromodiphényloxyde 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 Sb203.It should be noted 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 given results. bad. 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 Sb203.
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 given off during combustion, good mechanical and electrical qualities, 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 :
- - une matrice constituée par un polymère synthétique,
- - un agent ignifugeant constitué au moins en partie par un corps organique contenant du brome,
- - et un composé minéral d'antimoine susceptible de réagir avec le brome de l'agent ignifugeant lors d'une combustion.
- - a matrix consisting of a synthetic polymer,
- - a flame-retardant agent constituted at least in part by an organic body containing bromine,
- - and an inorganic antimony compound capable of reacting with the bromine of the flame retardant during combustion.
Le matériau isolant ignifugé selon l'invention est caractérisé en ce que le polymère synthétique de la matrice est un membre du groupe constitué par les copolymères de propylène et d'éthylène, le polyéthylène à haute densité et les polyesters thermoplastiques, et en ce que l'agent ignifugeant est un dérivé cyclique du pentaérythritol, un dérivé aliphatique ou un dériv4 cycloaliphatique, halogéné et 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 halogénés sont des atomes de brome.The flame retardant insulating material according to the invention is characterized in that the synthetic matrix polymer is a member of the group consisting of copolymers of propylene and ethylene, high density polyethylene and thermoplastic polyesters, and in that the the flame retardant is a cyclic derivative of pentaerythritol, an aliphatic derivative or a cycloaliphatic derivative, halogenated and stable at the extrusion temperature of the matrix, and decomposing at a higher temperature, and in which at least the majority of the halogenated substituents are bromine atoms.
Il répond en outre de préférence à au moins l'une des caractéristiques suivantes :
- - il comprend de plus 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. Ce générateur de radicaux libres est de préférence un hydrocarbure aliphatique ramifié contenant des noyaux phényles, et plus particulièrement le.2,3
- - diméthyl - 2,3 - diphénylbutane ou le 3,4 - diméthyl - 3,4 diphénylhexane.
- - le composé organique contenant du brome de l'agent ignifugeant contient également du phosphore dans sa molécule, ou bien l'agent ignifugeant est un mélange de composé organique contenant du brome et de phosphore rouge.
- - le composé organique contenant du brome est choisi dans le 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 - chloropropoxy) - 2,4,8,10 tétraoxa - 3, 9 - diphosphaspiro - (5,5) undécane - 3,9 - dioxyde et l'hexabromocyclododécane.
- - 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, ou bien 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.
- - la proportion d'agent ignifugeant est comprise entre 2% et 30% en 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 further comprises a free radical generator, this generator only decomposing at a temperature above the extrusion temperature of the matrix, and being capable of cutting homolytically between two carbon atoms at said higher temperature . This free radical generator is preferably a branched aliphatic hydrocarbon containing phenyl rings, and more particularly le.2,3
- - dimethyl - 2,3 - diphenylbutane or 3,4 - dimethyl - 3,4 diphenylhexane.
- - The organic compound containing bromine of the flame retardant also contains phosphorus in its molecule, or else the flame retardant is a mixture of organic compound containing bromine and red phosphorus.
- - the organic compound containing bromine is chosen from the group consisting of 3.9 - bis (2,3 - dibromopropoxy)
- - 2,4,8,10 - tetraoxa - 3,9 - diphosphaspiro (5,5) undécane -
- - 3.9 - dioxide, 3.9 - bis (2,2 - dibromomethyl) - 3 - chloropropoxy) - 2,4,8,10 tetraoxa - 3, 9 - diphosphaspiro - (5,5) undecane - 3, 9 - dioxide and hexabromocyclododecane.
- - its matrix is polypropylene or a thermoplastic polyester, and its flame-retardant agent is 3.9 - bis (2.2 - dibromomethyl- 3
- - chloropropoxy) - 2,4,8,10 tetraoxa - 3,9 diphosphaspiro (5,5) undécane - 3,9 dioxide, or its matrix is a copolymer of propylene and ethylene containing less than 10% by weight d ethylene, and its flame-retardant agent 3,9- bis (2,3 - dibromopropoxy) 2,4-8,10 -tetraoxa- 3,9 - diphosphaspiro (5,5) undécane
- -3,9 - dioxide or hexabromocyclododecane.
- - The proportion of flame retardant is between 2% and 30% by 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 a glass fiber envelope 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 - dibromcméthyl-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 parait 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 polytéré- phtalate de butane- 1,4 - diol et de tétraméthylène 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 - dibromcmethyl-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 spread 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 tetramethylene glycol terephthalate marketed under the trade designation Hytrel by the company DU PONT DE NEMOURS or that marketed under the designation 1010-5 by the 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 IOL of 25.5 to the test according to the American standard ASTMD-2863 of 1970. After adding 0.5 part by weight of 2,3-2,3-dimethyl-diphenylbutane (free radical generator) an oxygen index of 30 is obtained. 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 (2,2 - dibromométhyl) - 3 chloro-propoxy) 2,4,8,10 - tétroxa - 3,9 - diphosphaspiro (5,5) undécane-3,9 - dioxyde, qui sera désigné ci-après l'agent ignifugeant B, ou l'hexabromocyclododécane de formule
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 1mm sur un mandrin de diamètre 20mm pendant une heure à 135°C
- - une bonne résistance aux solvants, aux acides et aux bases.
- - 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 1mm on a mandrel of diameter 20mm for one hour at 135 ° C
- - good resistance to solvents, acids and bases.
Les matériaux dont l'agent ignifugeant organique ne comporte pas de phosphore dans sa molécule, notamment contenant l'agent C, ne présentent pas une résistance à la propagation de la flamme très élevée, mais on peut l'améliorer par addition d'une petite quantité, de l'ordre de 2% en poids, de phosphore rouge, ou bien par addition d'une autre charge minérale, telle qu'un gel de silice ou d'alumine ou de la magnésie, dans la mesure où elle est compatible avec le polymère constituant la matrice (la magnésie ne convenant par exemple pas avec les copolymères de propylène et d'éthylène).Materials whose organic flame retardant does not contain phosphorus in its molecule, in particular containing agent C, do not have a very high resistance to flame propagation, but it can be improved by adding a small amount, of the order of 2% by weight, of red phosphorus, or else by addition of another mineral filler, such as a silica or alumina gel or magnesia, insofar as it is compatible with the polymer constituting the matrix (magnesia not suitable, for example, with copolymers of propylene and ethylene).
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 (13)
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 true EP0010586A1 (en) | 1980-05-14 |
| EP0010586B1 EP0010586B1 (en) | 1983-12-21 |
| EP0010586B2 EP0010586B2 (en) | 1987-04-15 |
Family
ID=9214565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79103159A Expired EP0010586B2 (en) | 1978-11-07 | 1979-08-27 | Flame retardant insulating material for an electrical cable and electrical cable made with such a material |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4324863A (en) |
| EP (1) | EP0010586B2 (en) |
| JP (1) | JPS5565244A (en) |
| CA (1) | CA1129636A (en) |
| DE (1) | DE2966496D1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4659871A (en) * | 1982-10-01 | 1987-04-21 | Raychem Limited | Cable with flame retarded cladding |
| AU570261B2 (en) * | 1983-08-25 | 1988-03-10 | Alcatel N.V. | Fire and oil resistant cable |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017117343A1 (en) | 2015-12-31 | 2017-07-06 | Sabic Global Technologies B. V. | Polyetherimide compositions, methods of manufacture, and articles prepared therefrom |
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| US3908067A (en) * | 1974-09-12 | 1975-09-23 | Gen Electric | Flame resistant polyolefin, method of producing same, and insulated product |
| FR2303044A1 (en) * | 1975-03-03 | 1976-10-01 | Gen Electric | COMPOSITION OF IGNIFIGATED POLYOLEFIN |
| FR2310619A1 (en) * | 1975-05-05 | 1976-12-03 | Northern Telecom Ltd | METHOD FOR MANUFACTURING A THERMALLY INSULATED AND POLYMER-COATED ELECTRICAL CONDUCTOR AND CONDUCTOR SO OBTAINED |
| FR2314239A1 (en) * | 1975-06-09 | 1977-01-07 | Gen Electric | FIRE RETARDANT FOR POLYOLEFINIC POLYMERIC COMPOSITIONS AND COMPOSITIONS THUS OBTAINED |
| FR2396393A1 (en) * | 1977-06-30 | 1979-01-26 | Gen Electric | ELECTRIC CABLE, MULTI-CONDUCTOR, INSULATED AND FLAMMATION RESISTANT |
| FR2411475A1 (en) * | 1977-12-06 | 1979-07-06 | Thomson Brandt | ELECTRIC CABLE RESISTANT TO THE PROPAGATION OF FIRE, AND METHOD FOR MANUFACTURING SUCH A CABLE |
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| 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 |
-
1979
- 1979-08-27 EP EP79103159A patent/EP0010586B2/en not_active Expired
- 1979-08-27 DE DE7979103159T patent/DE2966496D1/en not_active Expired
- 1979-08-30 CA CA334,780A patent/CA1129636A/en not_active Expired
- 1979-09-05 US US06/072,814 patent/US4324863A/en not_active Expired - Lifetime
- 1979-09-07 JP JP11434279A patent/JPS5565244A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3908067A (en) * | 1974-09-12 | 1975-09-23 | Gen Electric | Flame resistant polyolefin, method of producing same, and insulated product |
| FR2303044A1 (en) * | 1975-03-03 | 1976-10-01 | Gen Electric | COMPOSITION OF IGNIFIGATED POLYOLEFIN |
| FR2310619A1 (en) * | 1975-05-05 | 1976-12-03 | Northern Telecom Ltd | METHOD FOR MANUFACTURING A THERMALLY INSULATED AND POLYMER-COATED ELECTRICAL CONDUCTOR AND CONDUCTOR SO OBTAINED |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4659871A (en) * | 1982-10-01 | 1987-04-21 | Raychem Limited | Cable with flame retarded cladding |
| AU570261B2 (en) * | 1983-08-25 | 1988-03-10 | Alcatel N.V. | Fire and oil resistant cable |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6234783B2 (en) | 1987-07-29 |
| US4324863A (en) | 1982-04-13 |
| CA1129636A (en) | 1982-08-17 |
| DE2966496D1 (en) | 1984-01-26 |
| EP0010586B2 (en) | 1987-04-15 |
| EP0010586B1 (en) | 1983-12-21 |
| JPS5565244A (en) | 1980-05-16 |
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