GB2127210A

GB2127210A - Insulated electrical article

Info

Publication number: GB2127210A
Application number: GB08324662A
Authority: GB
Inventors: Stephen Leroy Tondre; Hans Edmund Lunk
Original assignee: Raychem Corp
Current assignee: Raychem Corp
Priority date: 1982-09-15
Filing date: 1983-09-14
Publication date: 1984-04-04
Also published as: EP0103487A3; DE3365309D1; EP0103487A2; JPS5973807A; CA1214528A; GB8324662D0; JPH0517642B2; EP0103487B1; ATE21462T1; GB2127210B

Abstract

Electrical insulation comprises a conductor, a melt shaped inner layer of a cross-linked olefin polymer, e.g. an ethylene/tetrafluoroethylene or chlorotrifluoroethylene copolymer or a vinylidene fluoride polymer, and an outer layer of a linear aromatic polymer having a glass transition temperature of at least 100 DEG C, e.g. a polyether ether ketone, a polyether ketone or a polyether sulfone. Such insulation combines excellent properties under normal service conditions with low smoke evolution on burning, and is therefore particularly useful for aircraft wire and cable.

Description

1 GB 2 127 21 OA 1 1

SPECIFICATION

Electrical insulation This invention relates to insulation for electrical articles.

Electrical insulation must meet a variety of electrical and physical requirements under normal service conditions. In addition, for many purposes the insulation must meet test requirements which are intended to ensure that if the insulation is exposed to very high temperatures, e.g. in a fire, it will not evolve excessive amounts of toxic products or smoke. These requirements are particularly severe for electrical cable which is to be used in aircraft and similar equipment. The 10 term "cable" is used herein to include a single electrically insulated elongate conductor often referred to in the art as "wire"), an article comprising a plurality of separate elongate conductors each of which is separately insulated, and an article comprising a plurality of elongate conductors which are physically joined together but electrically insulated from each other by insulating material, e.g. ribbon cable.

Fluorocarbon polymers, especially ethylene /tetraf luoroethylene (ETFE) copolymers such as Tefzel, are used extensively for electrical insulation, in particular for aircraft wire. Particularly when cross-linked, such polymers can exhibit an excellent combination of physical and electrical properties under normal service conditions. In this connection, reference may be made to U.S.

Patents Nos. 3,580,829, 3,738,923, 3,763,222, 3,840,619, 3,894,118, 3,911, 192, 3,947,525, 3,970,770, 3,985,716, 3,995,091, 4,031,167, 4,155,823, 4, 121,001, and 4,176,027. Other polymers which have been used for electrical insulation include other olefin polymers (both homopolymers and copolymers) and various high-melting aromatic polymers.

We have discovered that insulation which has improved properties and which can be efficiently manufactured comprises an inner layer of a cross-linked melt- extruded olefin polymer covered by a layer of a melt extruded aromatic polymer having a glass transition temperature of at least 1 00C. Accordingly, the present invention provides an insulated electrical article, especially an insulated electrical wire or cable comprising:

(a) a conductor; (b) a melt-shaped, preferably melt-extruded, inner insulating layer which preferably contacts 30 the conductor and comprises a first organic polymer component which is a cross-linked olefin polymer, particularly an ETFE copolymer, and (c) a melt-shaped, preferably melt-extruded, outer insulating layer which contacts the inner insulating layer and which comprises a second organic polymer component which is a substantially linear aromatic polymer having a glass transition temperature of at least 1 OO'C, 35 preferably at least 1 30C.

The olefin polymer forming the inner layer preferably has a tensile (Young's) modulus of at least 138 MPa (20,000 p.s.i.) especially at least 207 MPa (30,000 p.s.i) and particularly at least 276 MPa (40,000 p.s.i) in order to minimize wrinkling of the outer layer when the article, e.g. in the form of a wire, is bent.

The insulation of the article to the invention provides a valuable combination of physical and electrical properties. The outer layer provides excellent resistance to physical abuse. The inner layer is more flexible than the outer layer and thus provides insulation which is more flexible, for a particular di-electric strength, than insulation which is composed only of the aromatic polymer.

Furthermore, the aromatic polymers often have poor resistance to stresscracking which can seriously reduce their dielectric strength, the olefin polymers do not suffer from this disadvan tage, and the inner jacket will therefore provide continuous insulation even in environments which cause stress-cracking of the outer jacket.

The term "olefin polymer" as used herein is defined as being a polymer of one or more unsubstituted and/or substituted olefins. Where the polymer includes substituted olefins as 50 monomers or comonomers they are preferably polar monomers and especially fluorine-contain ing monomers, e.g. tetrafluorethylene, or a carboxylic ester, in particular an alkyl acrylate, e.g.

methyl or ethyl acrylate, or a vinyl ester, e.g. vinyl acetate. The olefin is preferably a fluorcarbon polymer as explained below.

Particularly useful properties are obtained when the inner layer is composed of a cross-linked fluorocarbon layer. We have discovered that the combination of an inner layer of a cross-linked fluorocarbon polymer and an outer layer of an aromatic polymer results in a completely unexpected reduction in the smoke evolved under standard test condictions. Thus it is possible, through use of the present invention, to manufacture electrical wire which, when tested for smoke evolution by ASTM E 662-79 (flaming mode), has a Dm value of less than 50, preferably 60 less than 35, where Dm is the maximum specific optical density.

The term "fluorocarbon polymer" is used herein to denote a polymer or mixture of polymers which contains more than 10%, preferably more than 25%, by weight of fluorine. Thus the fluorocarbon polymer may be a single fluorine-containing polymer, a mixture of two or more fluorine-containing polymers, or a mixture of one of more fluorine- containing polymers with one 65 2 GB 2 127 21 OA 2 or more polymers which do not contain fluorine. In one preferred '61ass, the flutrocarbon polymer comprises at least 50%, particularly at least 75% especially at least 85%, by weight of one or more thermoplastic crystalline polymers each containing at least 25% by weight of fluorine, a single such crystalline polymer being preferred. Such a fluorocarbon polymer may contain, for example, a fluorine-containing elastomer and/of a polyolefin, preferably a crystalline polyolefin, in addition to the crystalline fluorine-containing polymer or polymers. The fluorinecontaining polymers are generally homoor copolymers of one or more fluorine-containing olefinically unsaturated monomers, or copolymers of one or more such monomers with one or more olefins. The fluorocarbon polymer usually has a melting point of at least 1 50C, and will often have a melting point of at least 250C, e.g. up to 350C, the melting point being defined 10 for crystalline polymers as the temperature above which no crystallinity exists in the polymer (or when a mixture of crystalline polymers is used, in the major crystalline component in the mixture). Preferably the polymeric composition, prior to cross-linking, has a viscosity of less than poise at a temperature not more than 60'C above its melting point. A preferred fluorocarbon polymer is a copolymer of ethylene and tetrafluoroethylene and optionally one or 15 more other comonomers (known as ETFE polymers), especially a copolymer comprising 35 to mole percent of ethylene, 35 to 60 mole percent of tetrafluoro-ethylene and up to 10 mole percent of one or more other comonomers. Other specific polymers which can be used include copolymers of ethylene and chlorotrifluoroethylene; polyvinylidene fluoride; copolymers of vinylidene fluoride with one or both of hexafluoropropylene and tetrafluoroethylene, or with 20 hexafluoroisobutylene; and copolymers of tetrafluoroethylene and hexafluoropropylene.

Either or both of the inner and outer insulating layers can optionally contain suitable additives such as pigments, antioxidants, thermal stabilisers, acid acceptors and processing aids.

The aromatic polymers which are used in this invention are will known to those skilled in the art, and reference may be made for example to U.S. Patents Nos. 3,025,605, 3,354,129, 3,441,538, 3,442,538, 3,446,654, 3,658,938, 3,838,097, 3,847,867, 3,953, 400, 3,956,240, 4,107,147, 4,108,837, 4,111,908, 4,175,175, 4,293,670, 4,320, 224, and 3,446,654 and British Patents Nos. 971,227, 1,369,210 and 1,599,106. Such polymers include polyketones, polyether ketones, polyether ether keton es and polyether sulfones, poly ether ketone/sulfone copolymers and polyether imides. Blends of different polymers can be 30 used. Preferred aromatic polymers are crystalline polymers with a melting point of at least 250C, particularly at least 300C. In one class of such polymers the polymer comprises, and preferably consists essentially of, units of the formula -AR-Q- 11 the units being the same or different, Ar being a divalent aromatic radical and a being 0-, -S-, -S02-1 -CO-, -NH-CO- or -COO-, or Ar being a polyvalent radical and G being CO_ -N CO_ the C radical preferably being directly bonded to aromatic carbon atoms in the Ar radical.

In another class of aromatic polymers the aromatic polymer is a crystalline polyarylene ether comprising recurring units of the formula -0-E-O-E'- where E is the residue of a dihydric phenol and E' is the residue of an aromatic compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, the E and E' radicals being linked to the -0- radicals through aromatic carbon 55 atoms. In one preferred sub-class, E is a radical of the formula -4RXp_ ( Y)y (Y1)z wherein R is a divalent radical; x is 0 or 1; Y is a radical selected from halogen btoms, alkyl radicals containing 1 to 4 carbon atoms and alkoxy radicals containing 1 to 4 carbon atoms; y is 0, 1, 2, 3 or 4; Y' is a radical selected from halogen atoms, alkyl radicals containing 1 to 4 carbon atoms and alkoxy radicals containing 1 to 4 carbon atoms; z is 0, 1, 2, 3 or 4, and E' is65 3 GB 2 127 21 OA 3 a radical of the formula n wherein R' is a sulfone, carbonyl, vinyl, sulfoxide, azo, saturated fluorocarbon, organic phosphine oxide or ethylidene radical. In this class preferred polysulfones are those in which y and z are 0, x is 1, RI is a sulfone radical and R is a radical of the formula W' 1 -C- 1 W.

wherein each of W' and R is independently selected from the group consisting of hydrogen; aikyl radicals containing 1 to 4 carbon atoms; halogen-substituted alkyl radical containing 1 to 4 carbon atoms; aryi, alkaryl and aralkyl radicals containing 6 to 10 carbon atoms; and halogen substituted aryl alkaryl and aralkyl radicals containing 6 to 10 carbon atoms.

In another class of aromatic polymers, the polymer is a polyether imide or polysulfone imide 20 which comprises recurring units of the formula 0 11 [1 _Q_Z -C \ N-R'-N,- "\ Z-0-R- \ c / 1\ c I 11 [1 0 0 where Q is -0- or -S02, Z is a trivalent aromatic radical, R is a divalent aromatic radical and R' is a divalent organic radical.

Preferred aromatic polymers consist essentially of repeating units having one of the following formulae M-0-0-0-0-co- (2) _0_0_&O_O_ (3) -// \-o Cof (4 _OM __W)_ _Cfo_orCo_ p Co + _CO wherein each of x, m and n is 0 or 1, with n being 0 when x is 1, p is an integer from 1 to 4, 50 with m being 1 and x being 0 when p is greater than 1, e.g., 0 0 11 11 - 1/7 \ 0 0-r\-C c \--i -0- (5) -0-o-O-SO 2_ 1 1; 'i 4 GB 2 127 21 OA 4 (6) C83 CE3 5 (7) 0 CE3 0 -N 11 _T 0 CHo _\.J_ 10 0- --' 3 00 0 0 The insulated articles of the present invention can be produced by conventional techniques; the inner layer usually contacts the conductor, and the inner and outer layers generally constitute the total insulation of the article; however, other insulating layers can be present. The 15 olefin polymer is preferably cross-linked by radiation, and cross-linking can be effected before or after the aromatic polymer (which is generally not cross-linked by radiation) is applied. For electrical cable, the inner layer will usually be of annular cross-section of thickness for example 76.2 to 381 micrometres (3 to 15 mils), preferably 101.6 to 177.8 micronletres (4 to 7 mils).

Alternatively, the cable can comprise a plurality of conductors, each of which has an inner;nsulating layer around it, with the conductors being joined together and further insulated by the outer insulating layer.

The invention is illustrated by the following Examples, Examples 1, 2, 3 and 8 of which are comparative.

Examples

In each of the Examples, a 20 AWG stranded (19/32) conductor was extrusion-coated with an inner insulating layer having the composition and thickess shown in the Table. Except in Examples 1 and 2, the inner insulating layer was then extrusion-coated with an outer insulating layer having the composition and thickness shown in the Table. In some of the Examples, as 30 designated in the Table, the coated conductor was irradiated to a dosage of about 10 Megarads to cross-link the inner coating; in these Examples, the inner coating also contained, when it was irradiated, a suitable amount of a radiation cross-linking agent. The outer coating was substantially unaffected by this irradiation. The coated conductor was annealed at 1 80C for 1 hour. Samples of the resulting cable were tested in accordance with the procedure of ASTIVI E662-79 (flaming mode), and the Table shows the values obtained for the minimum transmit tance, the transmittance after 10 minutes, the time taken to reach the point of minimum transmittance, and the maximum optical density (Dm).

The various polymers used in the Examples are further indentified below Tefzel 280 is a copolymer of ethylene and tetrafluoroethylene available from du Pont.

Haiar 300 is a copolymer of ethylene and chlorotrifluoroethylene available from Allied Chemical.

Kynar 450 is polyvinylidene fluoride available from Pennwalt.

PEEK is a polyether ether ketone available from ICL Ultern is a polyetherimide available from General Electric.

Victrex 200P a polyethersulphone available from ICI.

PEEK, Ultern and PES are substantially linear aromatic polymers.

GB 2 127 21 OA 5 TABLE

1 (C) 2(C) i- 3(C) 4 5 6 7 8 (C)9 INNER INSULATING LAYER Composition Tefzel 280 X X X X X X X Halar 300 - - - - - - - X X Thickness (mils) 10 10 4 4 4 4 4 4 4 10 OUTER INSULATING LAYER none none Composition PEEK - X X X - - X X Ultem - - - - - - X Victrex 200P - - - - - X - 15 Thickness (mils) - - 6 6 5 5 5 6 6 Cross-Linking no yes no yes yes yes yes no yes TRANSMITTANCE Minimum 0.18 0.46 10 67 47 59 71 32 59 at 10 minutes 4.5 4.5 60 96 90 90 96 88 91 20 Time to Min. Transmittance 19 16 25 26 23 26 30 25 27 (minutes) D. (Max Optical Density) 362 309 132 23 43 30 20 55 30 25

Claims

1. An insulated electrical article, comprising (a) a conductor; (b) a melt shaped inner insulating layer comprising a first organic polymer component which 30 is a cross-linked olefin polymer, and (c) a melt shaped outer insulating layer which contacts the inner insulating layer and which comprises a second organic polymer component which is a substantially linear aromatic polymer having a glass transition temperature of at least 1 OWC.

2. An article according to Claim 1, wherein the inner layer is in contact contact with the conductor.

3. An article according to Claim 1 or Claim 2, wherein the inner layer is radiation crosslinked.

4. An article according to any one of claims 1 to 3, wherein the olefin polymer contains more than 25% weight of fluorine. 40 5. An article according to any one of claims 1 to 3, wherein the olefin polymer comprises at 40 least 75% by weight of a thermoplastic crystalline polymer containing at least 25% by weight of fluorine. 6. An article according to any one of Claims 1 to 3, wherein the olefin polymer consists essentially of an ethylene /tetrafl uoroethyle ne copolymer. 7. An article according to any one of claims 1 to 3, wherein the olefin polymer consists essentially of an ethylene /chlorotrif 1 uorethylene copolymer or a vinylidene fluoride polymer. 8. An article according to any one of Claims 1 taL 7, wherein the olefin polymer has a melting point of at least 250C. 9. An article according to any one of claims 1 to 8, wherein the aromatic polymer has a glass transition temperature of at least 1 WC.

10. An article according to any one of Claims 1 to 9, wherein the aromatic polymer is a crystalline polymer having a melting point of at least 25WC.

11. An article according to any one of Claims 1 to 10, wherein the aromatic polymer comprises"units of the general formula:

-Ar-G- wherein Ar represents a polyvalent aromatic radical and G represents a radical of the formula 6 GB 2 127 21 OA 6 1 or N Co- co-, 1 12. An article according to Claim 11 wherein the aromatic polymer consists essentially of said units of formula -Ar-Q-.

13. An article according to Claim 11 or Claim 12, wherein the G radial is bonded directly to 20 aromatic carbon atoms.

14. An article according to any one of claims 1 to 10, wherein the aromatic polymer is a crystalline polyarylene ether comprising recurring units of the general formula wherein E is the residue of a dihydric phenol and E' is the residue of an aromatic compound having an electron-withdrawing group in at least one of the positions ortho and para to the valence bonds; the E and E' radicals being lined to the -0radicals through aromatic carbon atoms.

15. An article according to claim 14, wherein E is a radical of the formula is (Y) Y (Y 1) z 35 wherein R represents a divalent radical; x is 0 or 1; y is an alkyl radical containing 1 to 4 carbon atoms or an alkoxy radical containing 1 to 4 carbon atoms; y is 0 or an integer from 1 to 4; Y' is a halogen atom, an alkyl radical containing 1 to 4 carbon atoms or an alkoxy radical containing 1 to 4 carbon atoms; and z is 0 or an integer from 1 to 4, and E' is a radical of the 40 formula -f-R 1 -P\ - wherein RI represents a sulfone, carbonyl, vinyl, sulfoxide, azo, saturated fluorocarbon, organic phosphine oxide or ethylidene radical.

10. An article according to claim 15, wherein y and z are 0, x is 1, R' is a sulfone radical and R is a radical of the formula W' 1 -U- 1 K...

wherein each of W' and R... is a hydrogen atom,; an alkyl radical containing 1 to 4 carbon atoms; a halogen-substituted alkyl radical containing 1 to 4 carbon atoms; an aryl, alkaryl or aralkyl radical containing 6 to 10 carbon atoms; or a halogen-substituted aryl, alkaryl or aralkyl radical containing 6 to 10 carbon atoms.

17. An article according to any one of Claims 1 to 10, wherein the aromatic polymer consists essentially of repeating units of the formula 7 GB 2 127 21 OA 7 18. An article according to any one of Claims 1 to 10, wherein the aromatic polymer 5 consists essentially of repeating units of the general formula J/ \ - 0 - n\ -M- \-- F = 7 19. An article according to any one of Claims 1 to 10, wherein the aromatic polymer consists essentially of repeating units of the formula wherein each of x, m and n is 0 or 1, with n being 0 when x is 1, p is an integer from 1 to 4 with m being 1 and x being 0 when p is greater than 1.

20. An article according to any one of Claims 1 10 to, wherein the aromatic polymer 20 consists essentially of repeating units of the formula 0 co- 2 1. An article according to any one of Claims 1 to 10, wherein the aromatic polymer 25 consists essentially of repeating units of the formula 2_ \--i \C==/ 22. An article according to any one of Claims 1 to 10, wherein the aromatic polymer consists essentially of repeating units of the formula CH 3 5 7C 0 CB 3 23. An article according to any one of Claims 1 to 22 which is in the form of an electrical 40 wire or cable, the inner insulating layer being a melt-extruded layer which surrounds and contacts the conductor, and the outer insulating layer being a melt- extruded layer which surrounds and contacts the inner insulating layer.

24. An article according to Claim 23 wherein the inner layer is of annular cross-section with a wall thickness of 76.2 to 254 micrometres.

25. An article according to Claim 24 wherein the outer layer is of annular cross-section with a wall thickness of 76.2 to 381 micrometres.

26. An article according to Claim 25 wherein the wall thickness of the inner layer is from 101.6 to 77.8 micrometers and the wall thickness of the outer layer is from 101.6 to 177,8 micrometres.

27. An article according to Claim 22 which comprises a plurality of conductors, each of the conductors being surrounded by an inner layer which is of annular cross-section, and the conductors being joined together by the outer insulating layer.

28. An article according to any one of Claims 23 to 27, wherein the aromatic polymer is a 55 polyether sulphone.

29. An article according to any one of claims 23 to 27 wherein the aromatic polymer is a polyether ether ketone.

30. An article according to Claim 29 wherein the aromatic polymer is a polether ketone.

31. A wire or cable substantially as described in any one of Examples 4 to 7 or 9 herein.

Printed for Her Majesty's Stationery Office by Burgess Et Son (Abingdon) Ltd.-1 984Published at The Patent Office, 25 Southampton Buildings, London, WC2A 1AY, from which copies may be obtained.