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GB1569460A - Insulated electrical conductor - Google Patents

Insulated electrical conductor Download PDF

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Publication number
GB1569460A
GB1569460A GB4013777A GB4013777A GB1569460A GB 1569460 A GB1569460 A GB 1569460A GB 4013777 A GB4013777 A GB 4013777A GB 4013777 A GB4013777 A GB 4013777A GB 1569460 A GB1569460 A GB 1569460A
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GB
United Kingdom
Prior art keywords
crosslinking
product
coreactant
pvdf
wire
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
GB4013777A
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.)
International Standard Electric Corp
Original Assignee
International Standard Electric Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by International Standard Electric Corp filed Critical International Standard Electric Corp
Publication of GB1569460A publication Critical patent/GB1569460A/en
Expired legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/02Disposition of insulation
    • H01B7/0208Cables with several layers of insulating material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators 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
    • H01B3/44Insulators 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
    • H01B3/441Insulators 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

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Laminated Bodies (AREA)

Description

(54) INSULATED ELECTRICAL CONDUCTOR (71) We, INTERNATIONAL STANDARD ELECTRIC CORPORATION a corporation organised and existing under the laws of the State of Delaware, United States of America, of 320 Park Avenue, New York 22, State of New York, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to an insulated electrical conductor having a two-layer crosslinked polymeric coating.
The performance requirements at elevated temperatures of insulated wires are becoming increasingly more demanding. For certain military requirements, the insulating properties of polyethylene are excellant. However, at elevated temperatures, the polyethylene undergoes thermal oxidative degradation. A second polymeric coating, of e.g. polyvinylidene fluoride, has been used to protect the polyethylene from thermal degradation, but while this has provided a certain measure of protection. the elevated temperature properties of such insulated conductors are still not acceptable for many of the more demanding insulation requirements.
Other fluorocarbon polymers useful as wire insulation are known, including copolymers of ethylene and chlorotrifluoroethylene. However, the elevated temperature properties, and particularly the deformation resistance of the latter copolymers are not significantly different than those of polyvinylidene fluoride. There has therefore been a continuing need for an improved jacketing insulation for polyethylene coated wire.
We have now discovered that considerably improved elevated temperature properties are achieved in an insualted electrical conductor comprising a primary coating of a crosslinked polyolefin jacketed in a crosslinked copolymer of ethylene and chlorotrifluoroethylene containing from 1 to 10%, preferably 2 to 6% of certain crosslinking coreactants and from 1 to 10%, preferably 2 - 5% of certain stabilizers. Such insulated conductors equal or surpass the military specifications for insulated electrical wire for continued operation at temperatures as high as 150"C. In addition, such insualated conductors also have excellent subambient or low temperature properties. The invention is specific to the use of ethylene/chlorotrifluoroethylene copolymers.Equivalent results are not obtained with other chemically similar fluorocarbon polymers, including for example, copolymers of ethylene and tetrafluoroethylene.
The outer or jacketing layer contains, in addition to the fluorocarbon copolymer, a crosslinking coreactant and a stabilizer. The crosslinking coreactants used possess high temperature stability, and are not prone to polymerization at elevated temperatures and especially during extrusion processing. The useful crosslinking coreactants used possess high temperature stability, and are not prone to polymerization at elevated temperatures and especially during extrusion processing. The useful crosslinking coreactants are selected from the group consisting of (a) diallyl, dimethyallyl and triallyl esters of aryl polycarboxylic acids, (b) diallyl and dimethallyl esters of alkyl, cycloalkyl and aralkyl dicarboxylic acids, (c) dimethacrylate glycol esters and (d) blends of said crosslinking coreactants.The stabilizer is selected from the group consisting of alkaline earth metal oxides and lead salts. Suitable stabilizers are, for example, basic lead silicate, lead phthalate, magnesium oxide and calcium oxide.
Diallyl and dimethallyl esters of aryl polycarboxylic acids useful as crosslinking coreactants are typified by the diallyl and dimethyallyl esters of sulfonyl dibenzoic acid and the diallyl ester of 4,4'- dicarboxydiphenyl ether. The use of the diphenyl ethers as crosslinking coreactants is more fully disclosed in U.S. Patent 3,970,770. The triallyl esters of aryl polycarboxylic acids useful as a crosslinking coreactant are typified by triallyl trimesate and triallyl mellitate.
The use of these and other triallyl esters as crosslinking coreactants for fluorocarbon polymers is more fully disclosed in U.S. Patent 3,840,619. Typical diallyl and dimethallyl esters of alkyl dicarboxylic acids useful in the present process are the diallyl and dimethallyl esters of dodecandioic and brassylic acid. These and other useful esters of alkyl and cycloalkyl dicarboxylic acids are disclosed in U.S. Patent 4,051,003. Useful diallyl and methallyl esters of aralkyl dicarboxylic acids are the esters of phenyl indan and these esters are more fully disclosed in U.S. Patent 3,839,261. A preferred dimethacrylate ester is decamethylene glycol dimethacrylate. The dimethacrylate esters are preferably esters of a glycol containing at least 10 carbon atoms, as more fully disclosed in U.S. Patent 3,894,118.Reference to the foregoing patents should be made for a more complete description of the crosslinking coreactants.
The use of stabilizers with fluorocarbon polymers is known. However, the presence of the foregoing stabilizers in the extruded fluorocarbon coatings of the present products is unique in that many fluorocarbon polymers can't be successfully extruded when such stabilizers are present. It has been found that copolymers of ethylene and chlorotrifluoroethylene can be extruded with these stabilizers and that the resultant dual coating on wire forms an insulated wire of outstanding high temperature properties.
The copolymers useful as the jacketing layer are alternating copolymers of ethylene and chlorotrifluoroethylene having a mole ratio of monomeric units ranging from 40/60 to 60/40. Such copolymers and their use in irradiation crosslinked form as wire coatings is shown in U.S. Patent Re. 28628 and reference to that patent should be made for a more complete description of the copolymers and their preparation. The polyolefin coating is preferably polyethylene and even more preferably high density polyethylene. The polyethylene primary coating may optionally contain up to 60% of chlorinated polyethylene and in addition flame retardant agents such as antimony oxide, antioxidants and known polyethylene crosslinking agents.
In preparing the insulated wires of the invention, a powder blend of each of the polymeric coatings is prepared, rod extruded, pelletized and extruded onto wire. The polyolefin coating is extruded onto wire at temperatures of about 1700 to 182"C. The copolymeric jacketing material is rod extruded at 230"C to 2500C. and extruded onto wire at 270 to 300"C. The coated wire is then subjected to irradiation of from about 1 to 25 megarads with high energy electrons employing standard techniques.
The following examples illustrate the practice of the invention. Unless otherwise indicated, all parts are by weight.
Example 1 Samples were prepared from the following formulations: Primary Coating Composition: High Density Polyethylene 100 parts Antimony Oxide 5 parts Antioxidant1 5 parts Crosslinking Agent2 5 parts 1-Antioxidant was Irganox 1010, trademark for tetrakis (methylene 3- (3'5'-di-tert -butyl-4' -hydroxypheny) propionate) methane.
2-Crosslinking Agent was either trimethylol propane trimethacrylate or triallyl cyanurate.
Jacketing Coating Compositions: Poly (ethylene-chlorotrifluoroethylene) 100 parts Decamethylene glycol dimethacrylate 5 parts Basic Silicate of White Lead 5 parts
Dynamic t-Thwugh Test snsi nuiiu sd 4ui t0 SuM pdsu SMo11o; su ui.ui.uqmuq paads,Ejrle uur Test (snudiu SS ulelu!e5f/ttraqrir!y3 leuauryjihbbdd!nba laJsaL uol)sUI fuzzBu'(amleladuIa) puuS alnlelailiiral UI001 Y09 3e pamlOJlad u s)sa] o SSa4S uoiuInsuI ufrrsn S iM jo pgI.aq uo uo JBaAa aq aulurlaap or pasn ale s)sa y9n'8 3i.ru'uuAd Z aldure'x3'Jo puu T alcIuItxa Jo saTdureS ay uo iuò 2. PVDF 25 10 3- E/gB 3. r 150 12 10 0S150 12 150 12 10 4. PVDF sT OX 150 6 a cl Z 'sy3el .i These results indicate that the deformation the 15 15 invention is results indicate that the IS:- r resistance of the insulated conlda9ucMris WE CLAIM IS:: An insulated wire 0fPrisin an electrical conductor coated with a first and .PlfJJ6 OrpsjIdaEeaBtypl;ij;,c i~;UYti#Ini!tsoi8olcsi ga 20 iQ1Fihtasnsi slinked copolymer of ethylene and"cmaroltl8iI8!ltelta o weight of a crosslinking coreactant sed from the group consist lyl and triallyl esters of aryl polycarbox6?n()il pzrt!iPBYZ cycloanralkldicarboxylic acids, (c) dimethacrylate glycoleste S n? line getal said or adeandcSlaitm 1 and oxide in 10% by weight the salt. comprising an 25 alkaline etal oxide or a lead salt. 2. 3. A wir product as claimed in Claim 1, and in which; the polyd6lyethylene. 3. A wire product as claimed in Claim 2, inwhich the polyethylene ontans up to 60%by weight of product as claimed in Clam 1, 2 on 3, and in high the cfflorinateethylene. 30 4. A wire product as second in Claim 1, 2 or 3, and in triallyl crosslinking /ay3i7 30 in A the second as layer m Calm iiaQC353, and is high the triallyl coreactant 5. A wire product as claimed in Cla'in?13, and in which the crosslinking coreactant in in product the second in layer 1,2 on 3 and is =ne the crosslinkingglycol dimethacrylate 6. A wire product as claimed in Claim 1,2 or 3 and in which the crosslinking coreactant in 35 'ksPs'1 tri I tn' Sari'is . iaaiJ!SB;Liod"i8crl 35 spite ald w ; sa zelfloltpg asse atR pip pan)psqns selM nq guIYuIIsso.J oI pnjisqns SaM - aldrX3Ji%rJP.Etilf-13sOi 9ur;;l )3 sambo ayl IOJ .. 40 airrU03 auaPi.l/iulA/ilodx daDxaT < inc 40 us 12 IOJ .3002 le S1sal apd3 a3llpu "or 9 Sap saIdurts ayl 'illleoBI3adS 'Sar mIa .OOC.fe -sad paynsal AlIaiJtd asJnoq90 qrfPPIYPIUqerala33e pas uiga uiai1a p Sl auaT6ya6Tod pa)dreEPf diZP.lelPualsqns j-J800Zliuaw I1EtTIifPatt;;PiiaUallimaAOd ayl ST I Saldrues IIe 'uoIlrppe pOOZ a 3o aIodJo puayq eJo u9isqns aq S3lduias UI 'ssnoy u1 SJno4 291 oJ SJnoq s)sa ap63 ill aql pSsad 0 paelaTa33e ,yl pSsad s: ,113 pA aJII pua put! 9 O3 ?III llV a3UPlp1033e UI 4sal 5( 3laures I'tr 'suorJIJI3adss d5 0! Sarcas e ol paaeqns rrayl alaM a o saures alarm paleo:, a'lL 01: 4 aqlM 0 aYJI.(IIut 'Spele8auI 30 Jo sop uOIeIpelq ua o pai3afqns uq say e ze (I'.iu uaql sehl o) seal BulS pzzel lalDe na ax{qU < dt a Bu13eoo ulaysd,I S10.0 Jo pildda : sa paHddr? sM i 1 S uoysn;xlteJS,;6iZfIlrfa7tsmt4 3 'aqM laddo paleo UP (2/65) a9n9 OZ o Jo a3BJms am olUO paptuxa Sallad q ioj paz!lallad 0g9 Uatpli345ISEftau!3ayr!C "Y pa .3,OSZ PUF! ua qnoq qa leurtld aq 103 '3,S9I Jo Amird Ulpeay pue papyQdapMod.y3ea al;Z1PitJt,rtt84Uj 0/0 a hrruud 5f E/cTl'E Jo wV alorir OS/OSe uIAq) % 5fI 4qsun 2. PVDF 25 0969'I 133 10 3. E/CIFE 15a 12 4. PVDF 150 6
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (6)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    Dynamic t-Thwugh Test snsi nuiiu sd 4ui t0 SuM pdsu SMo11o; su ui.ui.uqmuq paads,Ejrle uur Test (snudiu SS ulelu!e5f/ttraqrir!y3 leuauryjihbbdd!nba laJsaL uol)sUI fuzzBu'(amleladuIa) puuS alnlelailiiral UI001 Y09 3e pamlOJlad u s)sa] o SSa4S uoiuInsuI ufrrsn S iM jo pgI.aq uo uo JBaAa aq aulurlaap or pasn ale s)sa y9n'8 3i.ru'uuAd Z aldure'x3'Jo puu T alcIuItxa Jo saTdureS ay uo iuò
  2. 2. PVDF 25 10 3- E/gB 3. r 150 12 10 0S150 12 150 12 10 4. PVDF sT OX 150 6 a cl Z 'sy3el .i These results indicate that the deformation the 15 15 invention is results indicate that the IS:- r resistance of the insulated conlda9ucMris WE CLAIM IS:: An insulated wire 0fPrisin an electrical conductor coated with a first and .PlfJJ6 OrpsjIdaEeaBtypl;ij;,c i~;UYti#Ini!tsoi8olcsi ga 20 iQ1Fihtasnsi slinked copolymer of ethylene and"cmaroltl8iI8!ltelta o weight of a crosslinking coreactant sed from the group consist lyl and triallyl esters of aryl polycarbox6?n()il pzrt!iPBYZ cycloanralkldicarboxylic acids, (c) dimethacrylate glycoleste S n? line getal said or adeandcSlaitm 1 and oxide in 10% by weight the salt. comprising an 25 alkaline etal oxide or a lead salt. 2. 3. A wir product as claimed in Claim 1, and in which; the polyd6lyethylene.
  3. 3. A wire product as claimed in Claim 2, inwhich the polyethylene ontans up to 60%by weight of product as claimed in Clam 1, 2 on 3, and in high the cfflorinateethylene. 30
  4. 4. A wire product as second in Claim 1, 2 or 3, and in triallyl crosslinking /ay3i7 30 in A the second as layer m Calm iiaQC353, and is high the triallyl coreactant
  5. 5. A wire product as claimed in Cla'in?13, and in which the crosslinking coreactant in in product the second in layer 1,2 on 3 and is =ne the crosslinkingglycol dimethacrylate
  6. 6. A wire product as claimed in Claim 1,2 or 3 and in which the crosslinking coreactant in 35 'ksPs'1 tri I tn' Sari'is . iaaiJ!SB;Liod"i8crl 35 spite ald w ; sa zelfloltpg asse atR pip pan)psqns selM nq guIYuIIsso.J oI pnjisqns SaM - aldrX3Ji%rJP.Etilf-13sOi 9ur;;l )3 sambo ayl IOJ .. 40 airrU03 auaPi.l/iulA/ilodx daDxaT < inc 40 us 12 IOJ .3002 le S1sal apd3 a3llpu "or 9 Sap saIdurts ayl 'illleoBI3adS 'Sar mIa .OOC.fe -sad paynsal AlIaiJtd asJnoq90 qrfPPIYPIUqerala33e pas uiga uiai1a p Sl auaT6ya6Tod pa)dreEPf diZP.lelPualsqns j-J800Zliuaw I1EtTIifPatt;;PiiaUallimaAOd ayl ST I Saldrues IIe 'uoIlrppe pOOZ a 3o aIodJo puayq eJo u9isqns aq S3lduias UI 'ssnoy u1 SJno4 291 oJ SJnoq s)sa ap63 ill aql pSsad 0 paelaTa33e ,yl pSsad s: ,113 pA aJII pua put! 9 O3 ?III llV a3UPlp1033e UI 4sal 5( 3laures I'tr 'suorJIJI3adss d5 0! Sarcas e ol paaeqns rrayl alaM a o saures alarm paleo:, a'lL 01: 4 aqlM 0 aYJI.(IIut 'Spele8auI 30 Jo sop uOIeIpelq ua o pai3afqns uq say e ze (I'.iu uaql sehl o) seal BulS pzzel lalDe na ax{qU < dt a Bu13eoo ulaysd,I S10.0 Jo pildda : sa paHddr? sM i 1 S uoysn;xlteJS,;6iZfIlrfa7tsmt4 3 'aqM laddo paleo UP (2/65) a9n9 OZ o Jo a3BJms am olUO paptuxa Sallad q ioj paz!lallad 0g9 Uatpli345ISEftau!3ayr!C "Y pa .3,OSZ PUF! ua qnoq qa leurtld aq 103 '3,S9I Jo Amird Ulpeay pue papyQdapMod.y3ea al;Z1PitJt,rtt84Uj 0/0 a hrruud 5f E/cTl'E Jo wV alorir OS/OSe uIAq) % 5fI 4qsun 2. PVDF 25 0969'I 133 10 3. E/CIFE 15a 12 4. PVDF 150 6
GB4013777A 1976-10-08 1977-09-27 Insulated electrical conductor Expired GB1569460A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US73079376A 1976-10-08 1976-10-08

Publications (1)

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GB1569460A true GB1569460A (en) 1980-06-18

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GB4013777A Expired GB1569460A (en) 1976-10-08 1977-09-27 Insulated electrical conductor

Country Status (6)

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BE (1) BE859469A (en)
CA (1) CA1110122A (en)
DE (1) DE2744904A1 (en)
ES (1) ES463010A1 (en)
FR (1) FR2367332A1 (en)
GB (1) GB1569460A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116082730A (en) * 2022-11-01 2023-05-09 广州敬信高聚物科技有限公司 Irradiation crosslinking type composition containing ECTFE and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6802188A (en) * 1967-03-01 1968-09-02
US3840619A (en) * 1972-07-28 1974-10-08 Itt Polymeric compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116082730A (en) * 2022-11-01 2023-05-09 广州敬信高聚物科技有限公司 Irradiation crosslinking type composition containing ECTFE and application thereof
CN116082730B (en) * 2022-11-01 2023-11-03 广州敬信高聚物科技有限公司 Irradiation crosslinking type composition containing ECTFE and application thereof

Also Published As

Publication number Publication date
FR2367332A1 (en) 1978-05-05
DE2744904A1 (en) 1978-04-13
ES463010A1 (en) 1978-06-16
BE859469A (en) 1978-04-07
CA1110122A (en) 1981-10-06

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Legal Events

Date Code Title Description
PS Patent sealed
732 Registration of transactions, instruments or events in the register (sect. 32/1977)
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19930927