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WO1996037899A1 - Compositions polymeres et cables electriques - Google Patents

Compositions polymeres et cables electriques Download PDF

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Publication number
WO1996037899A1
WO1996037899A1 PCT/GB1996/001252 GB9601252W WO9637899A1 WO 1996037899 A1 WO1996037899 A1 WO 1996037899A1 GB 9601252 W GB9601252 W GB 9601252W WO 9637899 A1 WO9637899 A1 WO 9637899A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
parts
filler
lead
surface treatment
Prior art date
Application number
PCT/GB1996/001252
Other languages
English (en)
Inventor
Stefan Verne
George Paul Richard Bielstein
Leon Panasiuk
Original Assignee
Bicc Public Limited Company
Katz, Maurice
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 Bicc Public Limited Company, Katz, Maurice filed Critical Bicc Public Limited Company
Priority to AU58267/96A priority Critical patent/AU5826796A/en
Priority to MX9708717A priority patent/MX9708717A/es
Priority to GB9722800A priority patent/GB2314562A/en
Priority to EP96919899A priority patent/EP0829090A1/fr
Publication of WO1996037899A1 publication Critical patent/WO1996037899A1/fr

Links

Classifications

    • 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

Definitions

  • This invention relates to polymer compositions for -use in electric cables, and more particularly as dielectric (insulation) in "medium voltage” power cables in which the dielectric is bounded by a conductor screen and a core screen both of conductive polymeric material; it also relates to the cables in which they are used.
  • compositions based on ethylene copolymer rubbers which may be defined for certainty in the context of this application as hydrocarbon copolymers of ethylene with at least one other alkene monomer having from 3 to 10 carbon atoms which copolymers have rubbery elastic characteristics .
  • the service life of medium-voltage cables is in many cases limited by the long term diminution of electric strength of the dielectric which is now attributed to the formation of water-trees (or electric trees, if water is absent) , and current EPR formulations generally contain an oxide of lead in an amount corresponding to several phr (parts per hundred of polymer) of lead, calculated as element, as the means of securing a sufficient stability of electrical strength (a tree suppressant) .
  • the amount of lead used in electric cables is small compared with other usages, it is now considered desirable to eliminate any avoidable source of lead in contact with the environment.
  • Zinc oxide is a conventional constituent of EPR- and EPDM-based compositions, used at a level around 5phr as a curing aid or pH stabiliser; but it has not been perceived as having a useful effect on electrical ⁇ tablility.
  • compositions in accordance with the present invention comprise, in parts by weight:
  • Polymer base of which at least
  • Zinc oxide 10-30 Lead compounds not to exceed 1 calculated as element and appropriate amounts of conventional ingredients comprising an antioxidant, a curing system and a processing aid.
  • the ethylene copolymer rubber may be an EPR or an
  • EPDM each of which may be either semi-crystalline or amorphous provided that it has rubbery elastic properties.
  • Ethylene copolymer rubbers made with "single-site" catalyst systems can also be used and may have advantages in some cases.
  • Preferably all the filler is calcined clay.
  • the surface treatment agent for the filler is preferably selected from silanes, siloxanes, metal salts of organic acids, and organic acids that are substantially insoluble in water. More than one surface treatment agent can be used. Silane surface treatment agents are preferred.
  • the filler is preferably pre-treated with the surface treatment agent (or with one of them) but preferably the composition includes free surface treatment agent as well. Appropriate amounts will vary somewhat from one surface treatment agent to another, but will typically be in the range from about 1-2 parts pre-coated on the filler and about 1-5 parts added separately.
  • Preferred content of zinc oxide is about 15-25 parts; conventional grades can be used, but grades of higher purity are preferred.
  • compositions based on semicrystalline EPR's or EPDM's preferably contain polyethylene, preferably in an amount in the range from 3 to 10 parts, as a processing aid; larger amounts, up to the limit of 50 parts, can be used for cost reduction and/or in the case of some amorphous EPR's or EPDM's to enable granulation of the composition.
  • the content of lead compounds should be as small as possible, and ideally zero; however, a small amount of certain lead compounds may achieve a major improvement in electrical stability with much less environmental hazard than conventional EPR or EPDM compositions for medium-voltage cables.
  • any of the conventional antioxidants can be used in their usual amounts; we particularly prefer antioxidants of the poly-dihydroxyguinoline class, in amounts in the range 0.5 to 3 parts.
  • compositions of the invention can be cured with peroxides, optionally with poly-unsaturated co-agents such as triallylisocyanurate, or with peroxides and sulfur; compositions based on EPDM's can also be cured with conventional sulfur-based systems.
  • Suitable processing aids apart from those already mentioned, include paraffin wax in conventional amounts up to around 6 parts and hydrocarbon oils in amounts up to around 30 parts (varying form oil to oil) .
  • compositions as detailed below were prepared on a 12-inch (300m) laboratory 2-roll mill; the polymer-base was plasticised and the other ingredients, except curing agents, added at a temperature controlled to be in the range 120- 130°; the curing agents were added in a separate step on the "cold" mill. It should be noted that a few ingredients used in experiments around 30 years ago are no longer available.
  • Example 1
  • the composition showed first signs of brittleness after about 35 days.
  • Deterioration was detectable in about weeks 60 to 70, when readings ranged from 0.49 to 1.0 x 10 14 ohm.cm, and gradually increased with the readings falling below 0.1 x 10 14 ohm.cm for the first time at week 74 and reaching 0.014 x 10 14 when the tests were discontinued at 120 weeks.
  • Specific inductive capacitance varied by no more than 5% from its value after one day's exposure until week 78, and had changed by only about 8% at the end of 120 weeks.
  • composition had a tensile strength of 7.07MPa (1025psi) , elongation of 390% and volume resistivity of 13 x 10 15 ohm.cm. This composition showed first signs of brittleness in the preliminary air ageing test after 48 days at 150°C. The volume resistivity in the wet electrical
  • Example 4 This was identical with Example 1, except that 1 part of lead stearate was added. After press cure for 45 minutes at 160°, the composition had a tensile strength of 6.4MPa (925p ⁇ i) , elongation of 515% and volume resistivity of 9.2 x 10 1E ohm.cm.
  • the volume resistivity remained in the range 1.1 to 3.6 x 10 14 ohm.cm throughout the 120-week period of the test in water, with values in the upper part of the' range (over 2.5) observed mostly in the period from 34 to 68 weeks.
  • Measurements of increase in specific inductive capacitance showed no very clear pattern, but were mostly below 5% for the first 64 weeks and mostly in the range 5-10% in weeks 65-120. Power factors observed were all in the range from 1.7 to 2.8, with only about five readings over 2.0% after week 30.
  • Example 5 The composition of this example comprises 95 parts of a semicrystalline EPR (Nordel® 2722), 5 parts of a low-density polyethylene of Melt Index 2.0, 60 parts of surface-treated calcined clay (Translink® 37), l part of vinyl tris i 2-methoxy ethoxy) silane, 20 parts zinc oxide, 5 parts paraffin wax, 1.5 parts antioxidant (Flectol ® H) and 2.5 parts of dicumyl peroxide (Dicup®) .
  • a semicrystalline EPR Naordel® 2722
  • 5 parts of a low-density polyethylene of Melt Index 2.0 60 parts of surface-treated calcined clay (Translink® 37), l part of vinyl tris i 2-methoxy ethoxy) silane, 20 parts zinc oxide, 5 parts paraffin wax, 1.5 parts antioxidant (Flectol ® H) and 2.5 parts of dicumyl peroxide (Dicup®) .
  • Example 6 Example 6
  • composition of this example comprises 100 parts of an amorphous EPR (Nordel ® 2522) , 60 parts of surface-treated calcined clay (Translink® 37) , 1 part of vinyl tris ( 2-methoxy ethoxy) silane, 20 parts zinc oxide, 5 parts paraffin wax, 1.5 parts antioxidant (Flectol® H) and 2.5 parts of dicumyl peroxide (Dicup®) .
  • Example 7 The composition of this example comprises 100 parts of an semicrystalline EPR (Nordel® 2722) , 60 parts of surface- treated calcined clay (Translink® 37) , 1 part of vinyl tris ⁇ 2-methoxy ethoxy) silane, 20 parts zinc oxide, 1.5 parts paraffin wax, 1.5 parts antioxidant (Agerite ® MA) and 2.5 parts of dicumyl peroxide (Dicup ® ) .
  • EPR semicrystalline EPR
  • Translink® 37 surface- treated calcined clay
  • vinyl tris ⁇ 2-methoxy ethoxy silane 20 parts zinc oxide
  • 1.5 parts paraffin wax 1.5 parts
  • antioxidant antioxidant
  • Dicup ® MA dicumyl peroxide
  • Example 9 This was identical with Example 7 except that the clay was a non-commercial untreated one, identical with Translink 37 except for the omission of the surface treatment normally applied to it.
  • Example 9 This was identical with Example 7 except that the clay was a non-commercial untreated one, identical with Translink 37 except for the omission of the surface treatment normally applied to it.
  • Comparison Example B dicumyl peroxide (Dicup ® ) (3 parts) and sulfur (0.3 part) . Both these comparison examples were rejected on the basis of preliminary screening tests in air at 150°C, and were not subjected to electrical stability tests; comparison Example A exhibited brittleness in this test at 11 days and Comparison Example B surface degradation at 6 days.
  • Example 2 This was identical with Example 1 except that a conventional

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

Abstract

La présente invention concerne une composition sans danger pour l'environnement, dont la stabilité électrique est suffisante pour pouvoir servir à fabriquer un matériau diélectrique (isolant) d'un câble à moyenne tension, cette composition étant constituée des éléments suivants: 100 parties en poids d'une base polymère dont au moins 50 parties sont constituées de caoutchouc de copolymère d'éthylène et le reste, le cas échéant, de polyéthylène 40 à 120 parties en poids d'une charge minérale dont au moins la moitié est composée d'argile calcinée, 1 à 6 parties en poids d'un agent de traitement de surface pour la charge minérale, 10 à 30 parties en poids d'oxyde de zinc, au plus 1 partie en poids de composés de plomb, calculés en tant qu'élément, ainsi que les quantités appropriées d'ingrédients traditionnels composés d'un antioxydant, d'un système de durcissement et d'un adjuvant.
PCT/GB1996/001252 1995-05-25 1996-05-24 Compositions polymeres et cables electriques WO1996037899A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU58267/96A AU5826796A (en) 1995-05-25 1996-05-24 Polymer compositions and electric cables
MX9708717A MX9708717A (es) 1995-05-25 1996-05-24 Composiciones polimericas y cables electricos.
GB9722800A GB2314562A (en) 1995-05-25 1996-05-24 Polymer compositions and electric cables
EP96919899A EP0829090A1 (fr) 1995-05-25 1996-05-24 Compositions polymeres et cables electriques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9510620.9 1995-05-25
GB9510620A GB9510620D0 (en) 1995-05-25 1995-05-25 Polymer compositions and electric cables

Publications (1)

Publication Number Publication Date
WO1996037899A1 true WO1996037899A1 (fr) 1996-11-28

Family

ID=10775029

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/001252 WO1996037899A1 (fr) 1995-05-25 1996-05-24 Compositions polymeres et cables electriques

Country Status (8)

Country Link
EP (1) EP0829090A1 (fr)
AR (1) AR010975A1 (fr)
AU (1) AU5826796A (fr)
CA (1) CA2222094A1 (fr)
GB (2) GB9510620D0 (fr)
MX (1) MX9708717A (fr)
PE (1) PE2798A1 (fr)
WO (1) WO1996037899A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6815062B2 (en) 1999-06-21 2004-11-09 Pirelli Cavi E Sistemi S.P.A. Cable, in particular for electric energy transportation or distribution, and an insulating composition used therein
US7985804B2 (en) 2006-11-06 2011-07-26 Exxonmobil Chemical Patents Inc. Rubber toughened compositions, articles, films, and methods of making the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2344613A1 (fr) * 1976-03-15 1977-10-14 Alcan Res & Dev Revetement a base de polyethylene et cable conducteur electrique comportant un tel revetement
US4204024A (en) * 1978-06-15 1980-05-20 Harvey Hubbell, Incorporated Electrical insulation composition having low power factor
EP0042440A1 (fr) * 1979-12-25 1981-12-30 Acome, Societe Cooperative De Travailleurs Composition organique de poids moleculaire eleve de retardement du feu

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2344613A1 (fr) * 1976-03-15 1977-10-14 Alcan Res & Dev Revetement a base de polyethylene et cable conducteur electrique comportant un tel revetement
US4204024A (en) * 1978-06-15 1980-05-20 Harvey Hubbell, Incorporated Electrical insulation composition having low power factor
EP0042440A1 (fr) * 1979-12-25 1981-12-30 Acome, Societe Cooperative De Travailleurs Composition organique de poids moleculaire eleve de retardement du feu

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6815062B2 (en) 1999-06-21 2004-11-09 Pirelli Cavi E Sistemi S.P.A. Cable, in particular for electric energy transportation or distribution, and an insulating composition used therein
US7985804B2 (en) 2006-11-06 2011-07-26 Exxonmobil Chemical Patents Inc. Rubber toughened compositions, articles, films, and methods of making the same

Also Published As

Publication number Publication date
EP0829090A1 (fr) 1998-03-18
AR010975A1 (es) 2000-08-02
GB9722800D0 (en) 1997-12-24
CA2222094A1 (fr) 1996-11-28
MX9708717A (es) 1997-12-31
PE2798A1 (es) 1998-02-28
GB2314562A (en) 1998-01-07
AU5826796A (en) 1996-12-11
GB9510620D0 (en) 1995-07-19

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