SE508564C3 - Composition for electrical cables comprising an ethylene copolymer, which as a comonomer comprises a polyalkylene glycol monomethacrylate - Google Patents
Composition for electrical cables comprising an ethylene copolymer, which as a comonomer comprises a polyalkylene glycol monomethacrylateInfo
- Publication number
- SE508564C3 SE508564C3 SE9700374A SE9700374A SE508564C3 SE 508564 C3 SE508564 C3 SE 508564C3 SE 9700374 A SE9700374 A SE 9700374A SE 9700374 A SE9700374 A SE 9700374A SE 508564 C3 SE508564 C3 SE 508564C3
- Authority
- SE
- Sweden
- Prior art keywords
- composition
- weight
- composition according
- polymer
- ethylene copolymer
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 60
- 229920001038 ethylene copolymer Polymers 0.000 title claims description 19
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 title description 8
- 229920001515 polyalkylene glycol Polymers 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- -1 alkylene glycol Chemical compound 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 239000004065 semiconductor Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 45
- 240000005572 Syzygium cordatum Species 0.000 description 19
- 235000006650 Syzygium cordatum Nutrition 0.000 description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000005977 Ethylene Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 229920001897 terpolymer Polymers 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 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 4
- UEQXEQXNHPQBQO-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOCCOCCO UEQXEQXNHPQBQO-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 210000002268 wool Anatomy 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
- 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
-
- 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
-
- 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
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2813—Protection against damage caused by electrical, chemical or water tree deterioration
Description
508 564 ningsförfarande och de använda materialens kvalitet och renhet. Dessa förbättringar har medfört en ökad livslängd hos de framställda kablarna. Trots detta finns emellertid ett uttalat behov av ytterligare förbättrade material med avseende på motståndskraft och vattenträdsbildning. En sådan förbättrad motståndskraft mot vattenträdsbildning är önskvärd inte bara för isolerskiktsmaterial, utan även för halvledarskiktsmaterial hos elektriska kablar. En annan viktig egenskap hos halvledarskiktsmaterial hos elektriska kablar är hög motståndskraft mot spännings- sprickbildning. 508 564 process and the quality and purity of the materials used. These improvements have led to an increased service life of the manufactured cables. Despite this, however, there is a pronounced need for further improved materials with respect to resilience and water tree formation. Such an improved resistance to water tree formation is desirable not only for insulating layer materials, but also for semiconductor layer materials of electrical cables. Another important property of semiconductor layer materials in electrical cables is high resistance to voltage cracking.
Genom den europeiska patentskriften EP-A-0 057 604 är det känt att motverka bildning av vattenträd genom att till en halvledande komposition, som i huvudsak består av en polyolefin och 5-50 vikt% kimrök, räknat på den totala kompositionens vikt, sätta en polyetylenglykol med en molekylvikt av ca 1000-20000 i en mängd av 0,1-20 vikt%.From the European patent specification EP-A-0 057 604 it is known to counteract the formation of water trees by adding to a semiconducting composition, which mainly consists of a polyolefin and 5-50% by weight carbon black, based on the weight of the total composition polyethylene glycol having a molecular weight of about 1000-20,000 in an amount of 0.1-20% by weight.
Denna komposition är avsedd för halvledande skikt hos elektriska kablar och genom tillsatsen av polyetylengly- kol uppges man kunna eliminera vattenträd som växer in i isoleringsskiktet från gränsytan mellan isoleringsskiktet och det halvledande skiktet.This composition is intended for semiconducting layers of electrical cables and by the addition of polyethylene glycol it is stated that it is possible to eliminate water trees growing into the insulating layer from the interface between the insulating layer and the semiconducting layer.
Genom den amerikanska patentskriften US-A-4 812 505 är vidare känt en komposition, som är användbar för iso- leringsskikt i elektriska kablar och som är motstånds- kraftig mot bildning av vattenträd. Kompositionen inbe- griper en sampolymer av eten och minst en alfa-olefin med 4-8 kolatomer, såsom 1-buten, l-hexen eller l-okten, och innehåller dessutom en polyetylenglykol med en molekyl- vikt i området ca 1000-20000 i en mängd av 0,1-20 vikt%.Furthermore, U.S. Pat. No. 4,812,505 discloses a composition which is useful for insulating layers in electrical cables and which is resistant to the formation of water trees. The composition comprises a copolymer of ethylene and at least one alpha-olefin having 4-8 carbon atoms, such as 1-butene, 1-hexene or 1-octene, and further contains a polyethylene glycol having a molecular weight in the range of about 1000-20000 in an amount of 0.1-20% by weight.
Nackdelen med att använda vattenträdsbildningsmot- verkande tillsatser, såsom polyetylenglykol, är att det finns risk, p g a polyetylenglykolens bristande kompati- bilitet med baspolymeren (polyeten), för utsvettning av polyetylenglykolen, särskilt om dess molekylvikt ej är hög. Om molekylvikten är hög påverkas å andra sidan möj- ligheten till effektiv inblandning negativt.The disadvantage of using water tree-forming additives, such as polyethylene glycol, is that there is a risk, due to the polyethylene glycol's lack of compatibility with the base polymer (polyethylene), of the polyethylene glycol sweating, especially if its molecular weight is not high. On the other hand, if the molecular weight is high, the possibility of effective mixing is negatively affected.
Sos 564 Genom den europeiska patentskriften EP-A-0 538 033 är en extruderbar eten-hydroxiakrylatsam- eller -terpoly- mer känd, vilken utöver eten innehåller 7-30 vikt% hydr- oxiakrylat samt 0-40 vikt% av en tredje monomer vald bland vinylestrar, allylestrar, och akryl- eller metak- rylestrar, som inte innehåller hydroxylgrupper. Hydroxi- akrylatet kan utgöras av varje ester av glykol eller polyglykol och akrylsyra eller metakrylsyra, men är före- trädesvis hydroxietylmetakrylat, hydroximetylmetakrylat, hydroxipropylakrylat eller hydroxipropylmetakrylat.Sos 564 From the European patent specification EP-A-0 538 033 an extrudable ethylene-hydroxyacrylate copolymer or terpolymer is known, which in addition to ethylene contains 7-30% by weight of hydroxyacrylate and 0-40% by weight of a third monomer selected among vinyl esters, allyl esters, and acrylic or methacrylic esters, which do not contain hydroxyl groups. The hydroxyacrylate may be any ester of glycol or polyglycol and acrylic acid or methacrylic acid, but is preferably hydroxyethyl methacrylate, hydroxymethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.
Enligt patentskriften är hydroxiakrylat tidigare känt i samband med smältlim, och den extruderade produkten enligt patentskriften, t ex en film, är hydrofil och absorberar och genomsläpper fuktighet, varvid etenhydr- oxiakrylatsampolymeren förbättrar vidhäftningen mot exempelvis polära plaster och andra material samt för- bättrar styrkeegenskaperna p g a vätebindningar. Patent- skriften anger inte användning av polymeren i kompositio- ner för elektriska kablar.According to the patent, hydroxyacrylate is previously known in connection with hot melt adhesives, and the extruded product according to the patent, for example a film, is hydrophilic and absorbs and permeates moisture, whereby the ethylene hydroxyacrylate copolymer improves adhesion to, for example, polar plastics and other materials. hydrogen bonds. The patent does not disclose the use of the polymer in compositions for electrical cables.
Genom Derwents abstract nr 77-85827Y/48 av den japanska patentansökan JP 7644050 är en etensampolymer känd, vilken innehåller 25-99,9 vikt% eten, 75-0,1 vikt% polyalkylenglykolmonoakrylat, samt 0-65 vikt% andra ete- niskt omättade monomerer. Denna polymer anges vara an- vändbar för målfärg, tryckfärg, etc, som beläggningsmedel för metall, papper, ull, etc, som bindemedel, etc. Det anges inte att polymeren skulle vara användbar i komposi- tioner för elektriska kablar.Derwent's patent No. 77-85827Y / 48 of Japanese Patent Application JP 7644050 discloses an ethylene copolymer containing 25-99.9% by weight of ethylene, 75-0.1% by weight of polyalkylene glycol monoacrylate, and 0-65% by weight of other ethylene unsaturated monomers. This polymer is stated to be useful for target paint, printing ink, etc., as a coating agent for metal, paper, wool, etc., as a binder, etc. It is not stated that the polymer would be useful in compositions for electrical cables.
Man har nu enligt föreliggande uppfinning överras- kande upptäckt att användning av (poly)alkylenglykolmono- (met)akrylat som sammonomer i etenpolymerer gör det möj- ligt att åstadkomma kompositioner för elektriska kablar med förbättrad motståndskraft mot bildning av vattenträd.It has now surprisingly been discovered according to the present invention that the use of (poly) alkylene glycol mono- (meth) acrylate as a comonomer in ethylene polymers makes it possible to provide compositions for electrical cables with improved resistance to the formation of water trees.
Enligt uppfinningen åstadkommes sålunda en komposi- tion för elektriska kablar, kännetecknad därav, att den inbegriper en etensampolymer, vilken som en sammonomer 508 564 inbegriper ett (poly)alkylenglykolmono(met)akrylat med formel I R1O R2 lll l H2C=C-C-O-(CH2CHO)n-H (I) där R1 = H eller CH; R2 = H eller Chy n = 1-20.According to the invention there is thus provided a composition for electrical cables, characterized in that it comprises an ethylene copolymer which as a comonomer 508 564 comprises a (poly) alkylene glycol mono (meth) acrylate of formula I R10 R ) nH (I) where R 1 = H or CH; R2 = H or Chy n = 1-20.
Mera speciellt avser man att använda kompositionen enligt uppfinningen i isolerande och halvledande skikt för elektriska kablar.More particularly, it is intended to use the composition according to the invention in insulating and semiconducting layers for electrical cables.
Andra utmärkande drag och fördelar hos uppfinningen kommer att framgå av den efterföljande beskrivningen och de bifogade patentkraven.Other features and advantages of the invention will become apparent from the following description and the appended claims.
Med det här använda uttrycket ”etensampolymer” avses en etenbaserad polymer, som erhållits genom polymerisa- tion av eten och en eller flera andra monomerer, varvid en av dessa andra monomerer utgöres av (poly)alkylengly- kolmono(met)akrylatet med formel I. Företrädesvis utgöres etensampolymeren av en polymer av eten och monomeren med formel I eller av eten, monomeren med formel I och ytter- ligare en monomer, dvs i det sistnämnda fallet en s k terpolymer.As used herein, the term "ethylene copolymer" refers to an ethylene-based polymer obtained by polymerizing ethylene and one or more other monomers, one of these other monomers being the (poly) alkylene glycol mono (meth) acrylate of formula I. Preferably, the ethylene copolymer consists of a polymer of ethylene and the monomer of formula I or of ethylene, the monomer of formula I and a further monomer, i.e. in the latter case a so-called terpolymer.
Med de här använda uttrycken ”(met)akrylsyra” och ”(met)akrylat” avses såväl akrylsyra och akrylat som met- akrylsyra och metakrylat.The terms “(meth) acrylic acid” and “(meth) acrylate” as used herein refer to acrylic acid and acrylate as well as methacrylic acid and methacrylate.
Såsom framgår av formel I ovan, är (poly)alkylengly- kolmono(met)akrylatet med formel I en ester av akryl- eller metakrylsyra med en (poly)alkylenglykol, där alky- lenglykolen väljs bland etylenglykol eller propylenglykol och antalet alkylenoxidenheter kan variera från l till , dvs n = l-20, företrädesvis l-10, i formel I. Före- trädesvis är R1 i formel I CH3, dvs den esterbildande syran är metakrylsyra, och R2 i formel I är H, dvs den 508 564 esterbildande (poly)alkylenglykolen är en (poly)etylen- glykol. När n=l är monomeren med formel I, med de an- givna föredragna betydelserna av R1 och R2, hydroxietyl- metakrylat (HEMA). När n=6 är monomeren med formel I hexaetylenglykolmetakrylat vid de angivna, föredragna betydelserna av R1 och R2.As shown in formula I above, the (poly) alkylene glycol mono (meth) acrylate of formula I is an ester of acrylic or methacrylic acid with a (poly) alkylene glycol, wherein the alkylene glycol is selected from ethylene glycol or propylene glycol and the number of alkylene oxide units may vary from 1 to, i.e. n = 1-20, preferably 1-10, in formula I. Preferably R 1 in formula I is CH 3, i.e. the ester-forming acid is methacrylic acid, and R 2 in formula I is H, i.e. the 508 564 ester-forming ( The poly) alkylene glycol is a (poly) ethylene glycol. When n = 1 is the monomer of formula I, with the indicated preferred meanings of R 1 and R 2, hydroxyethyl methacrylate (HEMA). When n = 6, the monomer of formula I is hexaethylene glycol methacrylate at the indicated, preferred meanings of R1 and R2.
Mängden av sammonomeren med formel I i etensampoly- meren kan variera inom vida gränser, men utgör företrä- desvis ca 0,l-l5 vikt%, mera föredraget ca 2-14 vikt% av sampolymeren.The amount of the comonomer of formula I in the ethylene copolymer can vary within wide limits, but preferably constitutes about 0.1 to 1.5% by weight, more preferably about 2-14% by weight of the copolymer.
Såsom angivits ovan, kan etensampolymeren eventuellt innehålla ytterligare sammonomerer utöver sammonomeren med formel I, och det föredrages att sampolymeren inne- håller en sådan ytterligare monomer, dvs att sampolymeren är en terpolymer. Denna ytterligare sammonomer kan väljas bland monomerer, som är sampolymeriserbara med eten och (poly)alkylenglykolmono(met)akrylatet med formel I. Sàda- na monomerer är välkända för fackmannen och torde inte behöva någon omfattande uppräkning, men som exempel kan nämnas vinyliskt omättade monomerer, såsom C3-CB alfa-c;e- finer, t ex propen, buten, etc; vinyliskt omättade mono- merer innehållande funktionella grupper, såsom hydroxyl- grupper, alkoxigrupper, karbonylgrupper, karboxylgrupper och estergrupper. Sådana monomerer kan t ex utgöras av (met)akrylsyra och alkylestrar därav, såsom metyl-, etyl- och butyl(met)akrylat; vinyliskt omättade, hydrolyserbara silanmonomerer, såsom vinyltrimetoxisilan; vinylacetat, m fi. Å Mängden ytterligare sammonomer(er) utöver (poly)- alkylenglykolmono(met)akrylat med formel I är från 0 till ca 40 vikt%, företrädesvis ca l-30 vikt% av etensampoly- meren.As stated above, the ethylene copolymer may optionally contain additional comonomers in addition to the comonomer of formula I, and it is preferred that the copolymer contain such an additional monomer, i.e. that the copolymer is a terpolymer. This additional comonomer can be selected from monomers which are copolymerizable with ethylene and the (poly) alkylene glycol mono (meth) acrylate of formula I. Such monomers are well known to those skilled in the art and should not require extensive listing, but for example vinyl unsaturated monomers may be mentioned. , such as C3-CB alpha-c; e-veneer, eg propylene, butene, etc .; vinylically unsaturated monomers containing functional groups such as hydroxyl groups, alkoxy groups, carbonyl groups, carboxyl groups and ester groups. Such monomers may be, for example, (meth) acrylic acid and alkyl esters thereof, such as methyl, ethyl and butyl (meth) acrylates; vinyl unsaturated hydrolyzable silane monomers such as vinyltrimethoxysilane; vinyl acetate, m fi. The amount of additional comonomer (s) in addition to (poly) -alkylene glycol mono (meth) acrylate of formula I is from 0 to about 40% by weight, preferably about 1-30% by weight of the ethylene copolymer.
För de ovan angivna monomererna gäller att summan av alla monomerhalterna är lO0 vikt%. r 508 564 Etensampolymeren enligt uppfinningen kan framställas genom ympsampolymerisation eller genom friradikalinitie- rad högtryckspolymerisation.For the above monomers, the sum of all the monomer contents is 10% by weight. 508 564 The ethylene copolymer according to the invention can be prepared by graft copolymerization or by free radical-initiated high-pressure polymerization.
Ympsampolymerisation är ett i sig välkänt polymeri- sationsförfarande inom tekniken och torde därför inte behöva beskrivas i detalj här. Allmänt tillgår ympsam- polymerisation så, att en vinylomättad monomer sampolyme- riseras med en etenpolymer, såsom en etenhomopolymer eller en etensampolymer, under inverkan av en friradikal- initiator, såsom en peroxid t ex dikumylperoxid (DCP).Graft copolymerization is a per se well-known polymerization process in the art and should therefore not need to be described in detail here. In general, graft copolymerization is such that a vinyl unsaturated monomer is copolymerized with an ethylene polymer, such as an ethylene homopolymer or an ethylene copolymer, under the action of a free radical initiator, such as a peroxide such as dicumyl peroxide (DCP).
Temperaturen vid ympsampolymerisationen skall vara till- räcklig för att sönderdelning av friradikalinitiatorn skall ske under bildning av fria radikaler, vilket med dikumylperoxid som initiator innebär ca 150-200°C, och polymerisationen kan praktiskt genomföras t ex genom blandning av komponenterna i en extruder.The temperature of the graft copolymerization must be sufficient for the free radical initiator to decompose to form free radicals, which with dicumyl peroxide as initiator means about 150-200 ° C, and the polymerization can be practically carried out, for example by mixing the components in an extruder.
Friradikalinitierad högtryckspolymerisation, som också är välkänt inom tekniken, tillgår allmänt så, att man i en reaktor, såsom en autoklav eller rörreaktor, vid ett högt tryck av ca 100-300 MPa och en förhöjd tempera- tur av ca 80-300°C bringar monomererna att reagera under inverkan av en radikalinitiator, såsom en peroxid, hydro- peroxid, syre eller azoförening. När reaktionen är avslu- tad sänks temperaturen och trycket och den erhållna, omättade polymeren utvinnes. För ytterligare detaljer beträffande framställning av etenpolymerer med högtrycks- polymerisation under friradikalinitiering kan hänvisas till Encyclopedia of Polymer Science and Engineering, Band 6 (1986), sid 383-410, särskilt sid 404-407.Free radical-initiated high-pressure polymerization, which is also well known in the art, is generally available so that in a reactor, such as an autoclave or tubular reactor, at a high pressure of about 100-300 MPa and an elevated temperature of about 80-300 ° C the monomers to react under the action of a radical initiator, such as a peroxide, hydroperoxide, oxygen or azo compound. When the reaction is complete, the temperature and pressure are lowered and the resulting unsaturated polymer is recovered. For further details regarding the preparation of ethylene polymers by high pressure polymerization during free radical initiation, reference may be made to the Encyclopedia of Polymer Science and Engineering, Volume 6 (1986), pages 383-410, especially pages 404-407.
Såsom nämnts tidigare, har man vid föreliggande upp- finning funnit att användning av (poly)alkylenglykolmono- (met)akrylatet med formel I i en etensampolymer åstadkom- mer förbättrad motståndskraft mot vattenträdsbildning (WTR) och en sådan etensampolymer är därför användbar som sus 564 material för elektriska kablar, t ex som isolerskikts- material eller som halvledarskiktsmaterial. Genom att (poly)alkylenglykolmono(met)akrylatet med formel I, som skapar motståndskraft mot vattenträdsbildning, är inpoly- meriserat i polymeren är det fast förankrad i polymer- molekylen och kan inte migrera eller utsvettas, såsom är fallet med konventionella WTR-tillsatser. Detta utgör en särskild fördel hos polymererna enligt uppfinningen.As mentioned previously, it has been found in the present invention that the use of the (poly) alkylene glycol mono- (meth) acrylate of formula I in an ethylene copolymer provides improved resistance to water tree formation (WTR) and such an ethylene copolymer is therefore useful as sus 564 materials for electrical cables, for example as insulating layer material or as semiconductor layer material. Because the (poly) alkylene glycol mono (meth) acrylate of formula I, which creates resistance to water tree formation, is polymerized in the polymer, it is firmly anchored in the polymer molecule and cannot migrate or sweat out, as is the case with conventional WTR additives. This is a particular advantage of the polymers according to the invention.
Utöver den fördelaktiga motståndskraften mot vattenträds- bildning har det visat sig att etensampolymeren enligt uppfinningen även medför andra gynnsamma och eftersträ- vade egenskaper vid användning som material i elektriska kablar. Sàlunda har det visat sig att etensampolymeren enligt uppfinningen medger en förbättrad elektrisk genom- slagshållfasthet, vilket är av värde för såväl det isole- rande skiktet som de halvledande skikten hos en elektrisk kabel. Vidare uppvisar etensampolymeren enligt uppfin- ningen en god beständighet mot miljöförorsakade spän- ningssprickor (ESCR), skikt hos elektriska kablar. vilket är av värde för halvledande För att ytterligare underlätta förståelsen av upp- finningen ges nedan några belysande, men ej begränsande exempel och jämförande exempel.In addition to the advantageous resistance to water tree formation, it has been found that the ethylene copolymer according to the invention also entails other favorable and sought-after properties when used as a material in electrical cables. Thus, it has been found that the ethylene copolymer of the invention allows an improved electrical breakdown strength, which is of value for both the insulating layer and the semiconducting layers of an electrical cable. Furthermore, the ethylene copolymer according to the invention has a good resistance to environmentally caused voltage cracks (ESCR), layers of electrical cables. which is of value for semiconductor In order to further facilitate the understanding of the invention, some illustrative but not limiting examples and comparative examples are given below.
Exempel l Motståndskraften mot vattenträdsbildning (WTR) be- stämdes för tre polymerkompositioner, Polymer 1, Polymer 2 och Polymer 3, med hjälp av s k Ashcraft-provning.Example 1 The resistance to water tree formation (WTR) was determined for three polymer compositions, Polymer 1, Polymer 2 and Polymer 3, using so-called Ashcraft testing.
Ashcraft-provning, som är en provningsmetod för be- stämning av WTR-egenskaperna hos polymerer, har beskri- vits av Ashcraft, A. C., "Water Treeing in Polymeric Dielectrics", World Electrotechnical Congress in Moscow, U.S.S.R., 22 juni 1977. Vid Ashcraft-provning åstadkommes väl karaktäriserade effekter, vatten- nämligen skarpa, fyllda intryckningar, med hjälp av en nål i formpressade koppar. En spänning av 5 kV/6 kHz pålägges över vattnet, 508 564 medan koppens botten är ansluten till jord. Temperaturen hålles konstant vid 65°C. Den genomsnittliga längden hos vattenträden efter 72 h åldring anses som ett mått på vattenträdens tillväxthastighet i det specifika isole- ringsmaterialet.Ashcraft testing, which is a test method for determining the WTR properties of polymers, has been described by Ashcraft, AC, "Water Treeing in Polymeric Dielectrics", World Electrotechnical Congress in Moscow, USSR, June 22, 1977. At Ashcraft -testation is achieved well-characterized effects, water- namely sharp, filled indentations, using a needle in molded copper. A voltage of 5 kV / 6 kHz is applied across the water, 508 564 while the bottom of the cup is connected to earth. The temperature is kept constant at 65 ° C. The average length of water trees after 72 hours of aging is considered as a measure of the growth rate of water trees in the specific insulation material.
För provningen framställdes formpressade provkroppar av de olika polymererna, varav Polymer 1 utgjordes av en (LDPE) med ett smältflöde (MFR) làgdensitetspolyeten av 2 g/10 min, som användes som referens, Polymer 2 utgjordes av 99,1 viktdelar av samma slag av LDPE, som tillsatts 0,56 viktdelar polyetylenglykol (PEG) med en molekylvikt av ca 20 000 som ett konventionellt medel mot bildning av vattenträd, och Polymer 3, som var en komposition enligt uppfinningen, utgjordes av 79,8 viktdelar av samma slag av LDPE som tillsatts 20,0 viktdelar av en terpolymer av eten, metylakrylat (13 vikt%), (3 vikt%) och hexaetylenglykolmono- metakrylat med formel I, vari R1 = CH3, R2 = H, och n = 6. Polymerkompositionerna innehöll dessutom ca 2 viktdelar dikumylperoxid samt stabilisator (ca 0,2 viktdelar). Resultaten från Ashcraft-provningen är sammanställda i nedanstående tabell.For the test, extruded specimens were prepared from the various polymers, of which Polymer 1 consisted of a (LDPE) with a melt flow (MFR) low density polyethylene of 2 g / 10 min, which was used as a reference, Polymer 2 consisted of 99.1 parts by weight of the same kind of LDPE, which was added with 0.56 parts by weight of polyethylene glycol (PEG) having a molecular weight of about 20,000 as a conventional agent for the formation of water trees, and Polymer 3, which was a composition according to the invention, consisted of 79.8 parts by weight of the same kind of LDPE to which 20.0 parts by weight of a terpolymer of ethylene, methyl acrylate (13% by weight), (3% by weight) and hexaethylene glycol monomethacrylate of formula I have been added, wherein R 1 = CH 3, R 2 = H, and n = 6. The polymer compositions further contained approx. 2 parts by weight of dicumyl peroxide and stabilizer (approx. 0.2 parts by weight). The results from the Ashcraft test are summarized in the table below.
Komposition Vattenträd Medellängd (um) Medellängd (%) Polymer l (referens) 374 100 Polymer 2 (jämförande) 149 40 Polymer 3 (uppfinningen) 126 34 Av försöksresultaten framgår de klart förbättrade WTR-egenskaperna hos kompositionen enligt uppfinningen.Composition Water tree Medium length (μm) Average length (%) Polymer 1 (reference) 374 100 Polymer 2 (comparative) 149 40 Polymer 3 (invention) 126 34 The test results show the clearly improved WTR properties of the composition according to the invention.
Exempel 2 I detta exempel jämfördes mostàndskraften mot vat- tenträdsbildning genom Ashcraft-provning hos två komposi- tioner enligt uppfinningen. Kompositionerna utgjordes av Sue 564 (LDPE) kombination med olika halter av en vattenträdsmotverkande làgdensitetspolyeten med en MFR = 2 g/10 min i polymer, vilken utgjordes av en terpolymer av eten, vikt% vinylacetat, och 9 vikt% hydroxietylmetakrylat (HEMA, R2 = H och n = 1). som är en sammonomer med formel I, vari R1 = CHW Den ena kompositionen innehöll 6,5 vikt% av den vattenträdsmotverkande polymeren, medan den andra kompositionen innehöll 14 vikt% därav. Vid Ashcraft-provning erhölls en medellängd hos vattenträden, räknat i % av medellängden hos vattenträden för referens- polymeren i exempel 1, av 46% för kompositionen med 6,5 vikt% EVA-HEMA och 21% för kompositionen med 14 vikt% EVA-HEMA. Det är således tydligt att motståndskraften mot bildning av vattenträd ökar med ökande halt av den vat- tenträdsmotverkande polymeren som innehåller monomeren med formel I.Example 2 In this example, the resistance to water tree formation was compared by Ashcraft testing of two compositions according to the invention. The compositions consisted of Sue 564 (LDPE) combination with different levels of an anti-water tree low density polyethylene with an MFR = 2 g / 10 min in polymer, which consisted of a terpolymer of ethylene,% by weight of vinyl acetate, and 9% by weight of hydroxyethyl methacrylate (HEMA, R2 = H and n = 1). which is a comonomer of formula I, wherein R 1 = CHW One composition contained 6.5% by weight of the anti-water tree polymer, while the other composition contained 14% by weight thereof. In the Ashcraft test, an average length of water trees, calculated in% of the average length of water trees for the reference polymer of Example 1, was obtained of 46% for the composition with 6.5% by weight of EVA-HEMA and 21% for the composition with 14% by weight of EVA. HEMA. It is thus clear that the resistance to the formation of water trees increases with increasing content of the water tree counteracting polymer containing the monomer of formula I.
Exempel 3 I detta exempel mättes den elektriska genomslags- hållfastheten hos tre halvledande polymerkompositioner, Polymer A, B och C, som utgjorde den inre halvledaren hos en elektrisk kabel.Example 3 In this example, the electrical breakdown strength of three semiconductor polymer compositions, Polymer A, B and C, which formed the inner semiconductor of an electrical cable, was measured.
Den första kompositionen utgjordes av en (EVA) med 18 vikt% vinylace- (Polymer A) eten-vinylacetatsampolymer tat, vilken komposition innehöll ca 40 vikt% kolsvart för att göra kompositionen halvledande. Denna komposition användes som referens.The first composition consisted of an (EVA) with 18% by weight of vinyl acetate (Polymer A) ethylene-vinyl acetate copolymer, which composition contained about 40% by weight of carbon black to make the composition semiconductive. This composition was used as a reference.
Den andra kompositionen (Polymer B) utgjordes av samma EVA-polymer som i den första kompositionen, med den (PEG) Dessutom innehöll skillnaden att 0,6 vikt% polyetylenglykol med en molekylvikt av ca 20 000 tillsatts. kompositionen ca 40 vikt% kolsvart. Denna komposition ut- gjorde ett exempel på tidigare känd teknik.The second composition (Polymer B) consisted of the same EVA polymer as in the first composition, with the (PEG) In addition, the difference contained that 0.6% by weight of polyethylene glycol having a molecular weight of about 20,000 was added. the composition about 40% by weight carbon black. This composition was an example of prior art.
Den tredje kompositionen (Polymer C) utgjordes av en terpolymer av eten, 18 vikt% vinylacetat och 3 vikt% av en monomer med formel I. Monomeren med formel I utgjordes 508 564 av hexaetylenglykolmonometakrylat, dvs R1 = CH3, R2 = H och n = 6 i formel I. Dessutom innehöll kompositionen ca 40 vikt% kolsvart. Denna komposition var en komposition enligt uppfinningen.The third composition (Polymer C) consisted of a terpolymer of ethylene, 18% by weight of vinyl acetate and 3% by weight of a monomer of formula I. The monomer of formula I consisted of 508 564 of hexaethylene glycol monomethacrylate, i.e. R1 = CH3, R2 = H and n = 6 in formula I. In addition, the composition contained about 40% by weight of carbon black. This composition was a composition according to the invention.
Var och en av de tre kompositionerna ovan införliva- des som inre halvledande skikt i elektriska kablar, som, räknat inifrån och ut, bestod av en 1,4 mm kopparledare, ett inre halvledande skikt med ytterdiametern 2,8 mm, ett isolerande skikt med ytterdiametern 5,8 mm, och ett yttre halvledande skikt med ytterdiametern 6,1 mm. Det isole- rande skiktet utgjordes av lågdensitetspolyeten med en MFR av 2 g/10 min och det yttre halvledande skiktet ut- gjordes av en eten-butylakrylatsampolymer med en inbland- ning av ca 40 vikt% kolsvart.Each of the above three compositions was incorporated as an inner semiconductor layer in electrical cables, which, calculated from the inside out, consisted of a 1.4 mm copper conductor, an inner semiconductor layer with an outer diameter of 2.8 mm, an insulating layer with the outer diameter 5.8 mm, and an outer semiconductor layer with the outer diameter 6.1 mm. The insulating layer consisted of low density polyethylene with an MFR of 2 g / 10 min and the outer semiconducting layer consisted of an ethylene-butyl acrylate copolymer with a mixture of about 40% by weight of carbon black.
Provningen av den elektriska genomslagshållfastheten genomfördes på dessa provkablar i enlighet med en metod som utarbetats av Alcatel AG & Co, Hannover, Tyskland och som finns beskriven i en artikel av Land H.G., Schädlich Hans, "Model cable test for evaluating the ageing behaviour under water influence of compounds for medium voltage cables”, Conference proceedings of Jlcable 91, 24-28 June 1991, slagshållfastheten anges 63% av Bmx från Weibull-diagram Versaille, France. Som värde på genom- i kV/mm. Genomslagshållfastheten mättes dels A) efter åldring i 16 h vid 90°C i luft, dels B) efter åldring i 1000 h vid 9 kV/mm i 85/70°C vatten. Resultaten av prov- ningen anges i nedanstående tabell ,08 564 ll Komposition Genomslagshållfasthet A (kV/mm) B (kV/mm) Polymer A 77,9 39,6 (Referens) Polymer B (känd 95,6 40,6 teknik) Polymer C 93,6 45,4 (uppfinningen) Såsom framgår av provningsresultaten, uppvisade kom- positionen enligt uppfinningen goda egenskaper som inre halvledande skikt och hade i synnerhet en mycket bra elektrisk genomslagshållfasthet efter åldring i 1000 h vid 9 kV/mm i 85/70°C vatten.The electrical impact test was performed on these test cables in accordance with a method developed by Alcatel AG & Co, Hanover, Germany and described in an article by Land HG, Schädlich Hans, "Model cable test for evaluating the aging behavior under water influence of compounds for medium voltage cables ”, Conference proceedings of Jlcable 91, 24-28 June 1991, the impact strength is stated 63% of Bmx from Weibull diagram Versaille, France. after aging for 16 hours at 90 ° C in air, partly B) after aging for 1000 hours at 9 kV / mm in 85/70 ° C water The results of the test are given in the table below, 08 564 ll Composition Impact strength A ( kV / mm) B (kV / mm) Polymer A 77.9 39.6 (Reference) Polymer B (known 95.6 40.6 technology) Polymer C 93.6 45.4 (invention) As can be seen from the test results, the composition according to the invention has good properties as inner semiconducting layers and had in particular a very good electrical breakdown strength after aging for 1000 hours at 9 kV / mm in 85/70 ° C water.
Exempel 4 I detta exempel provades den elektriska genomslags- hållfastheten på motsvarande sätt som i exempel 3 på en elektrisk kabel, vilken som inre halvledande skikt hade en komposition bestående av en terpolymer av eten, ca 15 vikt% metylakrylat, och ca 2 vikt% hexaetylenglykolmono- metakrylat, dvs samma monomer med formel I som i exempel kolsvart. 3, samt ca 40 vikt% Vid provningen erhölls en elektrisk genomslagshållfasthet (63% av Emm) av 59,4 kV/mm efter åldring i 1000 h vid 9 kV/mm i 85/70°C vatten.Example 4 In this example, the electrical breakdown strength was tested in a manner similar to that of Example 3 on an electrical cable which, as an inner semiconducting layer, had a composition consisting of a terpolymer of ethylene, about 15% by weight of methyl acrylate, and about 2% by weight of hexaethylene glycol mono methacrylate, ie the same monomer of formula I as in the example carbon black. 3, and about 40% by weight. In the test, an electrical breakdown strength (63% of Emm) of 59.4 kV / mm was obtained after aging for 1000 hours at 9 kV / mm in 85/70 ° C water.
Exempel 5 I detta exempel provades motstàndskraften mot miljö- förorsakade spänningssprickor (ESCR), vilket är en egen- skap som är viktig särskilt för det yttre halvledande skiktet hos en elektrisk kabel. Provningen genomfördes 508 564 12 enligt ASTM D 1693, dels med 10% Igepal vid 50°C, dels i luft vid 50°C.Example 5 In this example, the resistance to environmental cracking (ESCR) was tested, which is a property that is particularly important for the outer semiconductor layer of an electrical cable. The test was performed 508 564 12 according to ASTM D 1693, partly with 10% Igepal at 50 ° C, partly in air at 50 ° C.
Tre stycken halvledande polymerkompositioner (Poly- mer 1, 2 och 3) provades, och deras sammansättning var följande.Three semiconductor polymer compositions (Polymers 1, 2 and 3) were tested, and their composition was as follows.
Polymer 1 (jämförande komposition): eten-vinylacetatsam- polymer med 9 vikt% vinylacetat och en MFR = 9,5 dg/10 min. Dessutom innehöll kompositionen ca 36 vikt% kolsvart.Polymer 1 (comparative composition): ethylene-vinyl acetate copolymer with 9% by weight of vinyl acetate and an MFR = 9.5 dg / 10 min. In addition, the composition contained about 36% by weight of carbon black.
Polymer 2 (jämförande komposition): eten-vinylacetatsam- polymer med 18 vikt% vinylacetat och en MFR = 9 dg/10 min. Dessutom innehöll kompositionen ca 40 vikt% kolsvart.Polymer 2 (comparative composition): ethylene-vinyl acetate copolymer with 18% by weight of vinyl acetate and an MFR = 9 dg / 10 min. In addition, the composition contained about 40% by weight of carbon black.
Polymer 3 (enligt uppfinningen): eten-vinylacetat- hydroxietylmetakrylatterpolymer med 9 vikt% vinylacetat, vikt% hydroxietylmetakrylat och en MFR = 6 dg/10 min.Polymer 3 (according to the invention): ethylene-vinyl acetate-hydroxyethyl methacrylate polymer with 9% by weight of vinyl acetate,% by weight of hydroxyethyl methacrylate and an MFR = 6 dg / 10 min.
Dessutom innehöll kompositionen ca 36 vikt% kolsvart.In addition, the composition contained about 36% by weight of carbon black.
Resultatet av provningen av ESCR framgår i nedan- stående tabell och anges som det antal provkroppar av totalt 10 stycken provkroppar som brast vid provningen efter en viss tid mätt i timmar.The result of the test of ESCR is shown in the table below and is given as the number of test specimens out of a total of 10 test specimens that burst during the test after a certain time measured in hours.
Antal brustna prover/antal timmar Komposition ESCR, luft 50°C ESCR, 10%Igepa1 Polymer 1 10/0 9/0 Polymer 2 3/4 9/1,5 Polymer 3 1/6 7/24 Av provningsresultaten framgår att kompositionerna enligt uppfinningen har en avsevärt förbättrad ESCR och följaktligen lämpar sig väl som material för yttre halv- ledande skikt hos elektriska kablar.Number of broken samples / number of hours Composition ESCR, air 50 ° C ESCR, 10% Igepa1 Polymer 1 10/0 9/0 Polymer 2 3/4 9 / 1.5 Polymer 3 1/6 7/24 The test results show that the compositions according to the invention has a considerably improved ESCR and consequently is well suited as a material for outer semiconductor layers of electrical cables.
Claims (10)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9700374A SE508564C2 (en) | 1997-02-04 | 1997-02-04 | Composition for electric cables comprising an ethylene copolymer which, as a comonomer, comprises a polyalkylene glycol monomethacrylate |
| PCT/SE1998/000013 WO1998034236A1 (en) | 1997-02-04 | 1998-01-09 | Composition for electric cables |
| AU60082/98A AU6008298A (en) | 1997-02-04 | 1998-01-09 | Composition for electric cables |
| KR10-1999-7007023A KR100537287B1 (en) | 1997-02-04 | 1998-01-09 | Composition for electric cables |
| EP98903313A EP0962021A1 (en) | 1997-02-04 | 1998-01-09 | Composition for electric cables |
| JP53277298A JP2001509946A (en) | 1997-02-04 | 1998-01-09 | Compositions for cables |
| CN98802918A CN1099681C (en) | 1997-02-04 | 1998-01-09 | Composition for cables |
| US09/365,939 US6165387A (en) | 1997-02-04 | 1999-08-02 | Composition for electric cables |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9700374A SE508564C2 (en) | 1997-02-04 | 1997-02-04 | Composition for electric cables comprising an ethylene copolymer which, as a comonomer, comprises a polyalkylene glycol monomethacrylate |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| SE9700374D0 SE9700374D0 (en) | 1997-02-04 |
| SE508564C3 true SE508564C3 (en) | 1998-08-05 |
| SE9700374L SE9700374L (en) | 1998-08-05 |
| SE508564C2 SE508564C2 (en) | 1998-10-19 |
Family
ID=20405662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE9700374A SE508564C2 (en) | 1997-02-04 | 1997-02-04 | Composition for electric cables comprising an ethylene copolymer which, as a comonomer, comprises a polyalkylene glycol monomethacrylate |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0962021A1 (en) |
| JP (1) | JP2001509946A (en) |
| KR (1) | KR100537287B1 (en) |
| CN (1) | CN1099681C (en) |
| AU (1) | AU6008298A (en) |
| SE (1) | SE508564C2 (en) |
| WO (1) | WO1998034236A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE9800567L (en) * | 1998-02-25 | 1999-08-26 | Abb Ab | An electric DC cable with an insulation system comprising a composition based on extruded, cross-linked polyethylene and a method for making such a cable |
| KR100833444B1 (en) | 2006-03-28 | 2008-05-29 | 주식회사 하이닉스반도체 | Manufacturing Method of Flash Memory Device |
| US9058918B2 (en) * | 2008-06-05 | 2015-06-16 | Union Carbide Chemicals & Plastics Technology Llc | Method for producing water tree-resistant, TRXLPE-type cable sheath |
| WO2010112333A1 (en) * | 2009-03-30 | 2010-10-07 | Borealis Ag | Cable with high level of breakdown strength after ageing |
| BR112013016031B1 (en) | 2010-12-22 | 2020-04-07 | Basell Polyolefine Gmbh | process for preparing ethylene copolymer in the presence of free radical polymerization initiator by ethylene copolymerization, ethylene copolymer obtained by such a process and its use, as well as process for coating by extruding a substrate |
| EP3088427A1 (en) * | 2015-04-30 | 2016-11-02 | ARLANXEO Deutschland GmbH | Ethylene copolymer exhibiting improved low temperature and vulcanizable mixtures and vulcanizates based thereon |
| WO2017102506A1 (en) * | 2015-12-17 | 2017-06-22 | Sabic Global Technologies B.V. | Ethylene copolymers and process for the production thereof |
| EP3733763A1 (en) * | 2019-04-30 | 2020-11-04 | Borealis AG | Polyethylene composition for improving adhesion to polyurethane resins |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4312918A (en) * | 1980-09-15 | 1982-01-26 | Union Carbide Corporation | Compositions of polyethylene and a copolymer of ethylene-alkyl acrylate and the use thereof as jacketing about telephone wires and cables |
| US4812505A (en) * | 1987-05-18 | 1989-03-14 | Union Carbide Corporation | Tree resistant compositions |
| FI90986C (en) * | 1991-10-15 | 1994-04-25 | Neste Oy | Use of an extrudable ethylene hydroxyacrylate copolymer |
| IT1276762B1 (en) * | 1995-06-21 | 1997-11-03 | Pirelli Cavi S P A Ora Pirelli | POLYMER COMPOSITION FOR THE COVERING OF ELECTRIC CABLES HAVING AN IMPROVED RESISTANCE TO "WATER TREEING" AND ELECTRIC CABLE |
-
1997
- 1997-02-04 SE SE9700374A patent/SE508564C2/en not_active IP Right Cessation
-
1998
- 1998-01-09 CN CN98802918A patent/CN1099681C/en not_active Expired - Fee Related
- 1998-01-09 WO PCT/SE1998/000013 patent/WO1998034236A1/en not_active Ceased
- 1998-01-09 KR KR10-1999-7007023A patent/KR100537287B1/en not_active Expired - Fee Related
- 1998-01-09 EP EP98903313A patent/EP0962021A1/en not_active Withdrawn
- 1998-01-09 JP JP53277298A patent/JP2001509946A/en active Pending
- 1998-01-09 AU AU60082/98A patent/AU6008298A/en not_active Abandoned
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