CA1161589A - Electrical tree and water tree resistant polymer compositions - Google Patents
Electrical tree and water tree resistant polymer compositionsInfo
- Publication number
- CA1161589A CA1161589A CA000355215A CA355215A CA1161589A CA 1161589 A CA1161589 A CA 1161589A CA 000355215 A CA000355215 A CA 000355215A CA 355215 A CA355215 A CA 355215A CA 1161589 A CA1161589 A CA 1161589A
- Authority
- CA
- Canada
- Prior art keywords
- cnh2n
- composition
- containing radical
- methyl
- treeing
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 229920000642 polymer Polymers 0.000 title claims description 17
- 240000005572 Syzygium cordatum Species 0.000 title description 13
- 235000006650 Syzygium cordatum Nutrition 0.000 title description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 26
- -1 polyethylene Polymers 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000004104 aryloxy group Chemical group 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000004423 acyloxy group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000008240 homogeneous mixture Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 230000005764 inhibitory process Effects 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 4
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000002216 antistatic agent Substances 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000009413 insulation Methods 0.000 abstract description 9
- 229910000077 silane Inorganic materials 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000000523 sample Substances 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000654 additive Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 150000004756 silanes Chemical class 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229920006163 vinyl copolymer Polymers 0.000 description 2
- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- WLNBQNXELZHTAX-UHFFFAOYSA-N 8-(2-methylpropyl)-6-(3,6,6-trimethyl-4-oxo-5,7-dihydroindol-1-yl)-3,4-dihydro-2h-isoquinolin-1-one Chemical compound C1=C(C)C(C(CC(C)(C)C2)=O)=C2N1C(C=C1CC(C)C)=CC2=C1C(=O)NCC2 WLNBQNXELZHTAX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920000292 Polyquinoline Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- ZGSIAHIBHSEKPB-UHFFFAOYSA-N dodecan-4-ol Chemical compound CCCCCCCCC(O)CCC ZGSIAHIBHSEKPB-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XGMMKELBHRGYSB-UHFFFAOYSA-N ethenyl-tris(2-methylsulfanylethoxy)silane Chemical compound CSCCO[Si](OCCSC)(OCCSC)C=C XGMMKELBHRGYSB-UHFFFAOYSA-N 0.000 description 1
- NGSXJHBGCYVLMX-UHFFFAOYSA-N ethenyl-tris(2-phenoxyethoxy)silane Chemical compound C=1C=CC=CC=1OCCO[Si](OCCOC=1C=CC=CC=1)(C=C)OCCOC1=CC=CC=C1 NGSXJHBGCYVLMX-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- JSECNWXDEZOMPD-UHFFFAOYSA-N tetrakis(2-methoxyethyl) silicate Chemical compound COCCO[Si](OCCOC)(OCCOC)OCCOC JSECNWXDEZOMPD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical class CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- URRFGQHFJDWCFM-UHFFFAOYSA-N tris(2-butoxyethyl) phosphite Chemical compound CCCCOCCOP(OCCOCCCC)OCCOCCCC URRFGQHFJDWCFM-UHFFFAOYSA-N 0.000 description 1
- INWMKLWBJBCUIU-UHFFFAOYSA-N tris(2-ethoxyethyl) phosphite Chemical compound CCOCCOP(OCCOCC)OCCOCC INWMKLWBJBCUIU-UHFFFAOYSA-N 0.000 description 1
- OLTVTFUBQOLTND-UHFFFAOYSA-N tris(2-methoxyethoxy)-methylsilane Chemical compound COCCO[Si](C)(OCCOC)OCCOC OLTVTFUBQOLTND-UHFFFAOYSA-N 0.000 description 1
- DBXDLSPMDNQBBQ-UHFFFAOYSA-N tris(2-methoxyethoxy)-phenylsilane Chemical compound COCCO[Si](OCCOC)(OCCOC)C1=CC=CC=C1 DBXDLSPMDNQBBQ-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- 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
- 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
- H01B3/46—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 silicones
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Silicon Polymers (AREA)
- Laminated Bodies (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE An unfilled polymeric, composition having improved electrical treeing and water treeing properties comprising a polymeric component and effective amounts of an organic compound, such as, a specially defined silane. These compositions are particularly useful as insulation for high voltage transmission and distribution cables.
Description
1 ELECTRICAL TREE AND WATER TREE R~SISTANT POLYM~R
COMPO~ITIONS
This invention relates to polymeric compositions 5 having increased resistance to electrical treeing and water treeing properties, said compositions being useful as insulation for electrical cables.
Polymeric compositions are well-known and are used extensively as insulation materials for wire and 10 cable. As an insulator, it is important that the composition have various physical and electrical pxoperties, such as resistance to mechanical cut through, stress crack resistance and dielectric failure. Recent publi-cations have indicated that water tree growth and electrical 15 tree growth in the insulation are particularly important problems since they are associated with, though not necessarily totally responsible for, dielectric failure.
An important application for an insulation material is in high voltage transmission and distribution 20 cable, especially in direct buried underground service and three types of trees have been observed in power cables, to wit, electrical trees, water trees and electro-- chemical trees. It is generally believed that electrical trees are generated by corona discharges causing fusion 25 and breakdown of the polymer, whereas water trees are usually observed in cables buried in wet locations and have a different appearance comparea to the electrical trees. The electrochemical trees are similar to the water trees but are characterized by the presence 30 of metal ions in the trees.
.,5~
1 U.S. Pa-tent No. 4,144,202 gran-ted to Ashcraft et al. relates to inhibiting the electrical breakdown of insulation by water treeing in dielectric materials based on ethylene polymers. This patent discusses 5 electrical failures which are due to treeing and explains the concept of treeing and some of the causes for treeing.
In general, as the polymeric composition breaks down the damage progresses through the insulator, or dielectric, in a path that loo~s something like a tree, Txeeing lO usually is a slow type failure and may take years to cause a failure in the insulation~ As disclosed in the patent, water treeing is inhibited in the ethylene polymer com-positions by employing therein certain organo silane compounds, In particular, the organo silane is a silane 15 con~aining an epoxy containing radical. Suitable polymers, adjuvants and processing procedures for preparing the composition are described in the patent U.S. Patent 4,206,260 to 20 E.J. McMahon relatesto insulation particularly suit~bl~
for high voltage power cable containing an effective amount of an alcohol of 6 to 24 carbon atoms which imparts ~ electrical tree growth resistance to the composition.
~his Patent , as in U,S, No. 4,144~202, supra, con-25 tain a discussion of the electrical treeing problem in polymer compositions and cite numerous patents attempting to overcome this problem, German Offenlegungsschrift 2,737,430 discloses that certain alkoxysilanes added to polyolefin insulation prevent water-tree formation. Several trimethoxy and triethoxy silanes are said to be useful, No alkoxyalkoxy ~6~
l silanes are taught or suggested as having both water treeing and electrical treeing inhibiting properties.
U.S. Patent No. 3,553,34~ granted to Betts, 5 British Patent No. l,2a8,256 granted to General Electric Company and British Patent No. 1,277,378 gxanted to General Electric Company relate to mineral filled polymer compositions useful as electrical wire and cable insulation The mineral filler is treated with an organosilane such lO as an alkyl alkoxysilane or a vinyl alkoxysilane to decrease the porosity of the composition. None of these patents teach or suggest that addition of an organosilane to an unfilled polymer composition will beneficially enhance the water -treeing and electrical treeins resistance of the 15 polymer com~osition.
Unfortunately~ however, the prior art has not provided an insulation composition having both increased resistance to water treeing and electrical treeing.
As noted in U.S. No~ 4,144,202, supra, intrinsic electric 20 breakdown, failure by corona~ electrical treeing and water treeing are different and the mechanisms for each are different and a different solution is required to effect - an improvement in a dielectric material for each mode of failure involved. Thus, the problem of providing a 25 single composition capable of resisting both electrical treeing and water treeing is a formidable one confronting the art, It has now been unexpectedly discovered that 30 polymeric compositions comprising an effective amount of
COMPO~ITIONS
This invention relates to polymeric compositions 5 having increased resistance to electrical treeing and water treeing properties, said compositions being useful as insulation for electrical cables.
Polymeric compositions are well-known and are used extensively as insulation materials for wire and 10 cable. As an insulator, it is important that the composition have various physical and electrical pxoperties, such as resistance to mechanical cut through, stress crack resistance and dielectric failure. Recent publi-cations have indicated that water tree growth and electrical 15 tree growth in the insulation are particularly important problems since they are associated with, though not necessarily totally responsible for, dielectric failure.
An important application for an insulation material is in high voltage transmission and distribution 20 cable, especially in direct buried underground service and three types of trees have been observed in power cables, to wit, electrical trees, water trees and electro-- chemical trees. It is generally believed that electrical trees are generated by corona discharges causing fusion 25 and breakdown of the polymer, whereas water trees are usually observed in cables buried in wet locations and have a different appearance comparea to the electrical trees. The electrochemical trees are similar to the water trees but are characterized by the presence 30 of metal ions in the trees.
.,5~
1 U.S. Pa-tent No. 4,144,202 gran-ted to Ashcraft et al. relates to inhibiting the electrical breakdown of insulation by water treeing in dielectric materials based on ethylene polymers. This patent discusses 5 electrical failures which are due to treeing and explains the concept of treeing and some of the causes for treeing.
In general, as the polymeric composition breaks down the damage progresses through the insulator, or dielectric, in a path that loo~s something like a tree, Txeeing lO usually is a slow type failure and may take years to cause a failure in the insulation~ As disclosed in the patent, water treeing is inhibited in the ethylene polymer com-positions by employing therein certain organo silane compounds, In particular, the organo silane is a silane 15 con~aining an epoxy containing radical. Suitable polymers, adjuvants and processing procedures for preparing the composition are described in the patent U.S. Patent 4,206,260 to 20 E.J. McMahon relatesto insulation particularly suit~bl~
for high voltage power cable containing an effective amount of an alcohol of 6 to 24 carbon atoms which imparts ~ electrical tree growth resistance to the composition.
~his Patent , as in U,S, No. 4,144~202, supra, con-25 tain a discussion of the electrical treeing problem in polymer compositions and cite numerous patents attempting to overcome this problem, German Offenlegungsschrift 2,737,430 discloses that certain alkoxysilanes added to polyolefin insulation prevent water-tree formation. Several trimethoxy and triethoxy silanes are said to be useful, No alkoxyalkoxy ~6~
l silanes are taught or suggested as having both water treeing and electrical treeing inhibiting properties.
U.S. Patent No. 3,553,34~ granted to Betts, 5 British Patent No. l,2a8,256 granted to General Electric Company and British Patent No. 1,277,378 gxanted to General Electric Company relate to mineral filled polymer compositions useful as electrical wire and cable insulation The mineral filler is treated with an organosilane such lO as an alkyl alkoxysilane or a vinyl alkoxysilane to decrease the porosity of the composition. None of these patents teach or suggest that addition of an organosilane to an unfilled polymer composition will beneficially enhance the water -treeing and electrical treeins resistance of the 15 polymer com~osition.
Unfortunately~ however, the prior art has not provided an insulation composition having both increased resistance to water treeing and electrical treeing.
As noted in U.S. No~ 4,144,202, supra, intrinsic electric 20 breakdown, failure by corona~ electrical treeing and water treeing are different and the mechanisms for each are different and a different solution is required to effect - an improvement in a dielectric material for each mode of failure involved. Thus, the problem of providing a 25 single composition capable of resisting both electrical treeing and water treeing is a formidable one confronting the art, It has now been unexpectedly discovered that 30 polymeric compositions comprising an effective amount of
2 certain organic compound, such as a specially defined silane component, exhibit both enhanced resistance to water treeing and electrical treeing properties. The ~.~.6~
1 eomposition may also be cured using known techniques to provide a crosslinked composition having further improved properties for certain applications.
In general, the polymerie co~position comprises 5 per hundred par~s by weight polymer (phr) about 0,1 to 10 phr of a silane having the following formula A:
Rl R - Si - R2 - ' ~ 3 wherein R, Rl, R2 and R3 are eaeh independently selected from Cl to Cg alkyl, Cl to C8 alkoxy, Cl to C8 acyloxy, C6 to C18 aryloxy or substituted aryloxy, C6 to C18 15 aryl or substituted aryl, hydrogen, halogen, an epoxy containing radieal, C2 to C8 alkenyl, a nitrogen eontain-ing radical, a carboxy eontaining radieal, a mercapto eontaining radieal and an ether eontaining radical~ with the proviso that at least one, and preferably at least three, e.g.~ all of R, Rl, R2 and R3 be a group wherein the group contains at least one electron donating atom in the chain of the group and which is at a position other than the position ad~acent to the silicon atom.
The electron donating group may be, for example, oxygen, 25 nitrogen, sulphur and the like. Oxygen is preferred beeause of its demonstrated effeetiveness~ A highly preferred group has the electron donating atom separated from the silieon atom by three atoms~
A preferred eomposition comprises about 0.5 to 5 phr silane component, most preferably about 1 to
1 eomposition may also be cured using known techniques to provide a crosslinked composition having further improved properties for certain applications.
In general, the polymerie co~position comprises 5 per hundred par~s by weight polymer (phr) about 0,1 to 10 phr of a silane having the following formula A:
Rl R - Si - R2 - ' ~ 3 wherein R, Rl, R2 and R3 are eaeh independently selected from Cl to Cg alkyl, Cl to C8 alkoxy, Cl to C8 acyloxy, C6 to C18 aryloxy or substituted aryloxy, C6 to C18 15 aryl or substituted aryl, hydrogen, halogen, an epoxy containing radieal, C2 to C8 alkenyl, a nitrogen eontain-ing radical, a carboxy eontaining radieal, a mercapto eontaining radieal and an ether eontaining radical~ with the proviso that at least one, and preferably at least three, e.g.~ all of R, Rl, R2 and R3 be a group wherein the group contains at least one electron donating atom in the chain of the group and which is at a position other than the position ad~acent to the silicon atom.
The electron donating group may be, for example, oxygen, 25 nitrogen, sulphur and the like. Oxygen is preferred beeause of its demonstrated effeetiveness~ A highly preferred group has the electron donating atom separated from the silieon atom by three atoms~
A preferred eomposition comprises about 0.5 to 5 phr silane component, most preferably about 1 to
3 phr.
~6~5$~
l A particularly preferred unfilled polymeric composition comprises a homogeneous mixture of a polymeric component and an effective amount, as a water treeing and electrical treeing inhibitor, of an organic compound having 5 the following formula B;
R2 ~ 2 - Yl (-CnH2n) 2 6 (R3)a wherein Rl, R2 and R3 are the same or different and l n 2n~ Y2R6 r Cl to C8 alkyl, C1 to C8 alkoxy C
to C8 acyloxy, C6 to C18 aryloxy or substituted aryloxy, C6 to C18 aryl or substituted aryl, hydrogen, halogen 15 an epo~y containing radical, C2 to C8 alkenyl, a nitrogen containing radical, a carboxy containing radical, a mercapto containing radical or an ether containing radical;
R6 is Cl to C8 alkyl, Cl to C8 alkoxy, Cl to C8 acyloxy, C6 to Cl8 aryloxy or substituted aryloxy, C6 to C18 20 aryl or substituted aryl, hydrogen, halogen, an epoxy containing radical, C2 to C8 alkenyl, a nitrogen contain-ing radical, a carboxy containing radical, a mercapto containing radical or an ether containing radical;
. Yl and Y2 are the same or different and are 0, S or N~;
Z is Si, Sn, Ti, P or B
a is 0 or l; and n i5 l to 8.
This particularly preferred composition comprises 3 about 0.1 to lO parts (by weight) per hundred parts (phr) of polymer of the organic compound of formula B. An especially preferred composition comprises about 0.5 to 5 phr of organic compound component,-preferably about l to 3 phr, 5~
1 This invention is also directed to a method of stabilizing a polymeric insulated electrical conductor against water treeing and electrical treeing which comprises coating an electrical conductor ~ith an 5 insulating effective amount of a polymeric insulating composition, said composition comprising a homogeneous mixture of a polymeric component and an effective amount, as a water txeeing and electrical treeing inhibitor, of an organic compound having the following formula s:
Rl R2 - Z - Y1(CnH2n) Y2 6 (R3)a 15 wherein R1, R2 and R3 are the same or different and are Y1(CnH2n) Y2R6, Cl to C8 alkyl, Cl to C8 acyloxy~ C6 to C18 aryloxy or substituted aryloxy, C6 to Cl~ aryl or ~ahstituted aryl, hydrogen, halogen, an epoxy containing radical, C2 to C8 alkenyl, a nitrogen containing radical, 20 a carboxy containing radical, a mercapto containing radical or an ether containing radica~ R6 is Cl to C8 alkyl, Cl to C8 alkoxy, Cl to C8 acyloxy, C6 to C18 - aryloxy or substituted aryloxy, C6 to C18 aryl or substi-tuted aryl, hydrogen, halogen, an epoxy containing radical, 25 C2 to C8 alkenyl, a nitrogen containing radical,~a carboxy containing radical, a mercapto containing radical or an ether containing radical;
Yl an~ Y2 are the sa~e or different and are 0, S:or 3 a is 0 or 1; and~
n is 1 to 8, ~hereby said insulated electrical conductor exhibits water treeing and ~lectrical 1 treeing inhibition when exposed to an environment subject to water treeing and electrical treeing con-ditions.
The compositions of the invention find particular 5 utility in high voltage transmission and distribution cables but are useful in other electrical applications where a unique combination of enhanced water treeing and electrical treeing properties are needed.
In general, the polymers suitable for the practice of this invention include any normally solid synthetic organic polymeric thermoplastic resin, Included are polyolefins and copolymers thereofl vinyls, olefin-vinyl copolymers, olefin-allyl copolymers, poly-15 amides, acrylics, polystyrenes, cellulosics, polyesters and flurocarbons.
The polyolefins include normally solid polymers of olefins, particularly mono-alpha-olefins, which comprise from about two to about six carbon atoms, e.g., 20 polyethylene, polypropylene, polybutene, polyisobutylene, poly(4-methyl-pentene), and the like. Preferred poly-olefins are polyethylene and polypropylene. Polyethylene - is especially preferred~ An especially preferred poly-ethylene because of its demonstrated effectiveness is 25 termed NA 310*and is sold by National Distillers and Chemical Company.
Copolymers of ethylene, and other compounds interpolymerizable with ethylene such as butene-l, pentene-l, styrene and the like may be employed. In 30 general the ethylene will comprise about 50 to ~ 100 weight % ethylene.
* Trade Mark 1 Suitable vinyl polymers include polyvinyl chloride, polyvinyl acetate, vinyl chloride/vinyl acetate copolymers, polyvinyl alcohol and polyvinyl acetal.
Suitable olefin-vinyl copolymers include ethylene-5 vinyl acetate, ethylene-vinyl propionate, ethylene-vinyl isobutyrate, ethylene-vinyl alcohol, ethylene-methyl acrylate, ethylene-ethyl acrylate J ethylene-ethyl meth-acrylate, and the like. In general the ethylene consti-tutes at least about 25~ of the copolymer by weight.
Olefin-allyl copolymers include ethylene-allyl benzene, ethylene-allyl ether, ethylene-acrolein, and the like.
The silane employed in the polymeric compositions of the invention may be selected from one or more compounds 15 of the following formula A:
Rl R - Si - R2 wherein R, Rl, R2 and R3 are defined as hereina~ove in connection with formula A~
The organic compound employed in the particularly preferred unfilled polymeric compositions of the invention is 25 selected from one or more compounds of the following formula B:
Rl R2 ~ Z - Yl(CnH2n~ Y2 6 : 30 (R3)a Rl~ R2, R3, R6, Yl, Y2, Z, a and n are defined as hereinabove in connection with formula B~
~.~.6~
g 1 A number of R, Rl, R2 and R3 groups useful in connection with the present invention is shown in "Chemicals and Plastics Physical Properties. 1978-80" published by Union Carbide Company on page 43 Exemplary are chloro, methyl, ethyl, methoxy, ethoxy, phenyl,~hydrogen, chloropropyl, vinyl 2-methoxyethoxy, gamma-methacryloxy-propyl, beta-(3,~epoxycyclohexyl)-ethyl, gamma-glycidoxy-propyl, acetoxy, gamma-mercaptopropyl, gamma-aminopropyl, 10 bis-hydroxyethyl-gamma-amino-propyl, bis-acrylic acid gamma-amino-propyl, N-beta(aminoethyl~-gamma-amino-propyl, and methyl 12(gamma-trimethoxysilypropylamino~ethylamino]
3 propionate.
As noted hereinabove, at least one of the R, 15 Rl, R2 and R3 groups of formula A have an electron donating atom such as oxygen, nitrogen or sulphur atom in the chain of the groups. Preferably the electron donating atom is separated from the silicon atom by three atoms.
A preferred group has the following formula, (OR40R5) wherein R4 is Cl to C6 and R5 is a Cl to C8 alkyl, hydrogen, Cl to C8 alkoxy or C2 to C8 alkenyl. A particularly preferred group is 2 methoxyethoxy which has the formula, ( oC2~4CH3 ) 25 A preferred compound is sold under the name A--172*by Union Carbide Company and is chemically defined as vinyl-tris (2-methoxyethoxy) silane. Other R, Rl, R~ and R3 groups include gamma-methacryloxy-propyl, gamma-glycidoxy-propyl, gamma-aminopropyl, bis-hydroxy-ethyl-gamma-amino-30 propyl and N-béta(aminoethyl)-gamma-amino-propyl.
The Rl, R2 and R3 groups of formula B useful in connection with the present invention when Z is silicon, include examples of the groups discussed above * Trade Mark 5~3~
1 in connection with the Union Carbide Company publicaton, particularly when Yl(Cn~l2n) Y2R6 is an alkoxyalkoxy groups.
Among the useful silanes of formula B are gamma-meth-acryloxypropyl-tris(2-methoxyethoxy) silane, tetrakis-(2-methoxyethoxy) silane, methyl-tris (2-methoxyethoxy) silane, phenyl-tris(2 methoxyethoxy) silane, vinyl-tris (2-phenoxyethoxy) silane, vinyl-tris (2-methylthioethoxy) silane and vinyl-tris (2-methoxyethoxy) silane with the latter being particularly preferred. Replacing the silicon with such atoms as ~in, titanium, phosphorous or boron provides other useful compounds which find utility in the invention Thus, such compounds as tris (2-ethoxyethyl) phosphite, tris (2-n-butoxyethyl) phosphite, tetrakis (2 methoxyethoxy) titanium and the like may be employed 15 and are included with the scope of this invention.
Therefore, in the preferred organic compounds of formula ~, Rl, R2, and P~3 are each selected from Yl(CnH2n)~2R6, alkyl, alkoxy, acyloxy, aryl or alkenyl, R6 is alkyl or aryl, Yl and Y2 are o and Z is Si or P- Of eourse~when Z is Si, a is 20 1 and when Z is P, a is 0.
~ hen it is desired to use a polymerie composi-tiO}l whieh can be crosslinked, crosslinking can be accom-plished by any of the known proeedures sueh as ehemical means including peroxide eross-linking; by radiation using 25 eleetron aeeelerators, ~r-rays, high energy radiation, sueh as X-rays, mierowaves ete,; or by thermal erosslinking.
The basie proeedures for erosslinking polymers are ~:
extremely well known to the art and need not be described here in detail.
Conventional crosslinking agents sueh as organie peroxides may be suitably employed, Typieal organie peroxide.free radieal generators include dieumyl peroxide;
2,5-bis (tert.-butylperoxy)-2,5 dimethylhexane; di--t-butyl $~
1 peroxide benzoyl peroxide; J6, ~I bis(t-butyl peroxy) diisopropyl benzene and the like, as discussed in U.S.
Patent No. 3,287,312. The amount of organic peroxidel when employed, will range from about 0.5 to 5.0% by weight 5 based on the total weight of the composition, or about 0.5 to 10 phr, preferably 3 to 6 phr.
~ lhile the silanes and the organic compounds described hereinabove are useful for both thermoplastic and cured polymeric compositions, for compositions to 10 be cured it is preferred that one of the groups/ to wit, R, Rl, R2, or R3, be an organo functional group, e.g., a vinyl group, which group provides the composition with enhanced curing properties.
Minor amounts of other additives may also be 15 employed in conventional amounts to obtain the desired results, Conventional antioxidants such as the hindered phenols, polyquinolines and the like may be employed.
Other ingredients that may be included are plasticizers, dyes, pigments, heat and light stabilizers, antistatic 20 agents and the li~c~
The preferred compositions of this invention are unfilled polymer compositions~ The term 'unfilled" as applied to the - instant composition shall mean a composition which contains less than 10% of a conventional polymer filler. For certain 25 applications and to meet particular specifications the unfilled compositions herein may contain no filler. The compositions of this invention may contain, therefore, O to less than 10~ filler.
Accordingly, fillers, such as mineral fillers, may be employed to this limited extent in preparing the compositions of the 30invention, but in the particularly preferred embodiment and for certain uses, these compositions contain no fillers.
-12 -~ 5~
1 The polymer compositions of this invention can be prepared by mixing the various ingredients When the organic compound and the polymeric component are mixed together to form the instant compositions, the organic 5 compound and poly~eric component are homogeneously dispersed in each other. The order of mixing and specific procedure employed are not critical except to the extent that from the time the peroxide is added, if employed, the temperature is less than about 130~C. in order to prevent premature 10 curing of the composition. This precaution, however, is conventional in the art.
The components may be mixed on a variety of apparatus including multi-roll mills, screw mills, continuous mixers, compounding extruders and Banbury*mixers.
After being extruded onto wire or cable, or other substrate, the crosslinkable compositions are vul-canized at elevated temperatures, e.g., above about 180C.
using conventional vulcanizing procedures.
In order to determine the utility and effective-20 ness of the polymeric compositions of the present inventionwith regard to its inhibiting effect on the water treeing and the electrical treeing thereof, the co~positions - were evaluated by the use of accelerated tests.
Electrical tree tests were performed using the 25 method similar to that in IEEE Conference Paper No. C73, 257-3 1973 by E.J. McMahon and J.R. Perkins. Strips of material approximately 1" wide were cut from a 1/4"
thick compression molded plaque~ The block was machined to give a strip having parallel edges 1" apart, The strip 3 was then cut into 1" square blosks. A blunt needle and a sharp needle were inserted into opposite parallel edges, at elevated temperatures, so that the points were 1/8"
* Trade Mark ~6~5~
l apart. Nee~le insertion and cooling of the sample was performed slowly to avoid inducing thermal or mechanical stresses in the specimen. The sharp needle has a tip diameter of about 0.0002" while the diameter of the blunt 5 needle is 0.002"~ Eight specimens were prepared and tested simultaneously for each composition~ ~he electrical tree test was performed by energizing the sharp needle at 15 XV using a frequency of 60 ~z; the blunt needle was connected to ground. The time required for lO each of the eight specimens to fail by tree ~rowth and subsequent electrical short was re~orded. The time required for 50~ of the samples to fail was employed to characterize the effectiveness of the tree retardant being evaluated.
The water tree test is performed using a procedure similar to that described in ~,S. Patent 4,1~4,202. A
;compression molded disc about 150 millimeters (mm.) in diameter having 24 conical depressions was prepared for each co~.position. The geometry of the disc and dimensions 20 of the depressions are substantially the same as shown in USP 4,144~202. The base of the disc is sprayed with silver paint which serves as the ground electrode. An acrylic tube 6" long is clamped to the upper face forming a test cell. About 150 ml, of 0.01 N sodium chloride 25 solution was poured into the cell and the air bubbles trapped on the surface of the sample were removed.
A platinum wire ring was then immersed in the electrolyte and connected to the electrical supply which provides ,5KV at a frequency of 3KHz. Samples were energized for 30 22 hours after~which time they were removed from the test cell and washed with distilled water. The ten central depressions were cut from the disc and stained to s~
1 make the water trees more visible, Thin sections were obtained with a microtome, which were then examined microscopically (at 200X) and the tree size measured.
Normally four discs were made for each sample so that the 5laverage tree size is calculated from forty individual measurements. In evaluating different tree re-tardants, the relative tree size was determined by comparing the average tree size obtained on a standard thermoplastic high voltage insulation material containing no tree lO~retardant additivesO
Various embodiments of the present invention will now be illustrated by reference to the following specific examples. It is to be understood, however, that such examples are presented for purposes of illustration only, 15land the present invention is in no way to be deemed as limited thereby. A11 parts and percentages are by weight and temperatures in degrees Fahrenheit unless otherwise noted.
I
-15~ 5~
1 ~X~PL~ I
The compositions were prepared by milling a commercial grade of polyethylene (NA 310) and the treeing additive (2P6 by weight) on a 2-roll mill at about 5 300~F. for about 10 minutes to obtain a homoyeneous dis-persion, The crepe obtained was then used to prepare the samples for electric tree and water tree testing using the procedures described hereinabove. The test results are shown in Table 1. All the compositions have the same 10 formulation except for the "treeing" additive as noted in Table 1 and comprise a commercial grade of polyethylene having a Melt Index of about 0,20 to 0.35 g/10 min. and a density of about ,917 grams/cubic centimeter (g/cc).
The control sample does not contain a "treeing" additive.
-16~
1 TABL~ I
Sample Treeing Additive Double Needle Water Tree No. Test Time to (Relative 50% Failure Tree Size) (minutes) , _ A Vinyl-tris- ~ 12,700 0,23 (2-methoxy-ethoxy) silane (no failures) B Gamma-glycid- 2,800 0.34 oxypropyl -tri-methoxysilane 1 Control 80 (No Additive) 2 Vinyl triethoxy 30 0.29 silane ... . _ _ .. _ 3 Beta-(3,4-epoxy- 620 0.34 cyclohexyl)-ethyl-trimethoxysilane . . _ _ .
~6~5$~
l A particularly preferred unfilled polymeric composition comprises a homogeneous mixture of a polymeric component and an effective amount, as a water treeing and electrical treeing inhibitor, of an organic compound having 5 the following formula B;
R2 ~ 2 - Yl (-CnH2n) 2 6 (R3)a wherein Rl, R2 and R3 are the same or different and l n 2n~ Y2R6 r Cl to C8 alkyl, C1 to C8 alkoxy C
to C8 acyloxy, C6 to C18 aryloxy or substituted aryloxy, C6 to C18 aryl or substituted aryl, hydrogen, halogen 15 an epo~y containing radical, C2 to C8 alkenyl, a nitrogen containing radical, a carboxy containing radical, a mercapto containing radical or an ether containing radical;
R6 is Cl to C8 alkyl, Cl to C8 alkoxy, Cl to C8 acyloxy, C6 to Cl8 aryloxy or substituted aryloxy, C6 to C18 20 aryl or substituted aryl, hydrogen, halogen, an epoxy containing radical, C2 to C8 alkenyl, a nitrogen contain-ing radical, a carboxy containing radical, a mercapto containing radical or an ether containing radical;
. Yl and Y2 are the same or different and are 0, S or N~;
Z is Si, Sn, Ti, P or B
a is 0 or l; and n i5 l to 8.
This particularly preferred composition comprises 3 about 0.1 to lO parts (by weight) per hundred parts (phr) of polymer of the organic compound of formula B. An especially preferred composition comprises about 0.5 to 5 phr of organic compound component,-preferably about l to 3 phr, 5~
1 This invention is also directed to a method of stabilizing a polymeric insulated electrical conductor against water treeing and electrical treeing which comprises coating an electrical conductor ~ith an 5 insulating effective amount of a polymeric insulating composition, said composition comprising a homogeneous mixture of a polymeric component and an effective amount, as a water txeeing and electrical treeing inhibitor, of an organic compound having the following formula s:
Rl R2 - Z - Y1(CnH2n) Y2 6 (R3)a 15 wherein R1, R2 and R3 are the same or different and are Y1(CnH2n) Y2R6, Cl to C8 alkyl, Cl to C8 acyloxy~ C6 to C18 aryloxy or substituted aryloxy, C6 to Cl~ aryl or ~ahstituted aryl, hydrogen, halogen, an epoxy containing radical, C2 to C8 alkenyl, a nitrogen containing radical, 20 a carboxy containing radical, a mercapto containing radical or an ether containing radica~ R6 is Cl to C8 alkyl, Cl to C8 alkoxy, Cl to C8 acyloxy, C6 to C18 - aryloxy or substituted aryloxy, C6 to C18 aryl or substi-tuted aryl, hydrogen, halogen, an epoxy containing radical, 25 C2 to C8 alkenyl, a nitrogen containing radical,~a carboxy containing radical, a mercapto containing radical or an ether containing radical;
Yl an~ Y2 are the sa~e or different and are 0, S:or 3 a is 0 or 1; and~
n is 1 to 8, ~hereby said insulated electrical conductor exhibits water treeing and ~lectrical 1 treeing inhibition when exposed to an environment subject to water treeing and electrical treeing con-ditions.
The compositions of the invention find particular 5 utility in high voltage transmission and distribution cables but are useful in other electrical applications where a unique combination of enhanced water treeing and electrical treeing properties are needed.
In general, the polymers suitable for the practice of this invention include any normally solid synthetic organic polymeric thermoplastic resin, Included are polyolefins and copolymers thereofl vinyls, olefin-vinyl copolymers, olefin-allyl copolymers, poly-15 amides, acrylics, polystyrenes, cellulosics, polyesters and flurocarbons.
The polyolefins include normally solid polymers of olefins, particularly mono-alpha-olefins, which comprise from about two to about six carbon atoms, e.g., 20 polyethylene, polypropylene, polybutene, polyisobutylene, poly(4-methyl-pentene), and the like. Preferred poly-olefins are polyethylene and polypropylene. Polyethylene - is especially preferred~ An especially preferred poly-ethylene because of its demonstrated effectiveness is 25 termed NA 310*and is sold by National Distillers and Chemical Company.
Copolymers of ethylene, and other compounds interpolymerizable with ethylene such as butene-l, pentene-l, styrene and the like may be employed. In 30 general the ethylene will comprise about 50 to ~ 100 weight % ethylene.
* Trade Mark 1 Suitable vinyl polymers include polyvinyl chloride, polyvinyl acetate, vinyl chloride/vinyl acetate copolymers, polyvinyl alcohol and polyvinyl acetal.
Suitable olefin-vinyl copolymers include ethylene-5 vinyl acetate, ethylene-vinyl propionate, ethylene-vinyl isobutyrate, ethylene-vinyl alcohol, ethylene-methyl acrylate, ethylene-ethyl acrylate J ethylene-ethyl meth-acrylate, and the like. In general the ethylene consti-tutes at least about 25~ of the copolymer by weight.
Olefin-allyl copolymers include ethylene-allyl benzene, ethylene-allyl ether, ethylene-acrolein, and the like.
The silane employed in the polymeric compositions of the invention may be selected from one or more compounds 15 of the following formula A:
Rl R - Si - R2 wherein R, Rl, R2 and R3 are defined as hereina~ove in connection with formula A~
The organic compound employed in the particularly preferred unfilled polymeric compositions of the invention is 25 selected from one or more compounds of the following formula B:
Rl R2 ~ Z - Yl(CnH2n~ Y2 6 : 30 (R3)a Rl~ R2, R3, R6, Yl, Y2, Z, a and n are defined as hereinabove in connection with formula B~
~.~.6~
g 1 A number of R, Rl, R2 and R3 groups useful in connection with the present invention is shown in "Chemicals and Plastics Physical Properties. 1978-80" published by Union Carbide Company on page 43 Exemplary are chloro, methyl, ethyl, methoxy, ethoxy, phenyl,~hydrogen, chloropropyl, vinyl 2-methoxyethoxy, gamma-methacryloxy-propyl, beta-(3,~epoxycyclohexyl)-ethyl, gamma-glycidoxy-propyl, acetoxy, gamma-mercaptopropyl, gamma-aminopropyl, 10 bis-hydroxyethyl-gamma-amino-propyl, bis-acrylic acid gamma-amino-propyl, N-beta(aminoethyl~-gamma-amino-propyl, and methyl 12(gamma-trimethoxysilypropylamino~ethylamino]
3 propionate.
As noted hereinabove, at least one of the R, 15 Rl, R2 and R3 groups of formula A have an electron donating atom such as oxygen, nitrogen or sulphur atom in the chain of the groups. Preferably the electron donating atom is separated from the silicon atom by three atoms.
A preferred group has the following formula, (OR40R5) wherein R4 is Cl to C6 and R5 is a Cl to C8 alkyl, hydrogen, Cl to C8 alkoxy or C2 to C8 alkenyl. A particularly preferred group is 2 methoxyethoxy which has the formula, ( oC2~4CH3 ) 25 A preferred compound is sold under the name A--172*by Union Carbide Company and is chemically defined as vinyl-tris (2-methoxyethoxy) silane. Other R, Rl, R~ and R3 groups include gamma-methacryloxy-propyl, gamma-glycidoxy-propyl, gamma-aminopropyl, bis-hydroxy-ethyl-gamma-amino-30 propyl and N-béta(aminoethyl)-gamma-amino-propyl.
The Rl, R2 and R3 groups of formula B useful in connection with the present invention when Z is silicon, include examples of the groups discussed above * Trade Mark 5~3~
1 in connection with the Union Carbide Company publicaton, particularly when Yl(Cn~l2n) Y2R6 is an alkoxyalkoxy groups.
Among the useful silanes of formula B are gamma-meth-acryloxypropyl-tris(2-methoxyethoxy) silane, tetrakis-(2-methoxyethoxy) silane, methyl-tris (2-methoxyethoxy) silane, phenyl-tris(2 methoxyethoxy) silane, vinyl-tris (2-phenoxyethoxy) silane, vinyl-tris (2-methylthioethoxy) silane and vinyl-tris (2-methoxyethoxy) silane with the latter being particularly preferred. Replacing the silicon with such atoms as ~in, titanium, phosphorous or boron provides other useful compounds which find utility in the invention Thus, such compounds as tris (2-ethoxyethyl) phosphite, tris (2-n-butoxyethyl) phosphite, tetrakis (2 methoxyethoxy) titanium and the like may be employed 15 and are included with the scope of this invention.
Therefore, in the preferred organic compounds of formula ~, Rl, R2, and P~3 are each selected from Yl(CnH2n)~2R6, alkyl, alkoxy, acyloxy, aryl or alkenyl, R6 is alkyl or aryl, Yl and Y2 are o and Z is Si or P- Of eourse~when Z is Si, a is 20 1 and when Z is P, a is 0.
~ hen it is desired to use a polymerie composi-tiO}l whieh can be crosslinked, crosslinking can be accom-plished by any of the known proeedures sueh as ehemical means including peroxide eross-linking; by radiation using 25 eleetron aeeelerators, ~r-rays, high energy radiation, sueh as X-rays, mierowaves ete,; or by thermal erosslinking.
The basie proeedures for erosslinking polymers are ~:
extremely well known to the art and need not be described here in detail.
Conventional crosslinking agents sueh as organie peroxides may be suitably employed, Typieal organie peroxide.free radieal generators include dieumyl peroxide;
2,5-bis (tert.-butylperoxy)-2,5 dimethylhexane; di--t-butyl $~
1 peroxide benzoyl peroxide; J6, ~I bis(t-butyl peroxy) diisopropyl benzene and the like, as discussed in U.S.
Patent No. 3,287,312. The amount of organic peroxidel when employed, will range from about 0.5 to 5.0% by weight 5 based on the total weight of the composition, or about 0.5 to 10 phr, preferably 3 to 6 phr.
~ lhile the silanes and the organic compounds described hereinabove are useful for both thermoplastic and cured polymeric compositions, for compositions to 10 be cured it is preferred that one of the groups/ to wit, R, Rl, R2, or R3, be an organo functional group, e.g., a vinyl group, which group provides the composition with enhanced curing properties.
Minor amounts of other additives may also be 15 employed in conventional amounts to obtain the desired results, Conventional antioxidants such as the hindered phenols, polyquinolines and the like may be employed.
Other ingredients that may be included are plasticizers, dyes, pigments, heat and light stabilizers, antistatic 20 agents and the li~c~
The preferred compositions of this invention are unfilled polymer compositions~ The term 'unfilled" as applied to the - instant composition shall mean a composition which contains less than 10% of a conventional polymer filler. For certain 25 applications and to meet particular specifications the unfilled compositions herein may contain no filler. The compositions of this invention may contain, therefore, O to less than 10~ filler.
Accordingly, fillers, such as mineral fillers, may be employed to this limited extent in preparing the compositions of the 30invention, but in the particularly preferred embodiment and for certain uses, these compositions contain no fillers.
-12 -~ 5~
1 The polymer compositions of this invention can be prepared by mixing the various ingredients When the organic compound and the polymeric component are mixed together to form the instant compositions, the organic 5 compound and poly~eric component are homogeneously dispersed in each other. The order of mixing and specific procedure employed are not critical except to the extent that from the time the peroxide is added, if employed, the temperature is less than about 130~C. in order to prevent premature 10 curing of the composition. This precaution, however, is conventional in the art.
The components may be mixed on a variety of apparatus including multi-roll mills, screw mills, continuous mixers, compounding extruders and Banbury*mixers.
After being extruded onto wire or cable, or other substrate, the crosslinkable compositions are vul-canized at elevated temperatures, e.g., above about 180C.
using conventional vulcanizing procedures.
In order to determine the utility and effective-20 ness of the polymeric compositions of the present inventionwith regard to its inhibiting effect on the water treeing and the electrical treeing thereof, the co~positions - were evaluated by the use of accelerated tests.
Electrical tree tests were performed using the 25 method similar to that in IEEE Conference Paper No. C73, 257-3 1973 by E.J. McMahon and J.R. Perkins. Strips of material approximately 1" wide were cut from a 1/4"
thick compression molded plaque~ The block was machined to give a strip having parallel edges 1" apart, The strip 3 was then cut into 1" square blosks. A blunt needle and a sharp needle were inserted into opposite parallel edges, at elevated temperatures, so that the points were 1/8"
* Trade Mark ~6~5~
l apart. Nee~le insertion and cooling of the sample was performed slowly to avoid inducing thermal or mechanical stresses in the specimen. The sharp needle has a tip diameter of about 0.0002" while the diameter of the blunt 5 needle is 0.002"~ Eight specimens were prepared and tested simultaneously for each composition~ ~he electrical tree test was performed by energizing the sharp needle at 15 XV using a frequency of 60 ~z; the blunt needle was connected to ground. The time required for lO each of the eight specimens to fail by tree ~rowth and subsequent electrical short was re~orded. The time required for 50~ of the samples to fail was employed to characterize the effectiveness of the tree retardant being evaluated.
The water tree test is performed using a procedure similar to that described in ~,S. Patent 4,1~4,202. A
;compression molded disc about 150 millimeters (mm.) in diameter having 24 conical depressions was prepared for each co~.position. The geometry of the disc and dimensions 20 of the depressions are substantially the same as shown in USP 4,144~202. The base of the disc is sprayed with silver paint which serves as the ground electrode. An acrylic tube 6" long is clamped to the upper face forming a test cell. About 150 ml, of 0.01 N sodium chloride 25 solution was poured into the cell and the air bubbles trapped on the surface of the sample were removed.
A platinum wire ring was then immersed in the electrolyte and connected to the electrical supply which provides ,5KV at a frequency of 3KHz. Samples were energized for 30 22 hours after~which time they were removed from the test cell and washed with distilled water. The ten central depressions were cut from the disc and stained to s~
1 make the water trees more visible, Thin sections were obtained with a microtome, which were then examined microscopically (at 200X) and the tree size measured.
Normally four discs were made for each sample so that the 5laverage tree size is calculated from forty individual measurements. In evaluating different tree re-tardants, the relative tree size was determined by comparing the average tree size obtained on a standard thermoplastic high voltage insulation material containing no tree lO~retardant additivesO
Various embodiments of the present invention will now be illustrated by reference to the following specific examples. It is to be understood, however, that such examples are presented for purposes of illustration only, 15land the present invention is in no way to be deemed as limited thereby. A11 parts and percentages are by weight and temperatures in degrees Fahrenheit unless otherwise noted.
I
-15~ 5~
1 ~X~PL~ I
The compositions were prepared by milling a commercial grade of polyethylene (NA 310) and the treeing additive (2P6 by weight) on a 2-roll mill at about 5 300~F. for about 10 minutes to obtain a homoyeneous dis-persion, The crepe obtained was then used to prepare the samples for electric tree and water tree testing using the procedures described hereinabove. The test results are shown in Table 1. All the compositions have the same 10 formulation except for the "treeing" additive as noted in Table 1 and comprise a commercial grade of polyethylene having a Melt Index of about 0,20 to 0.35 g/10 min. and a density of about ,917 grams/cubic centimeter (g/cc).
The control sample does not contain a "treeing" additive.
-16~
1 TABL~ I
Sample Treeing Additive Double Needle Water Tree No. Test Time to (Relative 50% Failure Tree Size) (minutes) , _ A Vinyl-tris- ~ 12,700 0,23 (2-methoxy-ethoxy) silane (no failures) B Gamma-glycid- 2,800 0.34 oxypropyl -tri-methoxysilane 1 Control 80 (No Additive) 2 Vinyl triethoxy 30 0.29 silane ... . _ _ .. _ 3 Beta-(3,4-epoxy- 620 0.34 cyclohexyl)-ethyl-trimethoxysilane . . _ _ .
4 Dodecanol 127 0.34 3o 1 The results clearly show the improvement in both water treeing and electrical treeing properties o~
formulations prepared in accordance with the present inven-tion. Thus, comparing Samples A and B, o~ the invention,
formulations prepared in accordance with the present inven-tion. Thus, comparing Samples A and B, o~ the invention,
5 with Samples 1-~, which are outside the invention, the improvement is readily apparent. Comparing Sample A
with the control, Sample 1, shows the vast improvement in properties when vinyl-tris (2-methoxyethoxy) silane is employed. Similarly~ a comparison of Sample A wi-th Sample 10 2 shows the importance for utilizing a silane having an electron donor atom in the chain of the groups attached to the silicon atom. A comparison of Sample A with Sample B shows the advantage of employing three electron donating group radicals attached to the silicon atom.
In the same fashion as in Exam~le I, a number of organic compounds were evaluated as "treeing" additives.
In all instances the addi-tive was incorporated in the polyeth~lene at a concentration of 1.5%. The results of the electrical tree and water tree testing are shown in Table II.
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1 The silanes evaluated demonstrated a superiority in both water tree and electrical tree resistance for those silanes having alkoxyalkoxy substituents. (Samples
with the control, Sample 1, shows the vast improvement in properties when vinyl-tris (2-methoxyethoxy) silane is employed. Similarly~ a comparison of Sample A wi-th Sample 10 2 shows the importance for utilizing a silane having an electron donor atom in the chain of the groups attached to the silicon atom. A comparison of Sample A with Sample B shows the advantage of employing three electron donating group radicals attached to the silicon atom.
In the same fashion as in Exam~le I, a number of organic compounds were evaluated as "treeing" additives.
In all instances the addi-tive was incorporated in the polyeth~lene at a concentration of 1.5%. The results of the electrical tree and water tree testing are shown in Table II.
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1 The silanes evaluated demonstrated a superiority in both water tree and electrical tree resistance for those silanes having alkoxyalkoxy substituents. (Samples
6, 9, 10, 14, 22 and 23). This can be seen by comparing inter alia the silane pairs of samples 6 and 7, 9 and 11 and 13 and 14. It also appears tha-t there is an optimum number of alkoxy alkoxy substituents - compare samples 6, 9 and 10. The effect of a vinyl substituent as compared to an alkyl or aryl substituent is evident from comparing samplés 6~ 9 and 22, The location of a particular substituent, viz, an aryl group, can influence the inhibi-tion properties of the organic compound as seen ~rom samples 22 and 23, Samples 24 and 25 show that organic phosphites are effective in both water and electrical tree inhibition.
while sample 26 shows similar effectiveness for an organic titanium compound.
While the invention has been directed principally to the use of silanes, it will be understood by those skilled 20 in the art that other compounds containi.ng a multivalent atom such as titanium, tin, phosphorous, and the like may be employed.
while sample 26 shows similar effectiveness for an organic titanium compound.
While the invention has been directed principally to the use of silanes, it will be understood by those skilled 20 in the art that other compounds containi.ng a multivalent atom such as titanium, tin, phosphorous, and the like may be employed.
Claims (33)
- Claim 1 (continued) n is 1 to 8 with the proviso that when Z is P, a is 0, Y1 and Y2 are each 0 and R1 and R2 are the same and are Y1 (CnH2n)Y2R6), and when Z is P, R6 is not hydrogen, said composition containing from 0 to 10% by weight of filler.
- 2. A composition as in claim 1 wherein the polymer is polyethylene,
- 3. A composition as in claim 1 wherein R1, R2 and R3 are each selected from Y1(CnH2n) Y2R6, alkyl, alkoxy, acyloxy, aryl or alkenyl, R6 is alkyl or aryl, and Y1 and Y2 are each 0.
- 4. A composition as in claim 3 wherein Z is Si and a is 1.
- 5. A composition as in claim 4 wherein R1 is vinyl, R2 and R3 are each Y1(CnH2n) Y2R6, R6 is methyl and n is 2.
- 6. A composition as in claim 4 wherein R1 is methyl, R2 and R3 are each Y1(CnH2n) Y2R6, R6 is methyl and n is 2.
- 7. A composition as in claim 4 wherein R1, R2 and R3 are each Y1(CnH2n) Y2R6, R6 is methyl and n is 2.
- 8. A composition as in claim 4 wherein R1 is gamma-methacryloxypropyl, R2 and R3 are each Y1(CnH2n) Y2R6, R6 is methyl and n is 2.
- 9. A composition as in claim 4 wherein R1 is phenyl, R2 and R3 are each Y1(CnH2n) Y2R6, R6 is methyl and n is 2.
- 10. A composition as in claim 4 wherein R1 is vinyl, R2 and R3 are each Y1(CnH2n) Y2R6, R6 is phenyl and n is 2.
- 11. A composition as in claim 1, wherein z is P, R6 is ethyl and n is 2.
- 12. A composition as in claim 1, wherein Z is P, R6 is n-butyl and n is 2.
- 13. A composition as in claim 3 wherein Z is Ti and a is 1.
- 14. A composition as in claim 13 wherein R1, R2 and R3 are each Y1(CnH2n) Y2R6, R6 is methyl and n is 2.
15. A method of stabilizing a polymeric insulated electrical conductor against water treeing and electrical tree-ing which comprises:
coating an electrical conductor with an insulating effective amount of a polymeric insulating composition containing a homogeneous mixture of a polymeric component and an effective amount, as a water treeing and electrical treeing inhibitor, of an organic compound having the following formula:
wherein R1, R2 and R3 are the same or different and are Y1(CnH2n) Y2R6, C1 to C8 alkyl, C1 to C8 alkoxy, C1 to C8 acyloxy, C6 to C18 aryloxy or substituted aryloxy, C6 to C18 aryl or substituted aryl, hydrogen, halogen, an epoxy containing radical, C2 to C8 alkenyl, a nitrogen containing radical, a carboxy containing radical, a mercapto containing radical or an ether containing radical;
R6 is C1 to C8 alkyl, C1 to C8 alkoxy, C1 to C8 acyloxy, C6 to C18 aryloxy or substituted aryloxy, C6 to C18 aryl or substituted aryl, hydrogen, halogen, an epoxy containing radical, C2 to C8 alkenyl, a nitrogen containing radical, a carboxy containing radical, a mercapto containing radical or an ether containing radical:
Y1 and Y2 are the same or different and are O, S or NH;
Z is Si, Sn, Ti, P or B;
a is 0 or 1; and - Claim 15 (continued) n is 1 to 8 with the provision that when Z is P1, a is O, Y1 and Y2 are each o and R1 and R2 are the same and are Y
(CnH2n) Y2R6), and when Z is P, R6 is not hydrogen, the composition containing from 0 to 10% by weight of filler whereby said insulated electrical conductor exhibits water tree-ing and electrical treeing inhibition when exposed to an environ-ment subject to water treeing and electrical treeing conditions. - 16. A method as in claim 15 wherein the polymer is polyethylene.
- 17. A method as in claim 15 wherein R1, R2 and R3 are each selected from Y1(CnH2n)Y2R6, alkyl, alkoxy, acyloxy, and aryl or alkenyl, R6 is alkyl or aryl, and Y1 and Y2 are each 0.
- 18. A method as in claim 17 wherein Z is Si and a is y.
- 19. A method as in claim 18 wherein R1 is vinyl, R2 and R3 are each Y1(CnH2n)Y2R6, R6 is methyl and n is 2.
- 20. A method as in claim 18 wherein R1 is methyl, R2 and R3 are each Y1(CnH2n)Y2R6, R6 is methyl and n is 2.
- 21. A method as in claim 18 wherein R1, R2 and R3 are each Y1(CnH2n)Y2R6, R6 is methyl and n is 2.
- 22. A method as in claim 18 wherein R1 is gamma-methacryloxypropyl, R2 and R3 are each Y1(CnH2n)Y2R6, R6 is methyl and n is 2.
- 23. A method as in claim 20 wherein R1 is phenyl, R2 and R3 are each Y1(CnH2n)Y2R6, R6 is methyl and n is 2.
- 24. A method as in claim 20 wherein R1 is vinyl, R2 and R3 are each Y1(CnH2n)Y2R6, R6 is phenyl and n is 2.
- 25. A method as in claim 19 wherein Z is P and a is 0.
- 26. A method as in claim 25 wherein R6 is ethyl and n is 2.
- 27. A method as in claim 25 wherein R1 and R2 are each Y1(CnH2n)Y2R6, R6 is n-butyl and n is 2.
- 28. A method as in claim 17 wherein Z is Ti and a is 1.
- 29. A method as in claim 28, wherein R1, R2 and R3 are each Y1(CnH2n)Y2R6, R6 is methyl and n is 2.
- 30. A method in accordance with claims 15, 18 or 29, wherein the insulating composition is curable or cured.
- 31. A method according to claims 15, 18 or 29, wherein the composition contains an effective amount of crosslinking agent, antioxidant, plasticizer, stabilier and/or antistatic agent.
- 32. A method according to claim 15, 18 or 29, wherein the composition contains an effective amount of pigment or dye.
- 33. An electrical conductor coated with the compositions of claims 1, 2 or 14.
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polymeric composition having enhanced resistance to water treeing and electrical treeing comprising a homogeneous mixture of a polymeric component and an effective amount, as a water treeing and an electrical treeing inhibitor, of an organic compound having the formula:
wherein R1, R2 and R3 are the same or different and are Y1(CnH2n) Y2R6, C1 to C8 alkyl, C1 to C8 alkoxy, C1 to C8 acyloxy, C6 to C18 aryloxy or substituted aryloxy, C6 to C18 aryl or substituted aryl, hydrogen, halogen, an epoxy containing radical, C2 to C8 alkenyl, a nitrogen containing radical, a carboxy containing radical, a mercapto containing radical or an ether containing radical; R6 is C1 to C8 alkyl, C1 to C8-alkoxy, C1 to C8 acyloxy, C6 to C18 aryloxy or substituted aryloxy, C6 to C18 aryl or substituted aryl, hydrogen, halogen, an epoxy containing radical, C2 to C8 alkenyl, a nitrogen containing radical, a carboxy containing radical, a mercapto con-taining radical or an ether containing radical;
Y1 and Y2 are the same or different and are O, S or NH;
Z is Si, Sn, Ti, P or B;
a is 0 or 1; and
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US5887879A | 1979-07-19 | 1979-07-19 | |
US58,878 | 1979-07-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1161589A true CA1161589A (en) | 1984-01-31 |
Family
ID=22019465
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000355215A Expired CA1161589A (en) | 1979-07-19 | 1980-07-02 | Electrical tree and water tree resistant polymer compositions |
Country Status (18)
Country | Link |
---|---|
JP (1) | JPS5620057A (en) |
AT (1) | AT371830B (en) |
AU (1) | AU6028380A (en) |
BE (1) | BE884394A (en) |
BR (1) | BR8004510A (en) |
CA (1) | CA1161589A (en) |
DE (1) | DE3026586A1 (en) |
DK (1) | DK310280A (en) |
ES (1) | ES8105886A1 (en) |
FI (1) | FI802284A (en) |
FR (1) | FR2461734A1 (en) |
GB (1) | GB2055854B (en) |
IT (1) | IT1132208B (en) |
LU (1) | LU82641A1 (en) |
NL (1) | NL8004164A (en) |
NO (1) | NO802166L (en) |
NZ (1) | NZ194381A (en) |
SE (1) | SE8005265L (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0109797A3 (en) * | 1982-11-18 | 1984-06-27 | Dow Corning Corporation | Polymeric compositions resistant to electrical and water treeing |
EP0114495A3 (en) * | 1982-12-27 | 1984-10-17 | Dow Corning Corporation | Anti-treeing additives |
CA1222084A (en) * | 1983-04-08 | 1987-05-19 | Gary A. Vincent | Anti-treeing additives |
GB8617004D0 (en) * | 1986-07-11 | 1986-08-20 | Bp Chem Int Ltd | Polymer composition |
DE3628554A1 (en) * | 1986-08-22 | 1988-03-03 | Licentia Gmbh | PLASTIC INSULATION |
DE4023702B4 (en) * | 1990-07-26 | 2007-01-11 | Sonderhoff Gmbh | Use of a thermosetting one-component polyurethane composition as pourable and sprayable sealant for the production of inflatable rubber-like seals |
DE4204200A1 (en) * | 1992-02-13 | 1993-08-19 | Daimler Benz Ag | Liq. useful as heat transfer and insulating media - comprises mixt. of poly-alpha-olefin(s) and/or isoparaffin(s) with poly:di:methyl:siloxane(s) and/or poly:alkyl -/poly:aryl:siloxane(s) |
JP2007273277A (en) * | 2006-03-31 | 2007-10-18 | Furukawa Electric Co Ltd:The | Cable, and deterioration prevention method of cable |
ES2426666T3 (en) * | 2007-01-12 | 2013-10-24 | Utilx Corporation | Composition and procedure to restore an electric cable and inhibit corrosion in the aluminum conductor core |
US20230407063A1 (en) * | 2020-10-29 | 2023-12-21 | Dow Global Technologies Llc | Polyaminosiloxane Water Tree Repellant for Electrical Insulation |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4020214A (en) * | 1973-06-21 | 1977-04-26 | General Electric Company | Method of making an insulated electrical conductor using pressureless curing of filled ethylene containing polymeric compositions, and an insulated conductor formed thereby |
US4100089A (en) * | 1976-01-16 | 1978-07-11 | Raychem Corporation | High-voltage insulating material comprising anti-tracking and erosion inhibiting compounds with insulating polymers |
DE2737430C2 (en) * | 1977-08-19 | 1983-03-17 | Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt | Polyolefin insulation with a voltage stabilizer |
-
1980
- 1980-07-02 CA CA000355215A patent/CA1161589A/en not_active Expired
- 1980-07-09 AU AU60283/80A patent/AU6028380A/en not_active Abandoned
- 1980-07-14 DE DE19803026586 patent/DE3026586A1/en not_active Withdrawn
- 1980-07-17 AT AT0372680A patent/AT371830B/en not_active IP Right Cessation
- 1980-07-18 FI FI802284A patent/FI802284A/en not_active Application Discontinuation
- 1980-07-18 NL NL8004164A patent/NL8004164A/en not_active Application Discontinuation
- 1980-07-18 JP JP9770880A patent/JPS5620057A/en active Pending
- 1980-07-18 ES ES494311A patent/ES8105886A1/en not_active Expired
- 1980-07-18 BR BR8004510A patent/BR8004510A/en unknown
- 1980-07-18 IT IT23552/80A patent/IT1132208B/en active
- 1980-07-18 FR FR8015919A patent/FR2461734A1/en active Granted
- 1980-07-18 SE SE8005265A patent/SE8005265L/en not_active Application Discontinuation
- 1980-07-18 DK DK310280A patent/DK310280A/en not_active Application Discontinuation
- 1980-07-18 BE BE0/201467A patent/BE884394A/en not_active IP Right Cessation
- 1980-07-18 NO NO802166A patent/NO802166L/en unknown
- 1980-07-18 LU LU82641A patent/LU82641A1/en unknown
- 1980-07-18 NZ NZ194381A patent/NZ194381A/en unknown
- 1980-07-21 GB GB8023773A patent/GB2055854B/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
FI802284A (en) | 1981-01-20 |
LU82641A1 (en) | 1981-02-02 |
BE884394A (en) | 1981-01-19 |
IT8023552A0 (en) | 1980-07-18 |
ES494311A0 (en) | 1981-07-01 |
NL8004164A (en) | 1981-01-21 |
NO802166L (en) | 1981-01-20 |
DK310280A (en) | 1981-01-20 |
GB2055854A (en) | 1981-03-11 |
FR2461734B1 (en) | 1983-11-18 |
JPS5620057A (en) | 1981-02-25 |
DE3026586A1 (en) | 1981-02-05 |
SE8005265L (en) | 1981-02-04 |
AU6028380A (en) | 1982-01-28 |
BR8004510A (en) | 1981-02-03 |
ATA372680A (en) | 1982-12-15 |
AT371830B (en) | 1983-08-10 |
GB2055854B (en) | 1983-10-19 |
ES8105886A1 (en) | 1981-07-01 |
IT1132208B (en) | 1986-06-25 |
NZ194381A (en) | 1982-09-14 |
FR2461734A1 (en) | 1981-02-06 |
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