MXPA99009174A - Crosslinkable polyolefin-based polymeric composition with a high thermal coefficient of service in a motor vehicle cable and process for preparing the same - Google Patents
Crosslinkable polyolefin-based polymeric composition with a high thermal coefficient of service in a motor vehicle cable and process for preparing the sameInfo
- Publication number
- MXPA99009174A MXPA99009174A MXPA/A/1999/009174A MX9909174A MXPA99009174A MX PA99009174 A MXPA99009174 A MX PA99009174A MX 9909174 A MX9909174 A MX 9909174A MX PA99009174 A MXPA99009174 A MX PA99009174A
- Authority
- MX
- Mexico
- Prior art keywords
- phr
- ethylene
- copolymer
- composition
- clause
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 121
- 229920000098 polyolefin Polymers 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims description 37
- 229920001577 copolymer Polymers 0.000 claims description 29
- -1 polyethylene Polymers 0.000 claims description 21
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N Antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 150000004665 fatty acids Chemical class 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000005299 abrasion Methods 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 229920001567 Vinyl ester Polymers 0.000 claims description 7
- 238000007792 addition Methods 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims description 6
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 239000004700 high-density polyethylene Substances 0.000 claims description 6
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000004698 Polyethylene (PE) Substances 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000011256 inorganic filler Substances 0.000 claims description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims description 4
- GYLXWHLPLTVIOP-UHFFFAOYSA-N COC(OC)(OC)CO[SiH2]C=C Chemical compound COC(OC)(OC)CO[SiH2]C=C GYLXWHLPLTVIOP-UHFFFAOYSA-N 0.000 claims description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N Tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (N-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 2
- GRPTWLLWXYXFLX-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclodecane Chemical compound BrC1(Br)CCCCCCCC(Br)(Br)C1(Br)Br GRPTWLLWXYXFLX-UHFFFAOYSA-N 0.000 claims description 2
- XQKQZOLAVMIQHZ-UHFFFAOYSA-N 1,1-dibromo-3-(3,3-dibromopropoxy)propane Chemical compound BrC(Br)CCOCCC(Br)Br XQKQZOLAVMIQHZ-UHFFFAOYSA-N 0.000 claims description 2
- NDRKXFLZSRHAJE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br NDRKXFLZSRHAJE-UHFFFAOYSA-N 0.000 claims description 2
- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 claims description 2
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 claims description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-tris(prop-2-enoxy)-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims description 2
- WZHHYIOUKQNLQM-UHFFFAOYSA-L 3,4,5,6-tetrachlorophthalate Chemical compound [O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C([O-])=O WZHHYIOUKQNLQM-UHFFFAOYSA-L 0.000 claims description 2
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N Decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N Dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- CAYGQBVSOZLICD-UHFFFAOYSA-N Hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 claims description 2
- VUNCWTMEJYMOOR-UHFFFAOYSA-N Hexachlorocyclopentadiene Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)=C1Cl VUNCWTMEJYMOOR-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 2
- 150000002013 dioxins Chemical class 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 231100000331 toxic Toxicity 0.000 claims description 2
- 230000002588 toxic Effects 0.000 claims description 2
- DBXDLSPMDNQBBQ-UHFFFAOYSA-N tris(2-methoxyethoxy)-phenylsilane Chemical compound COCCO[Si](OCCOC)(OCCOC)C1=CC=CC=C1 DBXDLSPMDNQBBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- LLZHXQRNOOAOFF-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2NC(S)=NC2=C1 LLZHXQRNOOAOFF-UHFFFAOYSA-N 0.000 claims 4
- 239000002253 acid Substances 0.000 claims 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 3
- 229910052710 silicon Inorganic materials 0.000 claims 3
- 239000010703 silicon Substances 0.000 claims 3
- 150000007513 acids Chemical class 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims 1
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims 1
- YASDJUXENMYIBH-UHFFFAOYSA-N 3-methyl-3-phenyl-1,2-dihydroindene Chemical compound C1CC2=CC=CC=C2C1(C)C1=CC=CC=C1 YASDJUXENMYIBH-UHFFFAOYSA-N 0.000 claims 1
- 239000004641 Diallyl-phthalate Substances 0.000 claims 1
- STVZJERGLQHEKB-UHFFFAOYSA-N Ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims 1
- 229940116336 Glycol Dimethacrylate Drugs 0.000 claims 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N TMPTA Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (Z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 150000002193 fatty amides Chemical class 0.000 claims 1
- 229920002959 polymer blend Polymers 0.000 claims 1
- 239000002952 polymeric resin Substances 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 claims 1
- SSZBHSXTJWOAJR-UHFFFAOYSA-N tris(2-methoxyethoxy)-propylsilane Chemical compound COCCO[Si](CCC)(OCCOC)OCCOC SSZBHSXTJWOAJR-UHFFFAOYSA-N 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 2
- 241001367079 Una Species 0.000 abstract 7
- 241001282138 Antigonia capros Species 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 13
- 238000009413 insulation Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000000111 anti-oxidant Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 230000003078 antioxidant Effects 0.000 description 5
- 125000001246 bromo group Chemical group Br* 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- LGOPTUPXVVNJFH-UHFFFAOYSA-M CCCCCCCCCCCCCCC([O-])=S Chemical compound CCCCCCCCCCCCCCC([O-])=S LGOPTUPXVVNJFH-UHFFFAOYSA-M 0.000 description 3
- 239000004614 Process Aid Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-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
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N Antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ZDZOTLJHXYCWBA-VCVYQWHSSA-N Docetaxel Chemical compound O([C@H]1[C@H]2[C@@](C([C@H](O)C3=C(C)[C@@H](OC(=O)[C@H](O)[C@@H](NC(=O)OC(C)(C)C)C=4C=CC=CC=4)C[C@]1(O)C3(C)C)=O)(C)[C@@H](O)C[C@H]1OC[C@]12OC(=O)C)C(=O)C1=CC=CC=C1 ZDZOTLJHXYCWBA-VCVYQWHSSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N Hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N Lauric acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000007706 flame test Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000002195 synergetic Effects 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- GRKDVZMVHOLESV-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(COC(=O)C=C)C(Br)=C1Br GRKDVZMVHOLESV-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 1-butanal Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000010752 BS 2869 Class D Substances 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N Calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N Indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 102220432561 MEF2A S97G Human genes 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N Phosphite Chemical compound [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- ANXPQGGXFFHERW-UHFFFAOYSA-N SC1=C(C=CC=C1C=1NC=CN1)C.[Zn] Chemical compound SC1=C(C=CC=C1C=1NC=CN1)C.[Zn] ANXPQGGXFFHERW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 231100000078 corrosive Toxicity 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 230000001808 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- VOLSCWDWGMWXGO-UHFFFAOYSA-N cyclobuten-1-yl acetate Chemical compound CC(=O)OC1=CCC1 VOLSCWDWGMWXGO-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- FORHPIYYTQZPDW-UHFFFAOYSA-N ethyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](CC)(OCCOC)OCCOC FORHPIYYTQZPDW-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- OUHCLAKJJGMPSW-UHFFFAOYSA-L magnesium;hydrogen carbonate;hydroxide Chemical compound O.[Mg+2].[O-]C([O-])=O OUHCLAKJJGMPSW-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Una composición polimérica y proceso de preparación, la cual comprende una mezcla de poliolefinas reticulables con elevado coeficiente térmico de servicio en cable automotriz, caracterizado por una mayor resistencia al ataque químico de aceites a alta temperatura 150§C, resistencia a la propagación vertical de la flama, e incremento de la resistencia a la abrasión para aplicación en compuestos para aislamiento y cubierta de cables y conductores eléctricos. Las poliolefinas son una combinación químico sinergística entre una carga de hidrocarburos halogenada combinada con trióxido de antimonio un alcoxisilano, un agentede reticulación, una combinación de aditivos como ayuda de proceso y una combinación de tres agentes antioxidantes.
Description
POLEVÍERICA COMPOSITION BASED ON RETICULABLY POLIOLEPHINES WITH HIGH THERMAL COEFFICIENT OF SERVICE
IN AUTOMOTIVE CABLE AND PREPARATION PROCESS
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION: The invention relates to a polymeric composition based on crosslinkable polyolefins with high thermal coefficient of service up to 150 ° C as insulation in automotive cable and to the process of promoting in a mixture of crosslinkable polyolefins with halogens that are grafted to the chain of the polymer and that by means of a combination of additives they confer to the formulation for isolation and cover of cables and electrical conductors a temperature of higher thermal service with characteristics such as: temperature of service of 150 ° C, resistance to the vertical propagation of flame, resistance to oils at 136 ° C, and resistance to abrasion.
Description of the state of the art: A wide variety of inventions applicable to the formulation of various types of insulators for cable sheath and electric conductors are known, for example in the patent US 5,401787 there are described insulating compositions retardant to the f , improved to moisture and curable from ethylene-alkoxysilane-halogenated anhydride copolymers and antimony trioxide that complies with SAEJ-1 128.
US Pat. No. 5,439,965 describes flame-retardant and abrasion-resistant interlaced compositions as insulators for wires and cables based on ethylene vinyl acetate copolymer, a halogenated compound, antimony trioxide and an organic peroxide.
US Pat. No. 5,955525 describes a formulation for insulation and protection of cables and electric conductors resistant to the flame of low smoke emission with thermal coefficients of 135 ° C.
The above inventions are practically limited to the flame resistance or even the abrasion, but at lower thermal coefficients of service except the last invention owned by the applicant operating at thermal temperature coefficients of the product up to 135 ° C.
One of the main applications of the present invention is that the polymeric compositions of cross-linkable polyolefinic type with high thermal coefficient provide the insulation of electrical cables and conductors of automotive type, a greater security in the operation of the cables especially when these are in areas where the heating of the motor is high and therefore the physical properties, and the thermal stability of the compositions should not deteriorate under said operating conditions.
hot, as well as its resistance to flame and abrasion.
The compositions are applied as insulation in cables and electrical conductors to reduced thicknesses of 0.15 - 0.40 millimeters of thickness according to the standards for primary low voltage cables ISO 6722 Class D. RENAULT 36-05-009J and for UL 150 ° C cables according to to UL 3321. In addition it additionally fulfills the following specifications DELPHI ESM-3207, ESM-3300 and ESM-3269: CHRYSLER MS-9502 and FORD WSS 22P7 A4. The compositions present a good balance of the main properties such as processability, physical, chemical, and electrical with that of flame resistance, resistance to oils and resistance to abrasion. The main advantages obtained when developing said compositions are: (a) with the combination of additives they provide greater thermal stability and insulating compounds and / or thermal class covers 150 ° C (b) are obtained with the use of flame retardant agents based on halogens that are grafted to the polymer chain, greater resistance to vertical propagation of the flame (c) is obtained and colorable compositions can be obtained.
For the present invention, a wide variety of antioxidants were used, such as: I, 2-dihydro-2,2,4-trimethyl quinoline, and sterically hindered phenols combinations with distearil 3,3'thio-dipropianato (DSTDP), bis ( 2,4 di terbutyl) pentaerythritol diphosphite, tris (2,4-diterbutyl phenyl) phosphite, zinc salt 2, mercapto
benzimidazole, zinc salt 2-mercapto toluylmidazole, pentaerythritol tetra bis (betalaurylthiopropionate) and dilauryl 3,3'thio-dipropianate.
Combinations of di-alkyl-thio-dipropianate with hindered phenols provide high thermal stabilities
DETAILED DESCRIPTION OF THE INVENTION
The polymeric composition with resistance to vertical propagation of the flame, resistance to oils, resistance to abrasion and mainly with a high thermal stability at service temperatures up to 150 ° C, subjected to aging times of long duration at 3000 hours until cable operating temperatures of 150 ° C ± 5 ° C already aged for a short duration of 240 hours at a temperature of 180 ° C, ± 3 ° C is based on a copolymer of ethylene and vinyl ester of an aliphatic carboxylic acid alone or combined with another series of polyolefins with a series of active components that significantly improve thermal stability, resistance to vertical propagation of the flame, and resistance to oils at 136 ° C and resistance to abrasion. The amounts of the components are expressed in parts per hundred of resin or the sum of this with other resins involved
The components used in the composition of the present invention defined qualitatively and quantitatively are described below.
Ethylene copolymer The polymeric component of the present composition is a copolymer of ethylene and vinyl ester of the C 2-6 aliphatic carboxylic acid, such as vinyl acetate, vinyl propyanate, vinyl butyral vinyl pentanoate or vinyl hexanoate. The copolymer preferably used is an ethylene and vinyl acetate (EVA) wherein said copolymer (EVA) can contain vinyl acetate in an approximate ratio of 3% to 90% and preferably from 3% to 45% with the remainder being ethylene . The terpolymers of ethylene, vinyl acetate and other types of polymerizable olefinic monomers can be employed in suitable proportions.
It is also possible to use other types of polymers such as polyethylene, polypropylene, copolymers and ethylene-propylene terpolymer and acrylic copolymers. Low density polyethylenes, linear low density polyethylenes, and high density polyethylenes have melt indices of 0.5 to 20 g / 10 min. to promote uniform and acceptable blends, mainly when the proportions are 30% or less over the total polymer composition.
The ethylene copolymers and the mixtures have melt indices in the range 0.1 to 7 g / 10 min. EVA copolymers generally have a melt index of 0.5 to 5 g 10 min.
Active Components
Loading of halogenated organic compounds The fillers used in the composition of the present invention are brominated organic fillers that do not generate dioxins and furans upon combustion and in addition to being approved by the EPA. (Office of Environmental Protection USA for the Prevention of Pollution and Regularization of New Substances, Toxic Pending Information Development) The chemical structure of these charges is composed of a cycloaliphatic ring combined with bromine atoms, such as:
Octabromotrimethylphenyl Indane H18 Br? 2Br8-Br, 73.7% (Fusing temperature 240 ° C 256 ° C) FR-1808® trademark of Dead Sea Bromine Group.
Monomer Pentabromobenzyl acrylate C ^ H 5 Br 5 O-Br, 71.8% (melting temperature 117-120 ° C) .FR-1025® trademark of Dead Sea Bromine Group.
Among other halogenated compounds that can be used in the composition as a reference are the following:
• hexabromobenzene, tetrabromobisphenol A, tetrachlorobisphenol A, anhydrous tetrabromophthalate, hexabromo cyclodecane, octabromodiphenyl, perchloropentacyclohexane, octabromodiphenyl ether decabromodiphenyl ether, tribromo phenyl allyl ether, pentabromo ethylbenzene 2,4,6-tribromophenol, pentabromodi phenyl ether, ethylene bis (tetrabromophthalimide), anhydrous tetrachlorophthalate, poly (pentabromobenzyl) acylate, bis (dibromopropyl) ether of tetrabromobisphenol A, and Diels-Alder byproduct of hexachlorocyclopentadiene with maleic anhydride.
The brominated compounds used in the present invention allow obtaining grafts in the polymers used.
Antimony trioxide The use of antimony trioxide with the brominated compounds produces a chemical synergy effect that improves the resistance to the flame. The ratios employed of brominated compounds with antimony trioxide employed were 2: 1 to 5: 1 and more preferably 2.5: 1 to 4: 1. Other types of complementary additives can be used to achieve synergy between the brominated compounds, which may be: antimony pentoxide, antimony silicate, boron compounds, tin oxide, zinc oxide, zinc borate, aluminum trioxide, and aluminum trihydroxide.
The use of these charges will basically depend on the degree of flame retardancy to be achieved and on the viscosity that the polymer composition reaches by increasing the proportion of the same, therefore they can be included if complementary thermohorgonic loads are required. halogenated such as: alumina trihydrate (Al2? 3H2O or Al (OH) 3, magnesium hydroxide, calcium silicate hydrate, magnesium carbonate hydrate, etc. These charges are pretreated with an alkoxysilane. can obtain a physicochemical coupling that offers greater fixation of the charge to the polymer.
The particle size of the charge must be according to the Theological characteristics necessary to reach the processability conditions of the most optimal polymeric compositions, and with this also reach the physical-mechanical, flame-retardant and chemical characteristics necessary to satisfy the application requirements.
Alkisilanes The alkoxysilanes used were: vinyl trimethoxyethoxysilane, phenyl tris (2-methoxyethoxy) silane, methyl triethoxysilane, methyl-methyl tris- (2-methoxyethoxy) silane, dimethyl diethoxysilane, ethyl trimethoxysilane and viml trimethoxysilane.
Especially preferred alkoxysilanes by conferring better properties to the polymer composition are:
• Vinyl trimethoxyethoxysilane, of formula • Vinyl trimethoxysilane, of formula:
The proportions of the alkoxysilanes are between 0.5-5 phr. (Parts per cent of resin)
Crosslinking Agents Base compositions of ethylene and vinyl acetate can be crosslinked using the usual traditional crosslinking methods, such as by thermal moisture and / or radiation, the crosslinking agents employed in the present composition are: dicumyl peroxide and alpha, alpha'-bis (terbutyleneperoxy) diisopropylbenzene with the combination of coagents such as triallyl cyanurate, triallyl. ,,, tetracrilato, trimetilol propane triacrilato, trimetilol propane, trimetacrilato, tetretileno glycol dimethacriiate, low molecular weight polybutadiene and n, n'-m-fenilendimaleico in order to improve the state and speed of crosslinking, being the peroxide alpha, - alpha 'bis (terbutylperoxy) diisopropylbenzene and the n, n'-m-phenylenedimale coagent known commercially as HVA-2® are preferably used for the development of the present invention, the proportions of coagent and crosslinking agent can be 0.5-10 phr. The organic peroxides are activated during the vulcanization processes, producing chemical bonding between the ethylene vinyl acetate polymer chains in a three-dimensional matrix of carbon-carbon chains. In order to carry out the chemical crosslinking in the present invention, it will be possible to use other crosslinking agents that generate free radical radicals such as 2.5 - (tert-butylperoxy); 2,5-dimethylexin-3; di-tert-butylperoxide; 2,5- (tert-butylperoxy) -; -2,5-dimethylexane; tert-butylcumyl peroxide. For the selection of the crosslinking agents it is necessary to take into account the decomposition temperatures of the same to avoid undesirable effects during the mixing and extrusion processes, the amounts and / or proportions to be used of the curing agents will be defined in depending on the type of application, because in,. As the content of the agent increases in the formula, the following properties will be improved or reduced:
Higher and / or lower thermal stability after aging in short and long duration oven, and under operating temperatures of 150 ° C.
• Greater and / or lower resistance to ignition and resistance to combustion. • Greater and / or lower resistance to the attack of corrosive chemical fluids. • Greater and / or lower resistance to oils. • Greater and / or lower resistance to abrasion • Greater and / or lower dielectric strength. • Greater and / or lower resistance to humidity or to the gain and / or loss of electrical properties due to the absorption of water in the polymeric compositions.
Additive agents to apply the composition as an insulating compound with a high thermal coefficient at service temperatures of up to 150 ° C for cables or electrical conductors of the automotive type with ISO standards class D6722, FORD S97G 14401-AA RENAULT 36-05-009 / J , FORD 22P7 A4, DELPHI ESM 3207, ESM-3300 and ESM-3269 AND CHRYLER MS-95020
Process Additives The process additives used in the present invention allow the compositions to be easily mixed and / or prepared and / or extruded and / or shaped. The composition of the process additives is composed of the following components:
• A fatty acid and / or derivative of the fatty acids referred to the aliphatic carboxylic acid of 8 to 22 carbon atoms, saturated and unsaturated, such as stearic acid, caproic acid, isostearic acid, lauric acid STRUKTOL TR 016
(mixture of metallic soaps of fatty acids with an amide) and the latter being especially preferred, due to its ability to promote good Theological properties;
• A low molecular weight silicone oil, being an excellent promoter to avoid the adhesion of the compositions on metal surfaces, mixing equipment, extrusion and mainly in copper electrical conductors.
* An aliphatic resin (STRUKTOL TR 060) can be used preferably to improve the dispersion and / or homogeneity of the inorganic fillers, antioxidants, and crosslinking agents of the polymeric composition
The proportions employed in each system will be from fatty acid to silicone oil 1: 1 to approximately 1: 6, and preferably from fatty acid to silicone oil 1: 3. And with respect to the aliphatic resin to the fatty acid 1: 1 to about 1: 6 and preferably of hydrocarbon resin to fatty acid 1: 3. The total amount of the composition of the process additives is from 0.25 phr to 8 phr of the total polymer composition.
Antioxidants capable of withstanding continuous operating temperatures of 150 ° C ± 5 ° C for 3000 hours and / or aged in a 240 hour oven at 180 ° C ± 3 ° C were used in the present invention. Basically the invention contemplates the use of an oven of 240 hours at 180 ° C. ± 3 ° C Basically, the invention contemplates the use of a package of antioxidants capable of complying with the above requirements and also preventing the antioxidants used from discoloring and / or staining the copper of the electric conductor of the cable, as well as modifying the tone of the pigmented compound at the time of steam-crosslinking the polymer compositions containing said antioxidants.
The antioxidants especially preferred in the present invention are:
• 2 mercapto benzimidazole zinc sai (VULKANOX ZMB2) BAYER® • 2-mercaptotoluylimidazole zinc salt • 2,2'-thiodiethyl bis- (3,5-diterbutyl-4-hydroxyphenyl) propionate, and • Pentaerythritol tetra bis (beta-laurylthiopropionate)
The amounts and / or proportions employed in the polymer compositions are preferably 0.25-15 phr.
The invention is described below in order to illustrate the same but of course without reducing its scope, through the following examples of preparation and application process of the polymeric insulating composition that meet the following requirements:
Formulation, Experimentation and Preparation of the Composition. All the components described above can vary widely; however, the composition object of the invention is precisely the interaction of the vinyl alkoxysilane with the inorganic filler and the mixture of polymers used during the process of mixing and / or preparing the polymer composition. The wrong dosage of silane or quantities lower than 0.5 to 5.0 phr, may be insufficient to provide surface treatment to the inorganic filler and be sufficient to provide surface treatment to the inorganic filler, and amounts above these ranges may give us undesirable effects. in the physicomechanical properties after vulcanization of the material.
The mixture can be made in an internal mixer such as the mixers: Banbury, Boiling Mixtrumat, and in continuous mixer such as: Farrel, Wemer & Pfleider and Buss. The other components of the polymer composition are also mixed in the aforementioned mixing equipment, after the first addition of silane, filler and polymers. Once all the components of the different polymeric compositions expressed in the present invention are added, intensive mixing thereof is carried out (all the components must be mixed at the same time, this has the purpose of promoting a good dispersion). The duration of mixing will depend on the degree of dispersion and the sequence of mixing used for each type of equipment. In summary, any known processing equipment can be used, the main objective is to ensure an intimate mixture of the essential components. In addition to the essential components there are also other components, such as UV stabilizing pigments and / or fungicides, these components must be selected carefully because they can interfere with the crosslinking system of the polymer composition.
The amount and / or proportion of the curing agent will depend on the degree of crosslinking that is desired and / or is according to the type of application; insofar as the crosslinking agent is in greater quantity and / or proportion, the crosslinking density will be higher and the final properties of the composition such as hardness, resistance to attack by chemicals, abrasion resistance, resistance to the oils, and the electrical properties are better. And to the extent that the amount and / or proportion of the curing agent is lower the crosslinking density will decrease and therefore the final properties will also decrease (thermal stability loss at high temperatures and / or operating temperatures of the cable) . The density of crosslinking recommended to achieve a good balance in properties will be 85% and / or higher, in practice the typical values of the crosslink density are from 85% to 95%. The way to measure the crosslink density is by means of extraction of the undissolved crosslinked polymer in a solvent used to carry out the extraction, this procedure is according to the method ASTM D 2765, Method C. The levels employed of the agents of Cured of the present invention were from 0.5 phr to 10 phr, preferable from 1 phr to 6 phr or from 2 phr to 4.5 phr. The curing agents are according to the degree of crosslinking obtained.
The quantity and / or proportion of the process additives depends on the Theological properties necessary for the good processing of the material during the mixing and extrusion of the material. The addition of these additives to the process aid should not affect the speed and degree of crosslinking of the polymer composition. This amount and / or proportion of the process aid additives will be from 0.25 phr to 8 phr.
The present invention is not limited to the use of a single type of component for the process aid, but it is possible to use a system of two and up to three types of components, these can be conjugated in forms and quantities in such a way that synergistic effects are achieved that confer excellent Theological properties. The amount and type of antioxidants used will depend basically on the application and / or operation temperatures to which the polymeric compositions will be subject. The preferred antioxidants are: zinc salt 2 mercapto benzimidazole pentaerythritol tetra bis (betalaurylthiopropionate) and 2,2'-thiodiethyl bis (3,5-ditertiary 4-hydroxyphenyl) propionate. The amounts and / or amounts used of this antioxidant system is preferably 0.25 phr at 15 phr or 1.5 ph at 12 phr. The relationship between them will be between 1: 1 to 3: 1 and 1: 1 to 2.5: 1.
by using conventional crosslinking processes as long as they do not affect the speed and degree of crosslinking and therefore the final properties.
The final result is to have polymer compositions that meet the following requirements:
• Resistance to inclined and / or vertical propagation of the flame according to ISO 6722 and RENAULT 38-05-009J respectively. • Sufficient thermal stability to withstand oven aging temperatures of 150 ° C +/- 3 ° C and 240 hours at 180 ° C. • Electrical properties for voltages less than and equal to 600 volts and voltages less than and equal to 5000 volts. • Resistance to ASTM 1 oil under the following temperature and immersion period: 136 ° C-for 48 hours. • Resistance to fluids confora to ISO 6722 and RENAULT 38-05-009J. • Polymeric compositions should not discolor and / or stain copper and should not change colors when performing the curing of the same. • The compositions must have good Theological characteristics, to achieve mixing and extrusion and these compositions at high line speeds.
A copolymer of ethylene and vinyl ester of a C 2-6 aliphatic carboxylic acid was prepared, preferably vinyl acetate (EVA) in a proportion of 3% to 90% and preferably 3 to 12% of vinyl acetate and the copolymer moiety of ethylene, being mixed in the following way:
• Mixed in a Banbury, under controlled conditions of temperature and mixing time (110 ° C to 135 ° C discharge temperature of the material with period of 3-6 minutes of mixing). The mixing period and mixing temperature are limited to the quality and degree of dispersion of the components. Once mixed the polymer compositions are laminated and granulated for extrusion.
• When the tests are made in the form of a plate, they are molded according to the sum of two 90% curing times determined in the Monsanto ODR rheometer at 180 ° C. This is to ensure that for each type of formulation expressed in the examples a minimum 85% crosslinking is obtained. The plates are molded under pressure in laboratory presses, stress tensile properties and elongation at rupture are made according to the test method ASTM D 638. The crosslink density was determined by the method ASTM D 2765, Method C.
• When the tests are done as insulation in cable, the insulation is applied in a CV Continuous Reticulation Machine which has a Royle extruder with a diameter of 65 mm and with a L / D of 15: 1 and with extrusion screws with the compression ratio from 2.5: 1 to 3.5: 1 and with the vulcanization tube length of 65 m. At the moment of the extrusion of the formulations of the examples a pack of meshes 20 mesh + 40 mesh + 60 mesh was used; The extrusion temperature profiles used are from 90 ° C to 95 ° C in the areas of the extrusion chamber and in the head and given from 100 ° C to 105 ° C respectively. The extrusion speed is 30 rpm. The insulation thicknesses are 10 mils in 20 AWG gauges.
• Once the prototype cables have been manufactured, the tension stress retention and elongation to rupture properties after aging in ho or at the following test conditions are evaluated: 3000 hours for 150 ° C +/- 3 ° C; 342 hours at 150 ° C; and 240 hours at 180 ° C ± 3 ° C.
• Electrical tests are determined in accordance with ISO-6722 and ASTM D 150.
EXAMPLE I The following formulation was prepared as described above, the mixture contains a copolymer based on a polyolefin of ethylene and vinyl acetate (12% VA and melt index of 2.5 g / lOmin) With the following formulations resistance to the vertical propagation of the flame in accordance with the RENAULT standard 38-05-0091
FR-1808 is commercially known as a retardant to the crystalline flame FR-1025 is commercially known as a retardant to the crystalline flame The sterically hindered phenol used was the propianate 2'2 thiodetií bis (3,5 diterbutil 4 hydroxyphenyl)
The composition was prepared according to the description in the summary of cable examples.
, according to the RENAULT standard 38-05009J The results obtained after the evaluation are
Feature Unit Formula 1 Formula 2 Formula Formula 4
Vertical propagation to the Do not become extinct It is extinguished Flame is extinguished according to extinguish in in in RENAULT 38-05-009J 15 seconds 4 seconds 2 seconds
The results are satisfactory and demonstrate that the halogenated flame retardant materials used are suitable to comply with the Flame Test of the RENAULT standard. The operating voltages for this type of composition are 600 volts at 500 volts according to ASTM D 150
EXAMPLE p Example I formula 3 is repeated, only the type and amount of antioxidant is modified. The antioxidant tetra [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] was used.
methane for the purpose of carrying out a comparative study to demonstrate that the antioxidant propianate 2,2'thiodietil bis (3,5-tert-butyl 4-hirophenyl) is able to withstand aging in short (240 hours) and long-term (3000 hours) Different test temperatures (150 ° C and 180 ° C).
The measured properties are: tensile stress and elongation to rupture, tension stress retention and elongation to rupture.
The composition was prepared as described in the example summary in the form of a cable. The results are expressed in the following table:
The results obtained show that the use of antioxidant propianate 2'2 thiodietil bis (terbutylthio 4 hydro phenyl) Formula 1, good thermal stability is obtained As a result it is also observed that the polymer composition of Example I does not discolor and / or stain the copper a Once the material is vulcanized, it is also observed that the original tone of the material once vulcanized does not change.
EXAMPLE IH Four comparative formulations Formula 1 of Example 1 and three others were prepared using the following polymers
1. Ethylene Vinyl Copolymer (9% VA, Fluency Index of 2.2 g / 10 min) 2. Vinyl Ethylene Combination (12% VA, Fluency Index of 2.5 g / 10 min) with an INSITE® polyolefin (index of Fluidity of 0.75 g / 10 min).
3. Vinyl Ethylene Combination (12% VA, Fluency Index 2.5 g / 10 min) with a high density polyethylene with a flow rate of 0.5 g / 10 mm needle diameter):
Polyolefin INSITE ** polyolefin manufactured under the process known commercially as INSITE patented by DOW CHEMICAL
For this type of reduced wall cable the required value is 100 cycles; according to the result obtained in the invention there is the combination of INSITE® polyolefins and high density polyethylenes, there is a substantial increase in resistance to needle abrasion. This result is not intended to limit the state of the Art of the present invention.
EXAMPLE IV Five comparative formulations Formula 1 of Example I and four others were prepared using the following polymers: 1. Combination of Vinyl Ethylene (12% VA, Fluency Index of 2.5 g / 10 min) to 26% with a polyolefin INSITEF ( Fluidity index of 0.75 g / 10 min) to 9%. . min.) to 26% with a high density polyethylene with a flow rate of 0.5 g / 10 min. to 9%. 3. Combination of Vinyl Ethylene (12% VA, Fluency Index of 2.5 g / 10 min.) To 26% with VAMAC D® 9% acrylic ethylene copolymer.
As a result of these formulations applied as insulation in cable 22 AWG type TXL according to the specification of FORD S97GG 14401 AA the following results of resistance to oil absorption are obtained:
TYPE OF OIL
ASTM I IRM-902 IRM-903 TRANSMISSION
FORMULATION 136 ° C / 48 50 ° C / 20h 50 ° C 20 fa 50 ° C / 2O H
% increase in thickness of the insulation of the cab e Formula 1 Example 1 27.8 7.8 2.2 15.8 12% VA plus 4.0S 14.2 12.3 polyethylene INSITE 12% VA plus polyethylene afte 3.2 2.22 5.5 5.4 density 12% VA plus ethylene copolymer 1.22 0.78 3.5 2.21 acrylic or Vamac De®
Polyolefin? NSIT? ® Polyolefin manufactured under the process known commercially as INSITE patented by DOW CHEMICAL Vamac D 'name commercially known as a copolymer of ethylene acrylic.
Acrylic density and copolymers shows a substantial increase in resistance to oil absorption.
EXAMPLE V Based on all the formulations of the previous examples, a global polymeric composition is obtained, with which all the synergistic effects are achieved together that confer the resistance to hot oils, to abrasion of the needle, to the propagation to the flame. vertical, and mainly to a greater stability at 150 ° C to 3000 hours.
- It is commercially known as a challenge to a critical mistress. FR-1025® is commercially known as a crystalline flame retardant. The sterically hindered phenol used was propianate 2,2'-thiodiethyl bis (3,5-diterbu-4-hydroxyphenyl). STRUKTOL TR 016 is commercially known as a mixture of metal soaps of fatty acids and with an amide STRUKTOL TR 016® commercial product of aliphatic resin The results obtained after the evaluation are as follows:
• The measured properties were; resistance to vertical propagation to the flame in accordance with the RENAULT standard 38-05-009J
• The results are good and demonstrate that the material retardant to the halogenated flame used is appropriate to comply with the Flame Test of the RENAULT standard.
• The results obtained show that with the use of the thermal stabilizers proposed in the present example good results are obtained during a prolonged exposure in the furnace of 3000 hours at 150 ° C according to the RENAULT standards 38-05-009J FORD S97GG 14401- AA. and ISO 6722 (all the compositions were extracted in thin-gauge 22 AWG wire, and were evaluated according to the aforementioned standards as cable insulation with the entire copper core). As a result it also has that the three polymer compositions of Example V do not discolor and, or stain the copper once the material is crosslinked and likewise it is observed that the original tone of the material does not change.
As a result of these formulations applied as insulation in 22 AWG cable with reduced thickness according to the specification of RENAULT 38-05- 009J the following abrasion results are obtained (7 N applied weight, and 0.45 mm needle diameter):
For this type of reduced wall cable the required value is 100 cycles; according to the result obtained in the invention the high density polyethylenes give a substantial increase in resistance to needle abrasion.
* As observed in the results obtained the inclusion of high density polyolefins with acrylic copolymers there is a substantial increase in the resistance to absorption to oils.
As a result of these formulations applied as insulation in wire 22 AWG type TXL according to the specification of FORD S97GG14401 AA the following results of resistance to oil absorption are obtained:
Having described the invention, it is considered a novelty and therefore the content is claimed in the following:
Claims (2)
- R E I V I DI C A C I O N S A polymeric composition based on crosslinkable polyolefins with high thermal coefficient of service in automotive cable which comprises a copolymer (EVA) of ethylene and vinyl ester of aliphatic carboxylic acid of 2-6 carbon atoms, in a ratio of 3% to 90 % of the vinyl ester and the rest of ethylene; the composition being characterized because it comprises a mixture of additives that increase the thermal coefficient at temperatures up to 150 ° C ± 5 ° C of service in cables and electric conductors exposed in high temperature zones of internal combustion engines and which also improve the properties of : resistance to hot oils, to abrasion, and to propagation to the vertical flame after being crosslinked said composition, being the ratio of mixtures: copolymer (EVA) up to 50 parts / 100 polymeric resin (phr), high polyethylene density up to 40 phr, copolymer of ethylene acrylate up to lOphr, halogenated compounds of octabromo tri methyl phenyl indane 0-40 phr .; (FR 1808® monomer depentabromo benzyl acrylate 0 -40 phr (FR-3025R), antimony trioxide 10 - 20 phr, magnesium hydroxide treated with alkoxysilane 0 -75 phr, silicone oil 0-3 phr, aliphatic resin STRUKTÓL TR 060 Iphr, metallic soaps of fatty acids and amides (STRUKTOL TR 016®) 0.5 phr; phenol with steric hindrance 2 phr, zinc salt 2 mercapto benzylmidazole 6 phr; coagent n, n'-m-phenylene dimaleic -, benzene 2 phr. The polymer composition of clause 1, characterized in that the copolymer (EVA) is preferably a mixture of ethylene vinyl acetate copolymer in a proportion of 3 to 45% and the remainder being ethylene with melt indices of 0.5 to 5 g /10 minutes. The polymer composition of clause 2, characterized in that the polyethylene copolymer can also be selected from: polypropylene, copolymers and terpolymer of ethylene propylene and acrylic copolymers The polymer composition of clause 1, characterized in that the halogenated compounds can also be selected from: hexabromobenzene, tetrabromobisphenol A, tetrachlorobisphenol A, tetrahydromophthalate anhydrous, hexabromo cyclodecane, octabromodiphenyl, perchloropentacyclohecane, octabromodiphenyl ether decabromodiphenyl ether, tribromo phenyl ayl ether, pentabromo ethylbenzene 2,4,6-tribromophenol, pentabromodiphenyl ether, ethylene bis (tetrabromophthalimide), anhydrous tetrachlorophthalate, poly (pentabromobenzyl) acylate, bis (dibromopropyl) ether of tetrabromobisphenol A, and Diels-Alder byproduct of hexachlorocyclopentadiene with maleic anhydride. which favor grafting in the polymer composition. The polymer composition of clause 1, characterized in that the magnesium hydroxide treated with an alkoxysilane can be selected from vinyl trimethoxyethoxysilane, phenyl tris (2-methoxyethoxy) silane, ethyl methyl tris (2-methoxyethoxy) silane, dimethyl diethoxysilane, ethyl trimethoxysilane and vinyl trimethoxysilane The polymer composition of clause 5, characterized in that vinyl trimethoxyethoxysilane and vinyl t-methoxyethoxysilane and vinyl trimethoxy silane are preferably used, wherein the proportions of the alkoxysilanes with respect to the magnesium hydroxide are in a ratio of 0.5 to 5 phr. The polymeric composition of clause 1 characterized in that the poimeric composition is crosslinked by dicumyl peroxide, 2,5- (tert-butylperoxy) -, -2,5-dimethyl hexin-3, di-tert-butylperoxide, 2,5 - (tert-butylperoxy) -2,5-dimethylhexane, and tert-butyl cumyl peroxide and preferably alpha, alpha'-bis (tert-butyl peroxide) diisopropyl benzene; with the combination of coagent compounds such as: triallyl cyanurate, triallyl isocyanurate. diallyl maleate, diallyl phthalate, pentaerythritol triacrylate, pentaerythritol tetracrylate, trimethylol propane triacrylate, tpmethylol propane, trimethacrylate, tetrethylene glycol dimethacrylate, low molecular weight polybutadiene and n, n'-m-phenylendimaleic acid (HVA-2®) in a ratio of 0.5 - 10 phr with respect to the crosslinking agent. The polymer composition of clause 1, characterized in that the process additives are fatty acids or derivatives thereof and preferably a mixture of metal soaps of fatty acids with an amide in admixture with a low molecular weight silicon oil and a Aliphatic resin wherein: The proportions employed in each system will be from fatty acid to silicone oil 1: 1 to approximately 1: 6, and preferably from fatty acid to silicone oil 1: 3. And with respect to the aliphatic resin to the fatty acid 1: 1 to about 1: 6 and preferably of hydrocarbon resin to fatty acid 1: 3. The total amount of the composition of the process additives is from 0.25 phr to 8 phr of the total poimeric composition. The polymer composition of clause 1, characterized in that the antioxidant agents used are pentaerythritol tetra bis (beta-lauryl thio propyanate) and preferably zinc salt 2 mercapto benz imidazole and propionate 2,2'-thiodiethyl bis (3,5-diterbutyl 4 hydroxyphenyl in proportions with respect to the polymer composition preferably 0.25-15 phr. The polymeric composition of clause 1, characterized in that it preferably comprises the following mixture ratio: • EVA copolymer 50 phr high density polyethylene 40 phr ethylene-acrylate copolymer 10 phr halogenated compound (FR 1808®) 40 phr antimony trioxide 20 phr , 3 phr silicon oil aliphatic resin (SYTUKTOL TR 060) I hr, 0.5 phr fatty acid metal soaps, with amide (STRUKTOL TR 016) zinc salt 2 mercaptobenzimidazole 6 phr (VULKANOX ZMB2) sterically hindered phenol 2 phr, coagent (HVA-2®) l hr, and alpha, alpha 'bis (terbutilperoxide) diisopropyl benzene 2 phr. The polymeric composition of clause 1, characterized in that it preferably comprises the following mixture ratio: • EVA 50 phr copolymer, • high density polyethylene 40 phr. • ethylene acrylate copolymer 10 phr, • halogenated compound (FR-1025 * 40 phr. • antimony trioxide 20 phr, • silicone oil 3 phr, • aliphatic resin (STRUKTOL TR 060) 1 phr, • mix of metal soaps acids l phr, fatty acids with amide • (STRUKTOL TRO 16) 0.5 phr .. • 2 2 mercaptobenzimidazo zinc salt? 6 phr, (VULKANOX ZMB2) • phenol with steric hindrance 2 phr, • coagent (HVA-2 *) 1 phr, and • alpha, alfa'bis (terbutil peroxide) 2 phr. diisopropyl benzene)
- 2. The polymer composition of clause 1, characterized in that it preferably comprises the following mixture ratio; • 50 phr EVA copolymer, • 40 phr high density polyethylene • 10 phr ethylene acrylate copolymer, • halogenated compound (FR-1808F) 20 phr, • 10 phr antimony trioxide, • magnesium hydroxide treated with 75 phr alkoxysilane, • oil silicon 3 phr, • aliphatic resin (STRUKTOL TR060) 1 phr, • mixture of metallic soaps of acids 0.5 PHR, fatty acids with amide (STRUKTOL TRO 16) • sterically hindered phenol 2 phr, • zinc salt 2 mercaptobenzimidazole 6 phr. (VULKANOX ZMB 2) coagent (HVA-2 SN) 1 phr, alpha, alpha'bis (terbutylperoxide) diisopropyl benzene 2 phr. In order to prepare composites for polyolefins with a high thermal coefficient of service up to 150 ° C, for automotive cable clauses 1 to 12, which comprises mixing an EVA copolymer, based on a copolymer of ethylene and vinyl ester of an aliphatic carboxylic acid of C 2-6 in a ratio of 3 - 90% of the vinyl ester being the ethylene moiety, characterized in that a mixture of additives is incorporated that increase the thermal coefficient of service in the conductors and electric cables that are arranged in high temperature zones in internal combustion engines, and that also improve the resistance to hot oils, abrasion and propagation of the vertical flame, where said mixing is carried out at temperatures from 110 ° C -135 ° C for periods of 3-6 minutes, said addition of active components being based on: organic charge of halogenated compounds and antimony trioxide in a ratio of 2: 1 to 5: 1, preferably 2.5: 1 to 4: 1; interaction of vinyl alkoxysilane with the charge. .organic and polymer mixture used copolymer (EVA), high density polyethylene and ethylene acrylate copolymer, in the mixture in a ratio of 0.5 to 5 phr; addition of process additives preferably aliphatic ream, silicone oil in a ratio of 0.25 phr to 8 phr; addition of antioxidant agents, preferably zinc salt 2-mercaptobenzimidazole and 2,2'-thiodiethyl propylate bis- (3,5-diterbutyl-4-hydroxyphexyl) or penfaerythritol tetra-bis (beta-lauryl thiopropylate) in a ratio of 0.25-15 phr; after the first addition of silane, filler, polymers and addition of peroxide, - ux combination with coagents of preferably n, n'-m-phenylene dimaleic in a ratio of 0.5 - 10 phr, once all the components are added intensive mixing of the composition until total dispersion; once mixed the composition is laminated and granulated for extrusion. The process of clause 13, characterized in that the halogenated inorganic filler, are brominated compounds that do not generate toxic dioxins and furans when in combustion and are preferably used: octabromotrimethylphenyl mdane with melting temperature of 240 ° C - 256 ° C (FR) -1808 *) and pentabromo benzyl acrylate monomer with a melting point of 117 ° C - 120 ° C (FR-1025®). The method of clause 13, characterized in that the polymer component (EVA) is preferably a copolymer of ethylene and vinyl acetate in a proportion preferably of 3 to 45% of the acetate, the remainder being ethylene.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0003178A BR0003178B1 (en) | 1999-10-07 | 2000-07-27 | polymer composition based on crosslinkable polyolefins with high thermal coefficient of working in automotive cable, and process of preparation of a polymer composition. |
CA 2314814 CA2314814A1 (en) | 1999-10-07 | 2000-08-02 | Polymer composition based on crosslinkable polyolefins with high service thermal coefficient in automotive cables and manufacturing process thereof |
ARP000104824 AR025663A1 (en) | 1999-10-07 | 2000-09-14 | POLYMERIC COMPOSITION BASED ON RETICULABLE POLYOLEFINS WITH ELEVATED THERMAL COEFFICIENT SERVICE IN AUTOMOTIVE CABLE AND PREPARATION PROCESS |
EP00308237A EP1092752A3 (en) | 1999-10-07 | 2000-09-20 | Polymer composition |
JP2000306041A JP2001172447A (en) | 1999-10-07 | 2000-10-05 | Polymer composition based on cross-linking polyolefin having high service thermal expansion coefficient in vehicle cable |
Publications (1)
Publication Number | Publication Date |
---|---|
MXPA99009174A true MXPA99009174A (en) | 2001-07-31 |
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