CN110770288B - 聚烯烃组合物 - Google Patents
聚烯烃组合物 Download PDFInfo
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- CN110770288B CN110770288B CN201780092267.XA CN201780092267A CN110770288B CN 110770288 B CN110770288 B CN 110770288B CN 201780092267 A CN201780092267 A CN 201780092267A CN 110770288 B CN110770288 B CN 110770288B
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- polyolefin composition
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- polyolefin
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 286
- 239000000203 mixture Substances 0.000 title claims abstract description 226
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000004132 cross linking Methods 0.000 claims description 54
- 239000011256 inorganic filler Substances 0.000 claims description 50
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 50
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 229920001684 low density polyethylene Polymers 0.000 claims description 40
- 239000004702 low-density polyethylene Substances 0.000 claims description 40
- 239000004020 conductor Substances 0.000 claims description 35
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 35
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 25
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 20
- 239000004711 α-olefin Substances 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002671 adjuvant Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000001993 dienes Chemical class 0.000 claims description 11
- 229910020447 SiO2/2 Inorganic materials 0.000 claims description 10
- 239000003063 flame retardant Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000378 calcium silicate Substances 0.000 claims description 8
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 8
- 235000012241 calcium silicate Nutrition 0.000 claims description 8
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000391 magnesium silicate Substances 0.000 claims description 8
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 8
- 235000019792 magnesium silicate Nutrition 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 235000010215 titanium dioxide Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 4
- 150000001260 acyclic compounds Chemical class 0.000 claims description 3
- 150000001923 cyclic compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims 2
- 239000000047 product Substances 0.000 description 52
- 239000004615 ingredient Substances 0.000 description 38
- 239000010410 layer Substances 0.000 description 27
- -1 cyclic siloxanes Chemical class 0.000 description 24
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- 238000007142 ring opening reaction Methods 0.000 description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 15
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000010998 test method Methods 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 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 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 229920002521 macromolecule Polymers 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 230000005012 migration Effects 0.000 description 7
- 125000005375 organosiloxane group Chemical group 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 5
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
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- 238000009413 insulation Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000007655 standard test method Methods 0.000 description 5
- BVTLTBONLZSBJC-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 BVTLTBONLZSBJC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
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- 230000002829 reductive effect Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 3
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 3
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 125000003118 aryl group Chemical group 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
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- 239000002356 single layer Substances 0.000 description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- ZBXBDQPVXIIXJS-UHFFFAOYSA-N 2,4,6,8,10-pentakis(ethenyl)-2,4,6,8,10-pentamethyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 ZBXBDQPVXIIXJS-UHFFFAOYSA-N 0.000 description 2
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 2
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- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
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- 235000006650 Syzygium cordatum Nutrition 0.000 description 2
- 240000005572 Syzygium cordatum Species 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- LAUIXFSZFKWUCT-UHFFFAOYSA-N [4-[2-(4-phosphonooxyphenyl)propan-2-yl]phenyl] dihydrogen phosphate Chemical compound C=1C=C(OP(O)(O)=O)C=CC=1C(C)(C)C1=CC=C(OP(O)(O)=O)C=C1 LAUIXFSZFKWUCT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
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- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
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- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- NZHHDFRSEQSGLN-ZRDIBKRKSA-N tris(prop-2-enyl) (e)-prop-1-ene-1,2,3-tricarboxylate Chemical compound C=CCOC(=O)C\C(C(=O)OCC=C)=C/C(=O)OCC=C NZHHDFRSEQSGLN-ZRDIBKRKSA-N 0.000 description 1
- PLCFYBDYBCOLSP-UHFFFAOYSA-N tris(prop-2-enyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound C=CCOC(=O)CC(O)(CC(=O)OCC=C)C(=O)OCC=C PLCFYBDYBCOLSP-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010618 wire wrap Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- 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
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- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
一种聚烯烃组合物,其包含聚烯烃聚合物、烯基官能的单环有机硅氧烷和有机过氧化物;和由所述聚烯烃组合物制备的产物;制备和使用所述聚烯烃组合物的方法;以及含有所述聚烯烃组合物的物品。
Description
技术领域
范围包括聚烯烃组合物、由其制备的产物、制备和使用其的方法以及含有其的物品。
相关申请的交叉引用
本申请要求于2017年6月29日提交的PCT国际专利申请号PCT/CN2017/090770的优先权的权益,并且在此将其全部内容以引用的方式并入。
背景技术
绝缘电导体通常包含被绝缘层覆盖的导电芯。导电芯可为实心的或多股的(例如,一束导线)。一些绝缘电导体还可含有一个或多个额外元件,如一个或多个半导体层和/或保护套(例如,绕线、带或护套)。实例为涂层金属导线和电力电缆,包括用于低压(“LV”,>0至<5千伏(kV))、中压(“MV”,5至<69kV)、高压(“HV”,69至230kV)和超高压(“EHV”,>230kV)输电/配电应用中的金属导线和电力电缆。电力电缆的评估可使用AEIC/ICEA标准和/或IEC测试方法。
授予B.T.MacKenzie,Jr.的US 4,005,254(“MacKenzie”)涉及用于使含乙烯的聚合物化学交联的无压固化系统,以及由此形成的产物。可固化组合物包含含乙烯的聚合物、固化剂和用四甲基四乙烯基环四硅氧烷处理的矿物填料。在制备组合物时,将聚合物、矿物填料、四甲基四乙烯基环四硅氧烷和其它添加剂如在班伯里密炼机中那样紧密地掺合。在此混配操作期间,据说四甲基四乙烯基环四硅氧烷与填料相互作用或涂布填料,并且结果称为经硅氧烷处理的填料。如果期望,可在单独的操作中用四甲基四乙烯基环四硅氧烷对矿物填料进行预处理,并且然后将经硅氧烷处理的填料与聚合物和其它添加剂掺合。实例1(0.0重量%(wt%)的四甲基四乙烯基环四硅氧烷)的MacKenzie甲苯萃取物(化合物的%)数据为11.6%,并且实例2和3(按组合物重量计各自为0.97wt%的四甲基四乙烯基环四硅氧烷)的MacKenzie甲苯萃取物数据分别为9.6%和11.8%(表I)。考虑到比较例1的可萃取物的百分比相对于实例2和3的可萃取物的百分比,本领域技术人员将认识到,实例2和3中的四甲基四乙烯基环四硅氧烷无助于含乙烯的聚合物的交联。相反,如MacKenzie所教导的,四甲基四乙烯基环四硅氧烷涂布硅酸铝填料。
授予J.M.Cogen等人的US 8,426,519 B2涉及使用经济的反应器后反应性混合例如挤出制备的硅酮-热塑性聚合物反应性共混物和共聚物产物。程序基于热塑性聚合物基质内环状硅氧烷的开环聚合。在优选模式中,热塑性聚合物为聚烯烃,任选地含有可用于与原位形成的硅酮聚合物反应的硅烷基团。所得材料提供混杂性能,可将应用范围扩展到仅由热塑性聚合物或硅酮或它们的物理共混物提供的应用范围之外。
授予Z-l Wu等人的CN104277182A以及文章《用八乙烯基多面体低聚倍半硅氧烷作为交联剂交联低密度聚乙烯(Crosslinking of low density polyethylene withOctavinyl polyhedral oligomeric silsesquioxane as the crosslinker)》,J.Wu.等人,《英国皇家化学会进展(RSC Advances)》,2014,第4卷,第44030页涉及使用八乙烯基多面体低聚倍半硅氧烷作为交联剂制备交联低密度聚乙烯的方法。
发明内容
我们认识到损害现有聚烯烃的交联和性能的问题。可将助剂与聚烯烃共混以得到具有增加的交联能力的聚烯烃组合物,但是常规助剂具有其局限性。举例来说,常规助剂在聚烯烃组合物中的溶解性或混溶性通常是有限的。这限制助剂在组合物中的最大负载水平。其还使得助剂不当地迁移到组合物的表面(例如粒料的表面),从而限制组合物的储存寿命。常规助剂还造成其它问题。举例来说,其在固化后可产生交联程度不充分的交联产物。或者,组合物可能固化得太慢而无法用于某些制造操作(例如,电力电缆制造、注塑和膜挤出)。或者,组合物可能过早固化(即,在电缆挤出、注塑和膜挤出期间容易焦化)。毫不奇怪,这些问题限制已与聚烯烃一起使用的常规助剂的结构。通常,常规助剂包含键结至两个或更多个烯系交联基团的常规子结构基团。常规子结构基团为分别包含主链或环的非环状或环状多价基团,其在主链或环中含有碳原子和任选的氮和/或氧原子,而不含硅原子。
此问题损害在较高电压下操作的电力电缆的性能。可在绝缘层的挤出期间发生焦化,并且最终导致绝缘层的失效。通过在绝缘层中使用更具弹性的材料,可延长达到这种失效的时间,并且因此提高电力输送的可靠性,并且降低维护成本。
从现有技术来看,此问题的技术解决方案并不明显。然后,通过创造性要解决的问题为发现包含聚烯烃聚合物和改进的助剂的新聚烯烃组合物,其中聚烯烃组合物以及其固化的交联产物可用作高压下的电力电缆(HV或EHV电力电缆)中的绝缘层。我们的分析表明,新助剂理想地为环状分子,其环中不含有碳或氮原子。
我们针对此问题的技术解决方案包括:包含聚烯烃聚合物和烯基官能的单环有机硅氧烷的聚烯烃组合物;由其制备的交联聚烯烃产物;制备和使用其的方法;和含有其的物品。
本发明聚烯烃组合物和产物可用于任何利用聚烯烃(包括交联聚烯烃)的应用(包括挤出物品、涂层、膜、片材和注塑物品),以及输电应用和其它不相关的应用(如容器或车辆零件)。
具体实施方式
发明内容和摘要以引用的方式并入本文。
含有聚烯烃聚合物和烯基官能的单环有机硅氧烷的本发明聚烯烃组合物可经由辐射或有机过氧化物固化(交联),而无需烯基官能的单环有机硅氧烷的开环。固化反应以使得烯基官能的单环有机硅氧烷不产生聚合硅氧烷(硅酮聚合物)的方式进行。不受理论束缚,相信聚烯烃组合物的成分经选择使得在聚烯烃组合物的固化期间,烯基官能的单环有机硅氧烷不开环得到开环硅烷醇(S-OH)官能的有机硅氧烷低聚物(线性或分支),并且因此聚合硅氧烷(硅酮聚合物)不在聚烯烃聚合物内原位形成。烯基官能的单环有机硅氧烷不可进行开环,至少部分是因为聚烯烃组合物不含有开环催化剂,并且因此因为固化反应在不存在开环催化剂的情况下进行。所排除的开环催化剂为已知的并且包括磷腈碱。磷腈碱具有核心结构P=N,其中游离N价连接到氢、烃基、-P=N或=P-N,并且游离P价连接到=N或-N。磷腈碱的实例见于US 8,426,519B2第9栏第29行至第10栏第31行中。从聚烯烃组合物中排除并且因此从由其制备的交联聚烯烃产物中排除的其它类型的开环催化剂为已知的。举例来说,参见F.O.Stark等人,《硅酮:综合有机金属化学(Silicones,ComprehensiveOrganometallic Chemistry)》,第2卷,305,培格曼出版社(Pergamon Press)(1982)。实例为强酸,如三氟甲烷磺酸和其金属盐、硫酸、过氯酸和盐酸;阳离子开环催化剂,如金属卤化物;和阴离子开环催化剂,如有机锂、碱金属氧化物和碱金属氢氧化物。在不存在开环催化剂的情况下,本发明聚烯烃组合物经历烯基官能的单环有机硅氧烷经由自由基固化而与聚烯烃聚合物交联以形成交联聚烯烃产物。本发明交联在烯基官能的单环有机硅氧烷不开环的情况下发生有益,即使在环境水分存在下。本发明交联的实施例避免磷腈碱对交联水平(交联的程度或交联度)的一种或多种有害影响。
未能预测的是,相对于比较聚烯烃组合物,含有烯基官能的单环有机硅氧烷或由其制备的本发明交联聚烯烃产物的本发明聚烯烃组合物具有至少一种改进的特性,所述比较聚烯烃组合物或含有线性乙烯基甲氧基硅氧烷均聚物(低聚物)、乙烯基、甲基硅氧烷均聚物(低聚物),或笼样乙烯基官能的倍半硅氧烷,或分别由其制备的产物。与在聚烯烃聚合物中负载常规助剂具有的特性相比,改进的特性可为在交联聚烯烃产物中实现90%交联(“T90”)的更短的时间段,如通过稍后描述的T90交联时间测试方法所测量,这指示有益地更快的固化速率;更大的最大扭矩值(“MH”),如通过T90交联时间测试方法所测量,其指示在交联聚烯烃产物中有利地更大的交联程度;在140℃下焦化时间(“ts1”)增加,如通过稍后描述的焦化时间测试方法所测量,这指示在挤出期间聚烯烃组合物对过早固化的抗性有益地增加(例如,在挤出机中而不是在挤出机后操作中固化);和/或烯基官能的单环有机硅氧烷以更大的浓度负载到聚烯烃聚合物中而不会“渗出”烯基官能的单环有机硅氧烷的能力。“渗出”如在聚烯烃组合物储存一段时间期间通过稍后描述的迁移测量测试方法或表面迁移测试方法确定,这指示烯基官能的单环有机硅氧烷(作为硅基助剂)在聚烯烃组合物的聚烯烃聚合物中的相容性和/或溶解性更大。
本发明聚烯烃组合物含有有机过氧化物作为固化剂,并且所得本发明交联聚烯烃产物通过将本发明聚烯烃组合物固化而制备并且特征可在于交联程度大于(交联数目大于)通过使含有聚烯烃和有机过氧化物、但不含式烯基官能的单环有机硅氧烷的比较聚烯烃组合物固化而制备的比较交联聚烯烃产物所能实现的交联程度(交联数目)。所得本发明交联聚烯烃产物的交联程度可大于使用常规助剂代替烯基官能的单环有机硅氧烷可实现的交联程度。可能由于烯基官能的单环有机硅氧烷在聚烯烃聚合物中的溶解性高于常规助剂在聚烯烃聚合物中的溶解性,因此聚烯烃组合物可具有较长存放期而不经历“渗出”。与使用常规助剂代替烯基官能的单环有机硅氧烷可实现的T90交联时间相比,本发明聚烯烃组合物可具有更短的T90交联时间(更快的交联)。当比较交联聚烯烃产物经配制而具有与形成剂相同数目个交联时,本发明交联聚烯烃产物的抗焦化性(例如,在140℃下的ts1)大于比较交联聚烯烃产物的抗焦化性。
下文将某些本发明实施例描述为用于容易交叉引用的编号方面。额外的实施例在本文别处描述。
方面1.一种聚烯烃组合物,其包含(A)聚烯烃聚合物,所述聚烯烃聚合物为包含以下的低密度聚乙烯(LDPE)聚合物:50至100重量百分比(wt%)的烯键式单体单元、50至0wt%的(C3-C20)α-烯烃衍生的共聚单体单元,和20至0wt%的二烯共聚单体单元,其中总重量百分比为100.00wt%;交联有效量的(B)式(I)的单环有机硅氧烷:[R1,R2SiO2/2]n (I),其中下标n为大于或等于3的整数;每个R1独立地为(C2-C4)烯基或H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、(C1-C4)烷基、苯基或R1;和(C)有机过氧化物;条件是所述聚烯烃组合物不含(即缺乏)磷腈碱。在一些方面,聚烯烃组合物不含任何开环催化剂。在一些方面,当下标n为4时,聚烯烃组合物不含有24wt%或更多的无机填料、可替代地不含有22wt%或更多的无机填料、可替代地不含有20.0wt%或更多的无机填料、可替代地不含有15wt%或更多的无机填料、可替代地不含有10wt%或更多的无机填料、可替代地不含无机填料,所述无机填料选自由以下组成的组:氧化铝、硅酸铝、硅酸钙、硅酸镁、二氧化硅、二氧化钛以及其混合物。在一些方面,n为3、4、5或6;可替代地3、4或5;可替代地5或6;可替代地3或4;可替代地3;可替代地4;可替代地5;可替代地6。
方面2.一种聚烯烃组合物,其包含(A)聚烯烃聚合物,所述聚烯烃聚合物为包含以下的低密度聚乙烯(LDPE)聚合物:50至100重量百分比(wt%)的烯键式单体单元、50至0wt%的(C3-C20)α-烯烃衍生的共聚单体单元,和20至0wt%的二烯共聚单体单元,其中总重量百分比为100.00wt%;(B)式(I)的单环有机硅氧烷:[R1,R2SiO2/2]n (I),其中下标n为大于或等于3的整数;每个R1独立地为(C2-C4)烯基或H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、(C1-C4)烷基、苯基或R1;和(C)有机过氧化物;条件是当下标n为4时,所述聚烯烃组合物不含有24wt%或更多的无机填料、可替代地不含有22wt%或更多的无机填料、可替代地不含有20.0wt%或更多的无机填料、可替代地不含有15wt%或更多的无机填料、可替代地不含有10wt%或更多的无机填料、可替代地不含无机填料,所述无机填料选自由以下组成的组:氧化铝、硅酸铝、硅酸钙、硅酸镁、二氧化硅、二氧化钛以及其混合物;并且条件是所述聚烯烃组合物不含磷腈碱。在一些方面,聚烯烃组合物不含任何开环催化剂。在一些方面,n为3、4、5或6;可替代地3、4或5;可替代地5或6;可替代地3或4;可替代地3;可替代地4;可替代地5;可替代地6。
方面3.根据方面1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(i)至(x)中的任一项描述:(i)每个R1独立地为(C2-C3)烯基;并且每个R2独立地为H、(C1-C2)烷基或(C2-C3)烯基;(ii)每个R1为乙烯基;并且每个R2独立地为(C1-C2)烷基;(iii)每个R1为乙烯基;并且每个R2为甲基;(iv)每个R1为烯丙基;并且每个R2独立地为(C1-C2)烷基;(v)每个R1为烯丙基;并且每个R2为甲基;(vi)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、(C1-C2)烷基或(C2-C3)烯基;(vii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H并且下标m为3;并且每个R2独立地为(C1-C2)烷基;(viii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为甲基,并且下标m为3;并且每个R2独立地为(C1-C2)烷基;(ix)所述聚烯烃组合物不含有24wt%或更多的无机填料、可替代地不含有22wt%或更多的无机填料、可替代地不含有20.0wt%或更多的无机填料、可替代地不含有15wt%或更多的无机填料、可替代地不含有10wt%或更多的无机填料、可替代地不含无机填料,所述无机填料选自由以下组成的组:氧化铝、硅酸铝、硅酸钙、硅酸镁、二氧化硅、二氧化钛以及其混合物;和(x)限制(ix)与限制(i)至(viii)中的任一项的组合。
方面4.根据方面1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(i)至(x)中的任一项描述:(i)每个R1独立地为(C2-C3)烯基;并且每个R2独立地为H、(C1-C2)烷基或(C2-C3)烯基;(ii)每个R1为乙烯基;并且每个R2独立地为(C1-C2)烷基;(iii)每个R1为乙烯基;并且每个R2为甲基;(iv)每个R1为烯丙基;并且每个R2独立地为(C1-C2)烷基;(v)每个R1为烯丙基;并且每个R2为甲基;(vi)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、(C1-C2)烷基或(C2-C3)烯基;(vii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H并且下标m为3;并且每个R2独立地为(C1-C2)烷基;(viii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为甲基,并且下标m为3;并且每个R2独立地为(C1-C2)烷基;(ix)所述聚烯烃组合物不含有24wt%或更多的无机填料、可替代地不含有22wt%或更多的无机填料、可替代地不含有20.0wt%或更多的无机填料、可替代地不含有15wt%或更多的无机填料、可替代地不含有10wt%或更多的无机填料、可替代地不含任何无机填料;和(x)限制(ix)与限制(i)至(viii)中的任一项的组合。
方面5.根据方面1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(i)至(x)中的任一项描述:(i)每个R1独立地为(C2-C3)烯基;并且每个R2独立地为H、(C1-C2)烷基或(C2-C3)烯基;(ii)每个R1为乙烯基;并且每个R2独立地为(C1-C2)烷基;(iii)每个R1为乙烯基;并且每个R2为甲基;(iv)每个R1为烯丙基;并且每个R2独立地为(C1-C2)烷基;(v)每个R1为烯丙基;并且每个R2为甲基;(vi)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、(C1-C2)烷基或(C2-C3)烯基;(vii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H并且下标m为3;并且每个R2独立地为(C1-C2)烷基;(viii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为甲基,并且下标m为3;并且每个R2独立地为(C1-C2)烷基;(ix)所述聚烯烃组合物不含有24wt%或更多的无机填料、可替代地不含有22wt%或更多的无机填料、可替代地不含有20.0wt%或更多的无机填料、可替代地不含有15wt%或更多的无机填料、可替代地不含有10wt%或更多的无机填料、可替代地不含无机填料,所述无机填料选自由以下组成的组:氧化铝、硅酸铝、硅酸钙、硅酸镁、二氧化硅、二氧化钛以及其混合物;和(x)限制(ix)与限制(i)至(viii)中的任一项的组合。
方面6.根据方面1至5中任一项所述的聚烯烃组合物,所述聚烯烃组合物通过限制(i)至(vii)中的任一项描述:(i)所述(A)聚烯烃聚合物的特征在于密度为0.86至0.97克/立方厘米(g/cm3),如通过ASTM D792-13的方法B在2-丙醇中所测量;(ii)所述(A)聚烯烃聚合物为所述聚烯烃组合物的重量的80至99.89重量百分比(wt%);(iii)所述(B)式(I)的单环有机硅氧烷为聚烯烃组合物的0.1至3wt%;和所述(C)有机过氧化物为所述聚烯烃组合物的0.01至4.5wt%;(iv)(i)和(ii)两者;(v)(i)和(iii)两者;(vi)(ii)和(iii)两者;和(vii)(i)、(ii)和(iii)中的每一个。
方面7.根据方面1至6中任一项所述的聚烯烃组合物,其另外包含选自由以下组成的组的至少一种添加剂:(D)常规助剂;(E)抗氧化剂;(F)填料;(G)阻燃剂;(H)受阻胺稳定剂;(I)抗树剂;(J)甲基自由基清除剂;(K)防焦剂、(L)成核剂和(M)炭黑;条件是所述至少一种添加剂的总量为所述聚烯烃组合物的>0至70wt%、可替代地>0至60wt%、可替代地>0至40wt%、可替代地>0至20wt%,并且条件是所述(F)填料不包括任何省略的填料。在一些方面,聚烯烃组合物另外包含(E)抗氧化剂;可替代地(E)抗氧化剂和(H)受阻胺稳定剂。
方面8.一种制备聚烯烃组合物的方法,所述方法包含将以下混合在一起以制备根据方面1至6中任一项所述的聚烯烃组合物:(A)聚烯烃聚合物,所述聚烯烃聚合物为包含以下的低密度聚乙烯(LDPE)聚合物:50至100重量百分比(wt%)的烯键式单体单元、50至0wt%的(C3-C20)α-烯烃衍生的共聚单体单元,和20至0wt%的二烯共聚单体单元,其中总重量百分比为100.00wt%;(B)式(I)的单环有机硅氧烷:[R1,R2SiO2/2]n (I),和(C)有机过氧化物。下标n和基团R1和R2如方面1至5中任一项所定义。(A)聚烯烃聚合物如方面1、2和6中任一项所定义。方法可另外包含将方面7中所定义的添加剂中的至少一种与成分(A)、(B)和(C)混合以制备方面7的聚烯烃组合物。
方面9.一种将根据方面1至7中任一项所述的聚烯烃组合物自由基固化以制备交联聚烯烃产物的方法,所述方法包含在固化有效温度下加热所述聚烯烃组合物,其方式为以便使(A)聚烯烃聚合物与(B)式(I)的单环有机硅氧烷反应,从而制备交联聚烯烃产物。在一些方面,聚烯烃组合物和交联聚烯烃产物不含磷腈碱,可替代地不含任何开环催化剂。在一些方面,聚烯烃组合物为方面1至6中任一项的聚烯烃组合物。交联有效量的(B)和(C)有机过氧化物与固化有效温度以及任何其它期望的反应条件(例如压力或惰性气体气氛)的组合足以在这种情况下使聚烯烃组合物固化和制备交联聚烯烃产物。
方面10.一种交联聚烯烃产物,其通过根据方面9所述的固化方法制备。
方面11.一种制品,其包含成型形式的根据方面1至7中任一项所述的聚烯烃组合物或根据方面10所述的交联聚烯烃产物。在一些方面,制品选自:涂层、膜、片材、挤出物品和注塑物品。例如,涂层导体、用于传输电力或电信的导线和电缆的涂层、农用膜、食品包装、服装袋、杂货袋、重型麻袋、工业薄板、托盘和收缩包装、袋子、桶、冷冻容器、盖子、玩具。
方面12.一种涂层导体,其包含导电芯和至少部分地覆盖所述导电芯的绝缘层,其中所述绝缘层的至少一部分包含根据方面1至7中任一项所述的聚烯烃组合物或根据方面10所述的交联聚烯烃产物。导电芯的实施例可为具有近端和远端的导线,其中至少一个可不含绝缘层。
方面13.一种传输电的方法,所述方法包含在根据方面12所述的涂层导体的导电芯上施加电压,以便产生穿过所述导电芯的电流。导电芯可为具有近端和远端的导线,并且电流可从导线的一端流向另一端。
术语“助剂”意指增强交联的化合物,即固化助剂。“常规助剂”为增强交联并且在其各自的主链或环亚结构中含有碳原子的非环状或环状化合物。因此,常规助剂的主链或环亚结构为基于碳的(基于碳的亚结构)。相反,基于硅的助剂意指增强交联并且在其各自的主链或环亚结构中含有硅原子的非环状或环状化合物。(B)式(I)的单环有机硅氧烷为环状硅基助剂。
术语“固化”和“交联”在本文中可互换地使用,意指在不开环聚合的情况下形成交联产物(网络聚合物)。
表述“固化有效温度”为足以引发(C)有机过氧化物分解以便成为成分(A)和(B)之间的(自由基)反应的热能的程度或度。
术语“含乙烯的聚合物”意指含有衍生自H2C=CH2的重复单元的大分子。
术语“(甲基)丙烯酸酯”包括丙烯酸酯、甲基丙烯酸酯以及其组合。(甲基)丙烯酸酯可为未经取代的。
如本文所用,术语“开环催化剂”意指引发环状硅氧烷单体的开环聚合反应和/或增强环状硅氧烷单体的开环聚合反应的速率的物质。
如本文所用,术语“开环聚合”为一种类型的链增长聚合反应,其中聚合物链的反应性末端使环状单体的环打开而得到较长聚合物链。
聚烯烃组合物:单相或多相、均匀或不均匀、连续相或不连续相、可交联材料,其含有由衍生自一种或多种含碳-碳双键的单体的重复单元构成的大分子和烯基官能的单环有机硅氧烷的分子。在一些方面,聚烯烃组合物可另外含有一种、两种或更多种任选的配料或添加剂。聚烯烃组合物的重量为100.00wt%。
聚烯烃组合物可通过多种不同方式来制备。在一些方面,聚烯烃组合物可通过将(A)聚烯烃聚合物的熔体与(B)式(I)的单环有机硅氧烷和(C)有机过氧化物,以及任何任选的成分(例如,成分(D)至(M)中的任何零种、一种或多种)混合来制备,以得到作为成分(A)、(B)、(C)和任何任选的成分的掺合物的聚烯烃组合物。混合可包含混配、捏合或挤出。为了促进混合,可在(A)的一部分中以添加剂母料的形式提供一种或多种成分(例如,(B)、添加剂(C)、(D)、(E)等)。
在另一方面,聚烯烃组合物可通过使(B)式(I)的单环有机硅氧烷和任何任选的成分(例如,(D)抗氧化剂)中的任选的零种、一种或多种与未熔融形式的(A)聚烯烃聚合物接触来制备,以得到作为成分(A)、(B)和任何任选的成分的掺合物的聚烯烃组合物。接触可包含浸泡、吸收或注射。成分(B)和一种或多种任何任选的成分可通过混配、挤出、吸收、注射、捏合或浸泡来独立地组合。混合或接触可在约20℃至100℃的温度下进行0.1至100小时,例如在60℃至80℃下进行0.1至24小时。可使用更高的温度进行混合或接触,条件是(C)有机过氧化物不经受更高的温度。此后,如果需要,那么可将掺合物冷却至低于过氧化物分解温度的温度,然后与(C)有机过氧化物混合或接触。如果需要,那么可将聚烯烃组合物冷却至储存温度(例如23℃),并且储存1小时、1周、1个月或更长的时间段。
聚烯烃组合物可制备为单部分配制物,可替代地多部分配制物,如双部分配制物,可替代地三部分配制物。没有内在的原因为什么这些配制物的一部分或多个部分不可包括成分的任何组合。
成分(A)聚烯烃聚合物:由烯烃单体和任选的一种或多种烯烃官能的共聚单体构成的重复单元构成的可交联大分子(其中大分子具有基本上由碳原子组成或由碳原子组成的主链),或这类可交联大分子的集合(其当与成分(B)交联时产生网络结构)。(A)可为含有衍生自相同单体的重复单元的均聚物,或含有衍生自单体的重复单元和衍生自不同于所述单体的共聚单体的重复单元的互聚物,也称为共聚物。互聚物包括二元共聚物、三元共聚物等。在一些方面,(A)不含硅原子。
(A)聚烯烃聚合物可为含有99至100wt%的烯键式单体单元的聚乙烯均聚物。聚乙烯均聚物可为通过配位聚合而制备的高密度聚乙烯(HDPE)均聚物或通过自由基聚合而制备的低密度聚乙烯(LDPE)均聚物。
可替代地,(A)聚烯烃聚合物可为含有50至〈100wt%的烯键式单体单元和50至0wt%的(C3-C20)α-烯烃衍生的共聚单体单元的乙烯/α-烯烃共聚物。(A)乙烯/α-烯烃共聚物的乙烯/α-烯烃共聚物实施例可为线性低密度聚乙烯(LLDPE)、中密度聚乙烯(MDPE)或高密度聚乙烯(HDPE)。可替代地,聚烯烃聚合物可为低密度聚乙烯(LDPE)。按全部互聚物重量计,乙烯/α-烯烃(“α-烯烃”)互聚物的α-烯烃含量为至少1wt%、至少5wt%、至少10wt%、至少15wt%、至少20wt%或至少25wt%。按全部互聚物重量计,这些互聚物的α-烯烃含量可小于50wt%、小于45wt%、小于40wt%或小于35wt%。说明性乙烯/α-烯烃互聚物为乙烯/丙烯;乙烯/1-丁烯;乙烯/1-己烯;乙烯/1-辛烯;含有20至1wt%的二烯共聚单体单元的乙烯/二烯;乙烯/丙烯/1-辛烯;乙烯/丙烯/1-丁烯;乙烯/1-丁烯/1-辛烯;含有50至100wt%的乙烯单体单元、49至>0wt%的丙烯共聚单体单元和20至1wt%的二烯共聚单体单元的乙烯/丙烯/二烯(EPDM)。在乙烯/二烯共聚物中或在EPDM中用于制备二烯共聚单体单元的二烯可独立地为1,3-丁二烯、1,5-己二烯、1,7-辛二烯、亚乙基降冰片烯、二环戊二烯、乙烯基降冰片烯或其任何两种或更多种的组合。
乙烯/α-烯烃共聚物的(C3-C20)α-烯烃和(A)聚烯烃聚合物的聚(C3-C20)α-烯烃聚合物方面可为式(I)的化合物:H2C=C(H)-R (I),其中R为直链(C1-C18)烷基。(C1-C18)烷基为具有1至18个碳原子的一价未经取代的饱和烃。R的实例为甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基和十八烷基。在一些实施例中,(C3-C20)α-烯烃为1-丙烯、1-丁烯、1-己烯或1-辛烯;可替代地1-丁烯、1-己烯或1-辛烯;可替代地1-丁烯或1-己烯;可替代地1-丁烯或1-辛烯;可替代地1-己烯或1-辛烯;可替代地1-丁烯;可替代地1-己烯;可替代地1-辛烯;可替代地1-丁烯、1-己烯和1-辛烯中任何两种的组合。可替代地,α-烯烃可具有环状结构,如环己烷或环戊烷,产生如3-环己基-1-丙烯(烯丙基环己烷)和乙烯基环己烷的α-烯烃。(C3-C20)α-烯烃可与乙烯单体一起用作共聚单体。
可替代地,(A)聚烯烃聚合物可为具有至少一个选自丙烯酸酯、甲基丙烯酸酯和三烷氧基甲硅烷基的接枝官能团的聚烯烃。
(A)聚烯烃聚合物可为前述聚合物和共聚物中的两种或更多种的共混物或组合。
(A)聚烯烃聚合物可为两种或更多种不同聚烯烃聚合物的共混物或与两种或更多种不同催化剂的聚合反应的反应器产物。(A)聚烯烃聚合物可在两个或更多个反应器中制备,如来自陶氏化学公司(The Dow Chemical Company)的ELITETM聚合物。
(A)聚烯烃聚合物可通过任何合适的方法制备,其中许多为本领域众所周知的。用于生产聚烯烃聚合物的任何常规的或以后发现的生产方法均可用于制备(A)。通常,生产方法包含一个或多个聚合反应。举例来说,LDPE可使用高压聚合方法来制备。可替代地,LDPE可使用配位聚合方法来制备,所述配位聚合方法使用一种或多种聚合催化剂,如齐格勒-纳塔催化剂、氧化铬、茂金属、后茂金属催化剂进行。合适的温度为0℃至250℃,或30℃或200℃。合适的压力为大气压(101kPa)至10,000个大气压(大约1,013兆帕(“MPa”))。在大多数聚合反应中,采用的催化剂与可聚合烯烃的摩尔比为10-12:1至10-1:1,或10-9:1至10-5:1。
(A)聚烯烃聚合物在聚烯烃组合物中的量可为40至99.99wt%、可替代地55至99.00wt%、可替代地70至98wt%、可替代地80至97wt%;所有这些均按聚烯烃组合物的重量计。
成分(B)式(I)的单环有机硅氧烷:含有由硅和氧原子按照交替排列布置而构成的单环亚结构;和不饱和有机基团;以及任选的H、饱和或芳香族取代基的分子;其中存在至少两个不饱和有机基团并且环亚结构中的至少两个硅原子各自与至少一个不饱和有机基团键结并且其中在不饱和有机基团和氧原子占据之后,硅原子的任何剩余价键结至H、饱和或芳香族取代基;或这类分子的集合。成分(B)可为单环有机硅氧烷,所述单环有机硅氧烷由6元环(n=3)、8元环(n=4)、10元环(n=5)或12元环(n=6)构成。环亚结构由式(I)的单元构成:[R1,R2SiO2/2]n (I),其中下标n、R1和R2如先前所定义。在每个[R1,R2SiO2/2]单元中,其R1和R2基团键结至其硅原子。单元可使用常规的有机硅氧烷速记符号简单地表示为DR1,R2,使得式(I)变成[DR1,R2]n。R1和R2可相同,可替代地不同。
在(B)式(I)的单环有机硅氧烷的一些方面,R1为乙烯基并且R2为乙基,并且(B)为DVi,Et,其中Vi为乙烯基并且Et为乙基;可替代地R1为烯丙基并且R2为乙基,并且(B)为D烯丙基,Et;可替代地R1为丁烯基(H2C=C(H)CH2CH2-)并且R2为乙基,并且(B)是D丁烯基,Et。在一些方面,R1为乙烯基并且R2为乙烯基,并且(B)为DVi,Vi;可替代地R1为烯丙基并且R2为烯丙基,并且(B)为D烯丙基,烯丙基;可替代地R1为丁烯基(H2C=C(H)CH2CH2-)并且R2为丁烯基,并且(B)为D丁烯基,丁烯基。在一些方面,R1为乙烯基并且R2为苯基,并且(B)为DVi.Ph,其中Ph为苯基;可替代地R1为烯丙基并且R2为苯基,并且(B)为D烯丙基.Ph;可替代地R1为丁烯基(H2C=C(H)CH2CH2-)并且R2为苯基,并且(B)为D丁烯基,Ph。当R2为甲基(CH3)时,单元可更简单地表示为DR1,使得式(I)变成[DR1]n。在一些方面,R1为乙烯基并且R2为甲基,并且(B)为DVi;可替代地R1为烯丙基并且R2为甲基,并且(B)为D烯丙基;可替代地R1为丁烯基(H2C=C(H)CH2CH2-)并且R2为甲基,并且(B)为D丁烯基。在一些实施例中,(B)为2,4,6-三甲基-2,4,6-三乙烯基-环三硅氧烷,“(DVi)3”(CAS号3901-77-7);2,4,6,8-四甲基-2,4,6,8-四乙烯基-环四硅氧烷,“(DVi)4”(CAS号2554-06-5);或其组合。
在(B)式(I)的单环有机硅氧烷的一些方面,每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a和下标m如先前所定义。在一些方面,R1a为H,可替代地R1a为甲基。在一些方面,下标m为1、2或3;可替代地m为2、3或4;可替代地m为2或3;可替代地m为1;可替代地m为2;可替代地m为3;可替代地m为4。在一些方面,每个R2独立地为(C1-C2)烷基或(C2-C3)烯基;可替代地每个R2独立地为(C1-C2)烷基;可替代地每个R2独立地为甲基。
聚烯烃组合物中成分(B)式(I)的单环有机硅氧烷的量可为0.01至50wt%、可替代地0.1至25wt%、可替代地1.00至20wt%、可替代地1.05至15wt%、可替代地0.01至5wt%、可替代地0.05至4.0wt%、可替代地0.1至3wt%、可替代地0.10至2.0wt%、可替代地0.20至1.0wt%;所有这些均按聚烯烃组合物的重量计。
聚烯烃组合物中成分(B)式(I)的单环有机硅氧烷的量可为交联有效量。术语“交联有效量”意指在以下情况下足以使得聚烯烃大分子能够经由衍生自(B)的多价交联剂基团交联的量(以上所述的wt%)。情况可包括(B)的负载水平(wt%)、(C)有机过氧化物的负载水平(wt%)。与不含(B)式(I)的单环有机硅氧烷的比较组合物相比,在(C)有机过氧化物的特定负载水平(wt%)下,交联有效量的(B)式(I)的单环有机硅氧烷给出更大程度的交联。情况还可取决于存在于聚烯烃组合物中的(如果存在的话)任何任选的添加剂(如(E)抗氧化剂、(F)填料和/或(G)阻燃剂)的总量。为了确定聚烯烃组合物的特定实施例的交联有效量,聚烯烃组合物中(B)式(I)的单环有机硅氧烷的量最初可小于交联有效量。此后,(B)的量以增量增加(例如,每次增加一倍),直到达到这种情况下的交联效应量。
聚烯烃组合物中成分(B)式(I)的单环有机硅氧烷的交联有效量可为0.01至50wt%、可替代地0.1至25wt%、可替代地1.00至20wt%、可替代地1.05至15wt%、可替代地0.01至5wt%、可替代地0.050至4.0wt%、可替代地0.10至2.0wt%、可替代地0.20至1.0wt%;所有这些均按不含填料的聚烯烃组合物的重量计。聚烯烃组合物中成分(B)式(I)的单环有机硅氧烷的交联有效量可根据以上所述的情况而变化。举例来说,在含有(F)填料的聚烯烃组合物的实施例中(B)的交联有效量可高于在不含(F)填料的聚烯烃组合物的实施例中(B)的交联有效量。
关于确定成分(B)的交联有效量,交联的存在可通过使用动模流变仪(MDR)增加扭矩来检测。在一些方面,交联的存在可检测为溶剂萃取的百分比(Ext%)。Ext%=W1/Wo*100%,其中W1为萃取后的重量,Wo为萃取前的原始重量,/指示除法,并且*指示乘法。通过碳-13或硅-29核磁共振(13C-NMR光谱和/或29Si-NMR)光谱可检测在交联聚烯烃产物中由于与(A)聚烯烃聚合物的偶联而不存在或降低水平的(B)的不饱和有机基团(例如,R1)的碳-碳双键。
成分(C)有机过氧化物:含有碳原子、氢原子和两个或更多个氧原子,并且具有至少一个-O-O-基团的分子,条件是当存在多于一个-O-O-基团时,每个-O-O-基团经由一个或多个碳原子间接键结至另一个-O-O-基团,或这类分子的集合。可将(C)有机过氧化物添加到聚烯烃组合物中用于固化,包含将包含成分(A)、(B)和(C)的聚烯烃组合物加热至等于或高于(C)有机过氧化物的分解温度的温度。(C)有机过氧化物可为式RO-O-O-RO的单过氧化物,其中每个RO独立地为(C1-C20)烷基或(C6-C20)芳基。每个(C1-C20)烷基独立地为未经取代的或经1或2个(C6-C12)芳基取代。每个(C6-C20)芳基为未经取代的或经1至4个(C1-C10)烷基取代。可替代地,(C)可为式RO-O-O-R-O-O-RO的二过氧化物,其中R为二价烃基,如(C2-C10)亚烷基、(C3-C10)环亚烷基或亚苯基,并且每个RO如上文所定义。(C)有机过氧化物可为双(1,1-二甲基乙基)过氧化物;双(1,1-二甲基丙基)过氧化物;2,5-二甲基-2,5-双(1,1-二甲基乙基过氧)己烷;2,5-二甲基-2,5-双(1,1-二甲基乙基过氧)己炔;4,4-双(1,1-二甲基乙基过氧)戊酸;丁酯;1,1-双(1,1-二甲基乙基过氧)-3,3,5-三甲基环己烷;过氧化苯甲酰;过氧化苯甲酸叔丁酯;二-叔戊基过氧化物(“DTAP”);双(α-叔丁基-过氧异丙基)苯(“BIPB”);异丙基枯基叔丁基过氧化物;叔丁基枯基过氧化物;二-叔丁基过氧化物;2,5-双(叔丁基过氧)-2,5-二甲基己烷;2,5-双(叔丁基过氧)-2,5-二甲基己炔-3,1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷;异丙基枯基枯基过氧化物;4,4-二(叔丁基过氧)戊酸丁酯;或二(异丙基枯基)过氧化物;或二枯基过氧化物。(C)有机过氧化物可为二枯基过氧化物。在一些方面,仅使用两种或更多种(C)有机过氧化物的共混物,例如,叔丁基枯基过氧化物和双(叔丁基过氧异丙基)苯的20:80(wt/wt)共混物(例如,LUPEROX D446B,其可从阿科玛(Arkema)商购)。在一些方面,至少一种(可替代地)每种(C)有机过氧化物含有一个-O-O-基团。(C)有机过氧化物可为聚烯烃组合物的0.01至4.5wt%、可替代地0.05至2wt%、可替代地0.10至2.0wt%、可替代地0.2至0.8wt%。
任选的成分(D)常规助剂:含有主链或环亚结构以及与其键结的一个、可替代地两种或更多种丙烯基、丙烯酸酯和/或乙烯基的分子,其中亚结构由碳原子和任选的氮原子构成,或这类分子的集合。(D)常规助剂不含硅原子。(D)常规助剂可为如通过以下限制(i)至(iv)中的任一个描述的丙烯基官能的常规助剂:(i)(D)为2-烯丙基苯基烯丙基醚;4-异丙烯基-2,6-二甲基苯基烯丙基醚;2,6-二甲基-4-烯丙基苯基烯丙基醚;2-甲氧基-4-烯丙基苯基烯丙基醚;2,2'-二烯丙基双酚A;O,O'-二烯丙基双酚A;或四甲基二烯丙基双酚A;(ii)(D)为2,4-二苯基-4-甲基-1-戊烯或1,3-二异丙烯基苯;(iii)(D)为异氰脲酸三烯丙酯(“TAIC”);氰脲酸三烯丙酯(“TAC”);偏苯三酸三烯丙酯(“TATM”);N,N,N',N',N″,N″-六烯丙基-1,3,5-三嗪-2,4,6-三胺(“HATATA”;也称为N2,N2,N4,N4,N6,N6-六烯丙基-1,3,5-三嗪-2,4,6-三胺);原甲酸三烯丙酯;季戊四醇三烯丙基醚;柠檬酸三烯丙酯;或乌头酸三烯丙酯;(iv)(D)为(i)中的丙烯基官能助剂中的任两种的混合物。可替代地,(D)可为选自以下的丙烯酸酯官能的常规助剂:三羟甲基丙烷三丙烯酸酯(“TMPTA”)、三羟甲基丙烷三甲基丙烯酸酯(“TMPTMA”)、乙氧基化双酚A二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、三(2-羟乙基)异氰脲酸酯三丙烯酸酯和丙氧基化甘油三丙烯酸酯。可替代地,(D)可为选自以下的乙烯基官能的常规助剂:具有至少50wt%的1,2-乙烯基含量的聚丁二烯和三乙烯基环己烷(“TVCH”)。可替代地,(D)可为在US 5,346,961或US 4,018,852中描述的常规助剂。可替代地,(D)可为前述常规助剂的组合或其中的任何两种或更多种。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(D)。当存在时,(D)常规助剂可为聚烯烃组合物的0.01至4.5wt%、可替代地0.05至2wt%、可替代地0.1至1wt%、可替代地0.2至0.5wt%。
任选的成分(E)抗氧化剂:抑制氧化的有机分子,或这类分子的集合。(E)抗氧化剂用以向聚烯烃组合物和/或交联聚烯烃产物提供抗氧化特性。合适的(E)的实例为双(4-(1-甲基-1-苯基乙基)苯基)胺(例如,NAUGARD 445);2,2'-亚甲基-双(4-甲基-6-叔丁基苯酚)(例如,VANOX MBPC);2,2'-硫代双(2-叔丁基-5-甲基苯酚(CAS号90-66-4);4,4'-硫代双(2-叔丁基-5-甲基苯酚)(也称为4,4'-硫代双(6-叔丁基-间甲酚),CAS号96-69-5,商业上的LOWINOX TBM-6);2,2'-硫代双(6-叔丁基-4-甲基苯酚(CAS号90-66-4,商业上的LOWINOXTBP-6);三[(4-叔丁基-3-羟基-2,6-二甲基苯基)甲基]-1,3,5-三嗪-2,4,6-三酮(例如,CYANOX 1790);季戊四醇四(3-(3,5-双(1,1-二甲基乙基)-4-羟基苯基)丙酸酯(例如,IRGANOX 1010,CAS号6683-19-8);3,5-双(1,1-二甲基乙基)-4-羟基苯丙酸2,2'-硫代二乙二醇酯(例如,IRGANOX 1035,CAS号41484-35-9);硫代二丙酸二硬脂酯(“DSTDP”);硫代二丙酸二月桂酯(例如,IRGANOX PS 800);丙酸十八烷基3-(3,5-二-叔丁基-4-羟基苯基)酯(例如,IRGANOX 1076);2,4-双(十二基硫基甲基)-6-甲基苯酚(IRGANOX 1726);4,6-双(辛基硫基甲基)-邻-甲酚(例如,IRGANOX 1520);和2',3-双、[[3-[3,5-二叔丁基-4-羟基苯基]丙酰基]]丙酰肼(IRGANOX 1024)。在一些方面,(E)为4,4'-硫代双(2-叔丁基-5-甲基苯酚)(也称为4,4'-硫代双(6-叔丁基-间甲酚);2,2'-硫代双(6-叔丁基-4-甲基苯酚;三[(4-叔丁基-3-羟基-2,6-二甲基苯基)甲基]-1,3,5-三嗪-2,4,6-三酮;硫代二丙酸二硬脂酯;或硫代二丙酸二月桂酯;或其任何两种或更多种的组合。组合可为三[(4-叔丁基-3-羟基-2,6-二甲基苯基)甲基]-1,3,5-三嗪-2,4,6-三酮和硫代二丙酸二硬脂酯。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(E)。当存在时,(E)抗氧化剂可为聚烯烃组合物的0.01至1.5wt%、可替代地0.05至1.2wt%、可替代地0.1至1.0wt%。
任选的成分(F)填料:细分的颗粒状固体或凝胶,其在主体材料中占据空间并且任选地影响主体材料的功能。(F)填料可为煅烧粘土、有机粘土或疏水化的热解法二氧化硅,如可以商品名CAB-O-SIL从卡博特公司(Cabot Corporation)商购的那些。(F)填料可具有阻燃效果。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(F)。当存在时,(F)填料可为聚烯烃组合物的1至40wt%、可替代地2至30wt%、可替代地5至20wt%。
关于(F)填料,在一些方面,聚烯烃组合物不含有20wt%或更多的无机填料、可替代地不含有15wt%或更多的无机填料、可替代地不含有10wt%或更多的无机填料、可替代地不含无机填料,所述无机填料选自由以下组成的组:氧化铝、硅酸铝、硅酸钙、硅酸镁、二氧化硅、二氧化钛以及其混合物。在一些方面,聚烯烃组合物不含有20wt%或更多的无机填料、可替代地不含有15wt%或更多的无机填料、可替代地不含有10wt%或更多的无机填料、可替代地不含任何无机填料,所述无机填料选自由以下组成的组:含Al固体、含Ca固体、含Mg固体、含Si固体、含Ti固体以及其混合物。在一些方面,聚烯烃组合物不含倍半硅氧烷,可替代地除了成分(B)之外,不含任何硅氧烷。在一些方面,聚烯烃组合物不含倍半氧硅烷和上述群组的无机填料中的任一种。为了避免疑问,术语“无机填料”不包括炭黑。
任选的成分(G)阻燃剂:抑制燃烧的分子或物质,或这类分子的集合。(G)可为卤化或不含卤素的化合物。(G)卤化(G)阻燃剂的实例为有机氯化物和有机溴化物,有机氯化物的实例为氯菌酸衍生物和氯化石蜡。有机溴化物的实例为十溴二苯醚、十溴二苯乙烷、聚合溴化化合物如溴化聚苯乙烯、溴化碳酸酯低聚物、溴化环氧低聚物、四溴邻苯二甲酸酐、四溴双酚A和六溴环十二烷。通常,卤化(G)阻燃剂结合增效剂一起使用以提高它们的效率。增效剂可为三氧化锑。不含卤素的(G)阻燃剂的实例为无机矿物、有机氮膨胀化合物和磷基膨胀化合物。无机矿物的实例为氢氧化铝和氢氧化镁。磷基膨胀化合物的实例为有机膦酸、膦酸酯、亚膦酸酯、亚膦酸二酯、次膦酸酯、膦氧化物、膦、亚磷酸盐、磷酸盐、氯化磷腈、磷酯酰胺、磷酸酰胺、膦酸酰胺、次膦酸酰胺、三聚氰胺和三聚氰胺衍生物,包括三聚氰胺多磷酸盐、三聚氰胺焦磷酸盐和三聚氰胺氰尿酸盐,以及这些材料中的两种或更多种的混合物。实例包括磷酸苯基双十二烷基酯、磷酸苯基双新戊基酯、磷酸氢苯基乙烯酯、磷酸苯基-双-3,5,5'-三甲基己基酯)、磷酸乙基二苯酯、二(对甲苯基)磷酸2-乙基己酯、磷酸氢二苯酯、磷酸双(2-乙基-己基)对甲苯酯、磷酸三甲苯酯、磷酸双(2-乙基己基)-苯酯、磷酸三(壬基苯基)酯、磷酸氢苯基甲酯、磷酸二(十二烷基)对甲苯酯、磷酸三甲苯酯、磷酸三苯酯、磷酸三苯酯、磷酸二丁基苯酯、磷酸2-氯乙基二苯酯、磷酸对甲苯基双(2,5,5'-三甲基己基)酯、磷酸2-乙基己基二苯酯和磷酸氢二苯酯。美国专利号6,404,971中描述的类型的磷酸酯为磷基阻燃剂的实例。额外实例包括液体磷酸酯,例如双酚A二磷酸酯(BAPP)(艾迪科帕马乐(Adeka Palmarole))和/或间苯二酚双(磷酸二苯基酯)(Fyroflex RDP)(以色列化工有限公司的旭瑞达(Supresta,ICI))以及固体磷,如多磷酸铵(APP)、哌嗪焦磷酸酯和哌嗪多磷酸酯。多磷酸铵通常与阻燃剂共添加剂(如三聚氰胺衍生物)一起使用。Melafine(DSM)(2,4,6-三氨基-1,3,5-三嗪;精细研磨三聚氰胺)也适用。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(G)。当存在时,(G)的浓度可为聚烯烃组合物的0.01至70wt%、可替代地0.05至40wt%、可替代地1至20wt%。
任选的成分(H)受阻胺稳定剂:含有碱性氮原子的分子,所述碱性氮原子与至少一个空间上庞大的有机基团键结并且充当降解或分解的抑制剂,或这类分子的集合。(H)为具有空间受阻的氨基官能团并且抑制氧化降解并且还可增加含有(C)有机过氧化物的聚烯烃组合物的实施例的存放期的化合物。合适的(H)的实例为丁二酸二甲酯、具有4-羟基-2,2,6,6-四甲基-1-哌啶-乙醇的聚合物(CAS号65447-77-0,商业上的LOWILITE 62);和N,N'-双甲酰基-N,N'-双(2,2,6,6-四甲基-4-哌啶基)-六亚甲基二胺(CAS号124172-53-8,商业上的Uvinul 4050H)。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(H)。当存在时,(H)受阻胺稳定剂可为聚烯烃组合物的0.001至1.5wt%、可替代地0.002至1.2wt%、可替代地0.002至1.0wt%、可替代地0.005至0.5wt%、可替代地0.01至0.2wt%、可替代地0.05至0.1wt%。
任选的成分(I)抗树剂:抑制水和/或电树生长的分子,或这类分子的集合。抗树剂可为抗水树剂或抗电树剂。抗水树剂为抑制水树生长的化合物,水树生长为在暴露于电场和湿度或湿气的组合效应下时聚烯烃降解的过程。抗电树剂(也称为电压稳定剂)为抑制电树生长的化合物,电树生长为由于局部放电引起的固体电绝缘材料中的电预击穿过程。在没有水的情况下可发生电树生长。水树生长和电树生长为含有涂层导体的电缆的问题,其中涂层含有聚烯烃。(I)可为聚(乙二醇)(PEG)。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(I)。当存在时,(I)抗树剂可为聚烯烃组合物的0.01至1.5wt%、可替代地0.05至1.2wt%、可替代地0.1至1.0wt%。
任选的成分(J)甲基自由基清除剂:与甲基自由基反应的分子,或这类分子的集合。(J)与聚烯烃组合物或交联聚烯烃产物中的甲基自由基反应。(J)可为2,2,6,6-四甲基-1-哌啶基-N-氧基或1,1-二芳基乙烯的“TEMPO”衍生物。TEMPO衍生物的实例为4-丙烯酰氧基-2,2,6,6-四甲基-1-哌啶基-N-氧基(CAS号21270-85-9,“丙烯酸酯TEMPO”)、4-烯丙氧基-2,2,6,6-四甲基-1-哌啶基-N-氧基(CAS号217496-13-4,“烯丙基TEMPO”);癸二酸双(2,2,6,6-四甲基-1-哌啶基-N-氧基)酯(CAS号2516-92-9,“双TEMPO”));N,N-双(丙烯酰基-4-氨基)-2,2,6,6-四甲基-1-哌啶基-N-氧基(CAS号1692896-32-4,“二丙烯酰胺TEMPO”);和N-丙烯酰基-4-氨基-2,2,6,6-四甲基-1-哌啶基-N-氧基(CAS号21270-88-2,“单丙烯酰胺TEMPO”)。1,1-二芳基乙烯的实例为1,1-二苯乙烯和α-甲基苯乙烯。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(J)。当存在时,(J)甲基自由基清除剂可为聚烯烃组合物的0.01至1.5wt%、可替代地0.05至1.2wt%、可替代地0.1至1.0wt%。
任选的成分(K)防焦剂:抑制过早固化的分子,或这类分子的集合。防焦剂的实例为受阻酚;半受阻酚;TEMPO;TEMPO衍生物;1,1-二苯乙烯;2,4-二苯基-4-甲基-1-戊烯(也称为α-甲基苯乙烯二聚体或AMSD);和US 6277925B1第2栏第62行至第3栏第46行中所述的含烯丙基的化合物。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(K)。当存在时,(K)防焦剂可为聚烯烃组合物的0.01至1.5wt%、可替代地0.05至1.2wt%、可替代地0.1至1.0wt%。
任选的成分(L)成核剂:提高聚烯烃聚合物的结晶速率的有机或无机添加剂。(L)的实例为碳酸钙、二氧化钛、硫酸钡、超高分子量聚乙烯、邻苯二甲酸氢钾、苯甲酸化合物、苯甲酸钠化合物、双环[2.2.1]庚烷-2,3-二羧酸二钠、单甘油酸锌和1,2-环己烷二甲酸钙盐:硬脂酸锌。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(L)。当存在时,(L)的浓度可为聚烯烃组合物的0.01至1.5wt%、可替代地0.05至1.2wt%、可替代地0.1至1.0wt%。
任选的成分(M)炭黑:细分形式的次晶碳,具有高的表面积/体积比,但低于活性炭的表面积/体积比。(M)的实例为炉炭黑、乙炔炭黑、导电碳(例如,碳纤维、碳纳米管、石墨烯、石墨和膨胀石墨片)。在一些方面,聚烯烃组合物和交联聚烯烃产物不含(M)。当存在时,(M)的浓度可为聚烯烃组合物的0.01至40wt%、可替代地0.05至35wt%、可替代地0.1至20wt%、可替代地0.5至10wt%、可替代地1至5wt%。
另外,聚烯烃组合物可独立地另外包含0.001至50wt%、可替代地0.05至30wt%、可替代地0.1至20wt%、可替代地0.5至10wt%、可替代地1至5wt%的一种或多种选自以下的任选的添加剂中的每一种:载体树脂、润滑剂、加工助剂、增滑剂、增塑剂、表面活性剂、增量油、除酸剂和金属减活剂。例如,增量油可高达聚烯烃组合物的50wt%。在一些方面,聚烯烃组合物和交联聚烯烃产物不含紧接的前述添加剂中的任一种。
聚烯烃组合物的上述成分不被认为充当其中的环状硅氧烷的开环催化剂。然而,如果聚烯烃组合物的上述成分中的任何一种或多种意外地被发现充当环状硅氧烷的一种或多种开环催化剂,那么将一种或多种这类成分排除在聚烯烃组合物之外。
交联聚烯烃产物:含有网络聚烯烃树脂的反应产物,所述树脂含有在聚烯烃组合物的固化(交联)期间形成的C-C键交联。网络聚烯烃树脂可包含将(A)聚烯烃聚合物的大分子与(B)式(I)的单环有机硅氧烷的分子偶联的反应产物,以得到含有多价单环有机硅氧烷交联剂基团的网络结构,所述多价单环有机硅氧烷交联剂基团经由(A)聚烯烃聚合物的两个或更多个大分子与(B)式(I)的单环有机硅氧烷的分子的一个或多个R1基团的反应与来自(A)聚烯烃聚合物的两个或更多个大分子键结。在一些方面,可在一个R1的同一个碳-碳双键上添加(A)的两个大分子。举例来说,当两个或更多个R1为乙烯基并且零个、一个或多个R2为乙烯基时,交联聚烯烃产物的网络结构可含有两个或更多个式(II)的多价单环有机硅氧烷交联剂基团:[-CH2CH2(R2)SiO2/2] (II)和/或式(III)[CH3C(-)(H),(R2)SiO2/2](III)以及式(I)(如果存在的话)的n-2或更少(例如n-3)个未反应单元,其中下标n如对于式(I)所定义,并且“-”指示多价中的一个。当每个R2独立地为式(I)中的H、(C1-C4)烷基或苯基时,式(II)和(III)中的每个R2独立地为H、(C1-C4)烷基或苯基。
交联聚烯烃产物还可含有固化副产物,如(C)有机过氧化物反应的醇和酮副产物。当聚烯烃组合物另外含有任何任选的添加剂或成分中的一种或多种(如(E)抗氧化剂)时,交联聚烯烃产物也可含有任选的添加剂或成分中的任一种或多种(如(E))或在聚烯烃组合物的固化期间由其形成的一种或多种反应产物。交联聚烯烃产物可呈分开的固体形式或呈连续形式。分开的固体形式可包含颗粒、粒料、粉末或其任何两种或更多种的组合。连续形式可为模制零件(例如,注塑零件)或挤出零件(例如,涂层导体或电缆)。
交联聚烯烃产物可不含开环催化剂和/或硅氧烷聚合物分子(硅酮,其通过(B)的开环聚合来制备)。
涂层导体。涂层导体可为绝缘电导体。绝缘电导体可为涂层金属导线和电缆,包括用于低压(“LV”,>0至<5千伏(kV))、中压(“MV”,5至<69kV)、高压(“HV”,69至230kV)或超高压(“EHV”,>230kV)数据传输和输电/配电应用中的电力电缆。“导线”意指导电材料(例如,如铜或铝的导电金属)的单股或细丝。“电缆”和“电力电缆”为同义的并且意指绝缘电导体,所述绝缘电导体包含安置在可被称为护套、套(保护性外套)或涂层的覆盖物内的至少一根导线。绝缘电导体可被设计和构造用于中压、高压或超高压应用中。合适的电缆设计的实例在US 5,246,783;US 6,496,629;以及US 6,714,707中示出。
绝缘电导体可含有导体/发射器芯以及外部单层覆盖物或安置在其周围的外部多层覆盖物,以便保护和隔离导体/发射器芯免受外部环境的影响。导体/发射器芯可由一根或多根金属导线构成。当导体/发射器芯含有两根或更多根金属导线时,金属导线可细分为离散的导线束。无论是否捆扎,导体/发射器芯中的每一根导线可单独地涂布有绝缘层和/或离散的束可涂布有绝缘层。单层覆盖物或多层覆盖物(例如,单层或多层涂层或护套)主要用以保护或隔离导体/发射器芯免受如阳光、水、热、氧气、其它导电材料(例如,防止短路)和/或其它腐蚀材料(例如,化学烟雾)的外部环境的影响。
从一个绝缘电导体到下一个绝缘电导体的单层或多层覆盖物可根据其相应的预期用途而不同地配置。举例来说,在横截面中观察,绝缘电导体的多层覆盖物可从其最内层到其最外层依次配置有以下部件:内半导体层、包含交联聚烯烃产物(本发明交联产物)的交联聚烯烃绝缘层、外半导体层、金属屏蔽以及保护护套。层和护套为周向和同轴(纵向)连续的。金属屏蔽(接地)为同轴连续的,并且为周向连续的(层)或不连续的(带或导线)。根据预期的应用,用于绝缘光纤的多层覆盖物可省略半导体层和/或金属屏蔽。外半导体层(当存在时)可由过氧化物交联的半导体产物构成,所述外半导体层可与交联聚烯烃层键结或可从其剥离。
在一些方面,存在制备涂层导体的方法,方法包含:将包含一层聚烯烃组合物的涂层挤出到导体/发射器芯上以得到涂层芯;以及使涂层芯穿过连续硫化(CV)设备,所述设备配置有用于使聚烯烃组合物固化以得到涂层导体的合适的CV条件。CV条件包括温度、气氛(例如,氮气)以及穿过CV设备的线速度或通过时间段。合适的CV条件可使涂层导体离开CV设备,其中涂层导体含有通过使一层交联聚烯烃层固化而形成的交联聚烯烃层。
导电方法。本发明的导电方法可使用包含绝缘电导体实施例的本发明涂层导体。还设想使用包含绝缘电导体的本发明涂层导体来传输数据的方法。
密度根据ASTM D792-13,《用位移法测定塑料密度和比重(相对密度)的标准测试方法,方法B(Standard Test Methods for Density and Specific Gravity(RelativeDensity)of Plastics by Displacement,Method B)》(用于测试除水之外的液体中的固体塑料,例如在液体2-丙醇中)来测量。报告结果以克/立方厘米(g/cm3或g/cc)为单位。
熔融指数(I2)根据ASTM D1238-04(190℃,2.16kg),《用挤压式塑性计测定热塑性塑料的熔融流动速率的标准测试方法(Standard Test Method for Melt Flow Rates ofThermoplastics by Extrusion Platometer)》,使用190℃/2.16千克(kg)的条件来测量,以前称为“条件E”,并且也称为I2。报告结果以每10分钟洗脱的克数(克/10分钟)或相当于每1.0分钟的分克数(分克/1分钟)为单位。10.0dg=1.00g。
迁移测量测试方法。可通过将5克(g)粒料放入未使用的透明自密封聚乙烯袋中,并且压制粒料5次以查看任何标记(油迹)被压在袋上来观察迁移添加剂。如果观察到标记,那么记录为“是”,并且如果没有观察到标记,那么记录为“否”。
焦化时间测试方法。样品“X”的焦化时间或焦化的时间(ts1)通过MDR在140℃下进行测量并且缩写为ts1@140℃。根据ISO 6502在Alpha Technologies Rheometer MDR2000E上测量焦化时间如下。将5至6g的测试材料(粒料)放入MDR 200E仪器中。在140℃下在每分钟100个循环(cpm)下的0.5度弧的振荡变形测量作为0分钟(开始)至120分钟的时间的函数的扭矩,并且绘制扭矩相对于时间的曲线。ts1为从测试开始(0分钟)至观察到扭矩从扭矩曲线中的最小值增加1分牛顿米(dNm)所花费的时间长度。使用ts1@140℃来表征在熔融加工过程(例如,熔融混配或挤出)期间的耐焦化性。
T90交联时间测试方法:ASTM D5289-12,《橡胶特性的标准测试方法-使用无旋转固化仪进行硫化(Standard Test Method for Rubber Property-Vulcanization UsingRotorless Cure Meters)》。使用以下程序测量测试样品的扭矩。在动模流变仪(MDR)仪器MDR2000(阿尔法科技公司(Alpha Technologies))中在180℃下加热测试样品20分钟,同时监视在100cpm下的0.5度弧的振荡变形的扭矩改变。将最低的测量扭矩值指定为“ML”,以分牛顿米(dN-m)表示。随着固化或交联的进行,测得扭矩值增加,最终达到最大扭矩值。将最大或最高测量扭矩值指定为“MH”,以dN-m表示。在所有其它条件相同的情况下,MH扭矩值越大,交联程度越大。将T90交联时间确定为达到等于差值MH减去ML(MH-ML)的90%(即从ML至MH的路径的90%)的扭矩值所需的分钟数。T90交联时间越短,即扭矩值从ML至MH的路径达到90%越早,测试样品的固化速率越快。相反,T90交联时间越长,即扭矩值从ML至MH的路径达到90%所需的时间越长,测试样品的固化速度越慢。
以下数据预测本发明组合物在挤出和交联(例如,在CV设备中)以形成电缆的绝缘层时将如何表现。
实例
LDPE(A1):低密度聚乙烯(LDPE)通过将LDPE(A2)与0.12wt%的抗氧化剂(E1)、0.24wt%的抗氧化剂(E2)和百万分之50(wt)的受阻胺稳定剂(H1)混配而制备(关于(A2)、(E1)、(E2)和(H1)的描述,请参见下文),并且其密度为0.92g/cm3,并且熔融指数(I2)为2克/10分钟。
LDPE(A2):高压反应器制备的低密度聚乙烯(LDPE)产物,其每1000个碳原子具有平均大于0.3个碳-碳双键、密度为0.92g/cm3,并且熔融指数(I2)为2克/10分钟(190℃,2.16kg)并且获自美国密歇根州米德兰的陶氏化学公司(The Dow Chemical Company,Midland,Michigan,USA)。LDPE(A2)在管式高压反应器中制备并且方法类型描述于《聚合物化学导论(Introduction to Polymer Chemistry)》,Stille,威利父子公司(Wiley andSons),纽约(New York),1962,第149至151页中。方法为自由基引发的,并且在170至310兆帕(MPa,即25,000至45,000磅/平方英寸(psi))的压力和200℃至350℃的温度下进行。
LDPE(A3):低密度聚乙烯(LDPE)通过Brabender单螺杆挤出机在120℃下将已知量的LDPE(A2)共混到LDPE(A1)中,以得到负载为0.06wt%的抗氧化剂(E1)、0.09wt%的抗氧化剂(E2)和19ppm的受阻胺稳定剂(H1)的LDPE(A3)来制备,并且其密度为2.0g/cm3,并且熔融指数(I2)为0.92克/10分钟。
单环有机硅氧烷(B1):2,4,6-三甲基-2,4,6-三乙烯基-环三硅氧烷,获自盖勒斯特(Gelest)的“(DVi)3”(CAS号3901-77-7)。
单环有机硅氧烷(B2):2,4,6,8-四甲基-2,4,6,8-四乙烯基-环四硅氧烷,获自陶氏化学公司的“(DVi)4”(CAS号2554-06-5)。
单环有机硅氧烷(B3):2,4,6,8,10-五甲基-2,4,6,8,10-五乙烯基-环戊硅氧烷,获自盖勒斯特的“(DVi)5”(CAS号17704-22-2)。
有机过氧化物(C1):获自芳瑞达(Fangruida)的二枯基过氧化物(“DCP”)。
常规助剂(D1):获自中国芳瑞达(Fangruida,People’s Republic of China)的异氰脲酸三烯丙酯(TAIC)。
抗氧化剂(E1):Cyanox 1790,其可购自氰特工业有限公司(Cytec IndustriesInc)。
抗氧化剂(E2):DSTDP,其可购自Reagens有限公司。
受阻胺稳定剂(H1):来自巴斯夫(BASF)的Uvinul 4050。
八乙烯基多面体低聚倍半硅氧烷(OV-POSS):向500mL三颈烧瓶中添加无水甲醇(200mL)、去离子水(9mL)和浓盐酸(36wt%,2mL)。所得第一混合物在40℃下搅拌约10分钟。然后在4小时内向第一混合物中逐滴添加乙烯基三甲氧基硅烷(20mL,H2C=C(H)Si(OCH3)3)的甲醇(50mL)溶液。在乙烯基三甲氧基硅烷溶液添加完成后,立即全部添加额外部分的甲醇(30mL)。所得组合的混合物在40℃下搅拌5天。形成OV-POSS的沉淀物并且将其滤出。将所得滤饼溶解在最少量的四氢呋喃中,并且向所得溶液中添加乙醇以使OV-POSS再沉淀。将再沉淀的OV-POSS过滤并且减压干燥,以得到1g(11%收率)呈白色固体状的OV-POSS。
磷腈碱(“P4-t-Bu”):获自西格玛-奥德里奇公司(Sigma-Aldrich)的0.4摩尔的1-叔丁基-4,4,4-三(二甲氨基)-2,2-双[三(二甲氨基)正膦亚基氨基]-25,45-连二(磷腈)的己烷溶液。
比较例1和2(CE1和CE2):在独立的运行中,在Brabender内部混合器中在120℃下以每分钟40转(rpm)将OV-POSS添加到LDPE(A3)的熔体中5分钟以得到中间组合物。然后在120℃下将中间组合物压制2分钟以形成斑块。将斑块切成粒料,并且在80℃下将粒料用有机过氧化物(C1)浸泡6小时,以得到CE1和CE2。参见表1和3。
比较例3和4(CE3和CE4):在单独的运行中,在120℃下以每分钟50转(rpm)将LDPE(A2)在HAAKE内部混合物中熔融5分钟。然后添加单环有机硅氧烷(B3)和磷腈碱P4-t-Bu(不同的量),并且混合所得组合30秒。然后添加有机过氧化物(C1),并且将所得组合混合30秒,以得到中间组合物。在120℃下于10兆帕(MPa)的压力下将中间组合物压制30秒,以分别得到呈斑块状的CE3和C4。参见表1和3。
比较例5和6:将LDPE(A3)粒料与有机过氧化物(C1)在80℃下浸泡6小时以得到组合物CE5和CE6。参见表1和3。
表1:CE1至CE6的组成。(0=0.00)
成分(重量份) | CE1 | CE2 | CE3 | CE4 | CE5 | CE6 |
LDPE(A3) | 98.40 | 98.55 | 0 | 0 | 98.65 | 98.85 |
LDPE(A2) | 0 | 0 | 98.20 | 97.80 | 0 | 0 |
二枯基过氧化物(C1) | 0.50 | 0.50 | 0.50 | 0.50 | 1.35 | 1.15 |
OV-POSS | 1.10 | 0.50 | 0 | 0 | 0 | 0 |
P4-t-Bu | 0 | 0 | 0.10 | 0.50 | 0 | 0 |
(B1)=(D<sup>Vi</sup>)<sub>3</sub> | 0 | 0 | 0 | 0 | 0 | 0 |
(B2)=(D<sup>Vi</sup>)<sub>4</sub> | 0 | 0 | 0 | 0 | 0 | 0 |
(B3)=(D<sup>Vi</sup>)<sub>5</sub> | 0 | 0 | 1.20 | 1.20 | 0 | 0 |
TAIC(D1) | 0 | 0.45 | 0 | 0 | 0 | 0 |
总计 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
乙烯基含量(mmol) | 13.9 | 12.4 | 13.9 | 13.9 | 0 | 0 |
本发明实例1至6(IE1至IE6):在单独的运行中,在80℃下在烘箱中将单环有机硅氧烷(B1)、(B2)或(B3)和任选的异氰脲酸三烯丙酯(TAIC)以及有机过氧化物(C1)浸泡到LDPE(A3)或(A2)的粒料中6小时,以得到呈粒料形式的本发明组合物IE1至IE6。参见表2和4。
表2:IE1至IE6的组成。(0=0.00)
成分(重量份) | IE1 | IE2 | IE3 | IE4 | IE5 | IE6 |
LDPE(A3) | 98.30 | 0 | 0 | 98.55 | 98.30 | 0 |
LDPE(A2) | 0 | 98.30 | 98.80 | 0 | 0 | 98.30 |
二枯基过氧化物(C1) | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 |
(B1)=(D<sup>Vi</sup>)<sub>3</sub> | 0 | 0 | 0 | 0 | 1.20 | 0 |
(B2)=(D<sup>Vi</sup>)<sub>4</sub> | 1.20 | 1.20 | 0.70 | 0.50 | 0 | 0 |
(B3)=(D<sup>Vi</sup>)<sub>5</sub> | 0 | 0 | 0 | 0 | 0 | 1.20 |
TAIC(D1) | 0 | 0 | 0 | 0.45 | 0 | 0 |
总计 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
乙烯基含量(mmol) | 13.9 | 13.9 | 8.1 | 11.2 | 13.9 | 13.9 |
根据T90交联时间测试方法、焦化时间测试方法和迁移测量测试方法中的一种或多种,表征CE1至CE6和IE1至IE6的组合物的粒料的测试样品。参见表3和4。
表3:CE1至CE6的表征。
表征 | CE1 | CE2 | CE3 | CE4 | CE5 | CE6 |
在180℃下的最低扭矩ML(dN-m) | 0.22 | 0.20 | 0.21 | 0.21 | 0.21 | 0.21 |
在180℃下的最高扭矩MH(dN-m) | 3.56 | 3.52 | 2.95 | 1.89 | 3.39 | 2.93 |
在180℃下的T90交联时间(分钟) | 4.64 | 3.93 | 3.57 | 2.60 | 4.36 | 4.41 |
是否观察到表面迁移?* | 否 | 否 | 否 | 否 | 否 | 否 |
在140℃下的焦化时间ts1(分钟) | 26.5 | 34.8 | 28.3 | 30.5 | 34.6 | 41.3 |
*初始迁移在17小时后确定。
表4:IE1至IE6的表征。
*初始迁移在17小时后确定。
如通过比较CE1的数据与CE5的数据所指示,为了达到相同的固化水平,OV-POSS损害耐焦化性,如通过CE5在140℃下的焦化时间ts1(分钟)值比CE1的焦化时间值短所指示。如通过比较CE6的数据与IE1的数据所指示,为了达到相同的固化水平,(B)单环有机硅氧烷改进耐焦化性,如通过IE1在140℃下的焦化时间ts1(分钟)值比CE6的焦化时间值长所指示。如通过比较CE2的数据与CE5的数据所指示,在存在另一种助剂异氰脲酸三烯丙酯的情况下,OV-POSS不损害耐焦化性,这通过CE5在140℃下的焦化时间ts1(分钟)值与CE2的焦化时间值相当所指示。如通过比较CE6的数据与IE4的数据所指示,在存在另一种助剂异氰脲酸三烯丙酯的情况下,(B)单环有机硅氧烷仍然改进耐焦化性,这通过IE4在140℃下的焦化时间ts1(分钟)值比CE6的焦化时间值长所指示。如通过比较CE3和CE4的数据与IE6的数据所指示,CE3和CE4中的磷腈碱(P4-t-Bu)无助于交联,并且实际上损害(降低)交联水平,如通过在180℃下的最高扭矩MH所指示。CE3和CE4的值显著低于IE6在180℃下的最高扭矩MH值。随着磷腈碱浓度的增加,磷腈碱对交联水平的有害影响逐渐增大(CE3对CE4)。
除分别用“方面(aspect或aspects)”替换“权利要求(claim和claims)”之外,在本文中以引用的方式并入下文权利要求作为编号方面。
Claims (41)
1.一种聚烯烃组合物,其包含(A)聚烯烃聚合物,所述聚烯烃聚合物为包含以下的低密度聚乙烯(LDPE)聚合物:50至100重量百分比(wt%)的烯键式单体单元、50至0wt%的C3-C20α-烯烃衍生的共聚单体单元,和20至0wt%的二烯共聚单体单元,其中总重量百分比为100.00wt%;交联有效量的(B)式(I)的单环有机硅氧烷:[R1,R2SiO2/2]n(I),其中下标n为大于或等于3的整数;每个R1独立地为C2-C4烯基或H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、C1-C4烷基、苯基或R1;和(C)有机过氧化物;条件是所述聚烯烃组合物不含磷腈碱,
其中所述(A)聚烯烃聚合物为所述聚烯烃组合物的重量的80至99.89重量百分比(wt%),所述(B)式(I)的单环有机硅氧烷为聚烯烃组合物的0.1至3wt%,和所述(C)有机过氧化物为所述聚烯烃组合物的0.01至4.5wt%。
2.一种聚烯烃组合物,其包含(A)聚烯烃聚合物,所述聚烯烃聚合物为包含以下的低密度聚乙烯(LDPE)聚合物:50至100重量百分比(wt%)的烯键式单体单元、50至0wt%的C3-C20α-烯烃衍生的共聚单体单元,和20至0wt%的二烯共聚单体单元,其中总重量百分比为100.00wt%;(B)式(I)的单环有机硅氧烷:[R1,R2SiO2/2]n(I),其中下标n为大于或等于3的整数;每个R1独立地为C2-C4烯基或H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、C1-C4烷基、苯基或R1;和(C)有机过氧化物;条件是所述聚烯烃组合物不含磷腈碱;并且条件是当下标n为4时,所述(A)聚烯烃组合物不含有24wt%或更多的选自由以下组成的组的无机填料:氧化铝、硅酸铝、硅酸钙、硅酸镁、二氧化硅、二氧化钛以及其混合物,
其中所述(A)聚烯烃聚合物为所述聚烯烃组合物的重量的80至99.89重量百分比(wt%),所述(B)式(I)的单环有机硅氧烷为聚烯烃组合物的0.1至3wt%,和所述(C)有机过氧化物为所述聚烯烃组合物的0.01至4.5wt%。
3.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(i)描述:(i)每个R1独立地为C2-C3烯基;并且每个R2独立地为H、C1-C2烷基或C2-C3烯基。
4.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(ii)描述:(ii)每个R1为乙烯基;并且每个R2独立地为C1-C2烷基。
5.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(iii)描述:(iii)每个R1为乙烯基;并且每个R2为甲基。
6.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(iv)描述:(iv)每个R1为烯丙基;并且每个R2独立地为C1-C2烷基。
7.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(v)描述:(v)每个R1为烯丙基;并且每个R2为甲基。
8.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(vi)描述:(vi)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、C1-C2烷基或C2-C3烯基。
9.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(vii)描述:(vii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H并且下标m为3;并且每个R2独立地为C1-C2烷基。
10.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(viii)描述:(viii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为甲基,并且下标m为3;并且每个R2独立地为C1-C2烷基。
11.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(ix)描述:(ix)所述聚烯烃组合物不含有24wt%或更多的选自由以下组成的组的无机填料:氧化铝、硅酸铝、硅酸钙、硅酸镁、二氧化硅、二氧化钛以及其混合物。
12.根据权利要求1或2所述的聚烯烃组合物,其中下标n为3并且所述(B)式(I)的单环有机硅氧烷通过以下限制(x)描述:(x)如权利要求11中所限定的限制(ix)与分别如权利要求3-10中所限定的限制(i)至(viii)中的任一项的组合。
13.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(i)描述:(i)每个R1独立地为C2-C3烯基;并且每个R2独立地为H、C1-C2烷基或C2-C3烯基。
14.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(ii)描述:(ii)每个R1为乙烯基;并且每个R2独立地为C1-C2烷基。
15.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(iii)描述:(iii)每个R1为乙烯基;并且每个R2为甲基。
16.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(iv)描述:(iv)每个R1为烯丙基;并且每个R2独立地为C1-C2烷基。
17.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(v)描述:(v)每个R1为烯丙基;并且每个R2为甲基。
18.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(vi)描述:(vi)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、C1-C2烷基或C2-C3烯基。
19.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(vii)描述:(vii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H并且下标m为3;并且每个R2独立地为C1-C2烷基。
20.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(viii)描述:(viii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为甲基,并且下标m为3;并且每个R2独立地为C1-C2烷基。
21.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(ix)描述:(ix)所述聚烯烃组合物不含有24wt%或更多的任何无机填料。
22.根据权利要求1或2所述的聚烯烃组合物,其中下标n为4并且所述(B)式(I)的单环有机硅氧烷通过以下限制(x)描述:(x)如权利要求21中所限定的限制(ix)与分别如权利要求13-20中所限定的限制(i)至(viii)中的任一项的组合。
23.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(i)描述:(i)每个R1独立地为C2-C3烯基;并且每个R2独立地为H、C1-C2烷基或C2-C3烯基。
24.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(ii)描述:(ii)每个R1为乙烯基;并且每个R2独立地为C1-C2烷基。
25.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(iii)描述:(iii)每个R1为乙烯基;并且每个R2为甲基。
26.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(iv)描述:(iv)每个R1为烯丙基;并且每个R2独立地为C1-C2烷基。
27.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(v)描述:(v)每个R1为烯丙基;并且每个R2为甲基。
28.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(vi)描述:(vi)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H或甲基,并且下标m为1至4的整数;并且每个R2独立地为H、C1-C2烷基或C2-C3烯基。
29.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(vii)描述:(vii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为H并且下标m为3;并且每个R2独立地为C1-C2烷基。
30.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(viii)描述:(viii)每个R1独立地为H2C=C(R1a)-C(=O)-O-(CH2)m-,其中R1a为甲基,并且下标m为3;并且每个R2独立地为C1-C2烷基。
31.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(ix)描述:(ix)所述聚烯烃组合物不含有24wt%或更多的选自由以下组成的组的无机填料:氧化铝、硅酸铝、硅酸钙、硅酸镁、二氧化硅、二氧化钛以及其混合物。
32.根据权利要求1或2所述的聚烯烃组合物,其中下标n为5或6并且所述(B)式(I)的单环有机硅氧烷通过以下限制(x)描述:(x)如权利要求31中所限定的限制(ix)与分别如权利要求23-30中任一项所限定的限制(i)至(viii)中的任一项的组合。
33.根据权利要求1或2所述的聚烯烃组合物,所述聚烯烃组合物通过如下描述:所述(A)聚烯烃聚合物的特征在于密度为0.86至0.97克/立方厘米(g/cm3),如通过ASTM D792-13的方法B在2-丙醇中所测量。
34.根据权利要求1或2所述的聚烯烃组合物,其另外包含选自由以下组成的组的至少一种添加剂:(D)常规助剂,所述常规助剂为在其各自的主链或环亚结构中含有碳原子的非环状或环状化合物;(E)抗氧化剂;(F)填料;(G)阻燃剂;(I)抗树剂,所述抗树剂是抑制水和/或电树生长的分子;(K)防焦剂和(L)成核剂;条件是所述至少一种添加剂的总量为所述聚烯烃组合物的>0且≤70wt%,并且条件是所述(F)填料不包括任何省略的填料。
35.根据权利要求34所述的聚烯烃组合物,其中所述(E)抗氧化剂是(H)受阻胺稳定剂或(J)甲基自由基清除剂,并且所述(F)填料是(M)炭黑。
36.一种制备聚烯烃组合物的方法,所述方法包含将(A)聚烯烃聚合物和(B)式(I)的单环有机硅氧烷:[R1,R2SiO2/2]n(I)混合在一起以制备根据权利要求1至35中任一项所述的聚烯烃组合物。
37.一种将根据权利要求1至35中任一项所述的聚烯烃组合物自由基固化以制备交联聚烯烃产物的方法,所述方法包含在固化有效温度下加热具有(C)有机过氧化物的所述聚烯烃组合物,其方式为以便使(A)聚烯烃聚合物与(B)式(I)的单环有机硅氧烷反应,从而制备交联聚烯烃产物。
38.一种交联聚烯烃产物,其通过根据权利要求37所述的固化的方法制备。
39.一种制品,其包含成型形式的根据权利要求1至36中任一项所述的聚烯烃组合物或根据权利要求38所述的交联聚烯烃产物。
40.一种涂层导体,其包含导电芯和至少部分地覆盖所述导电芯的绝缘层,其中所述绝缘层的至少一部分包含根据权利要求1至35中任一项所述的聚烯烃组合物或根据权利要求38所述的交联聚烯烃产物。
41.一种传输电的方法,所述方法包含在根据权利要求40所述的涂层导体的导电芯上施加电压,以便产生穿过所述导电芯的电流。
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