CN105814134A - 包含含有可水解硅烷基团的可交联聚烯烃、催化剂和表面活性剂相互作用添加剂的聚合物组合物 - Google Patents
包含含有可水解硅烷基团的可交联聚烯烃、催化剂和表面活性剂相互作用添加剂的聚合物组合物 Download PDFInfo
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- CN105814134A CN105814134A CN201480067492.4A CN201480067492A CN105814134A CN 105814134 A CN105814134 A CN 105814134A CN 201480067492 A CN201480067492 A CN 201480067492A CN 105814134 A CN105814134 A CN 105814134A
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- polymer composition
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- silanol condensation
- alkyl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000000654 additive Substances 0.000 title claims abstract description 51
- 230000000996 additive effect Effects 0.000 title claims abstract description 39
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 36
- 229920000098 polyolefin Polymers 0.000 title claims description 31
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims description 22
- 238000009833 condensation Methods 0.000 claims abstract description 52
- 230000005494 condensation Effects 0.000 claims abstract description 52
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- -1 amine salt Chemical class 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 9
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 230000003993 interaction Effects 0.000 claims description 34
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 23
- 238000004132 cross linking Methods 0.000 claims description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- 239000004596 additive masterbatch Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000004595 color masterbatch Substances 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- XSCFNOMFYIWSOB-UHFFFAOYSA-N ethenyl-bis(2-methoxyethoxy)silane Chemical compound COCCO[SiH](C=C)OCCOC XSCFNOMFYIWSOB-UHFFFAOYSA-N 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000515 huntite Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
本发明涉及一种聚合物组合物;一种包含所述聚合物组合物的制品,例如,涂层、导线或电缆;一种制备制品的方法和所述聚合物组合物的用途,所述聚合物组合物包含表面活性剂相互作用添加剂,以及其中所述聚合物组合物进一步包含至少一种硅烷醇缩合催化剂,其中每种催化剂选自:i)式ArSO3H(I)的化合物或其前体,其中Ar是1至4个烷基取代的芳基,其中所述芳基是苯基或萘基,并且其中各烷基独立地为含有10至30个碳的直链或支链烷基,其中在所述烷基中的碳的总数在20至80个碳的范围内;ii)选自i)的酸酐、酯、乙酰化物、环氧封端酯和胺盐的i)的衍生物,其可水解为相应的式(I)化合物;以及iii)i)的金属盐,其中金属离子选自铜、铝、锡和锌。
Description
技术领域
本发明涉及一种新的聚合物组合物,包含该聚合物组合物的制品,例如,涂层、导线或电缆,制备制品的方法以及该聚合物组合物的用途。
背景技术
已知利用添加剂交联聚合物。交联改善了聚合物诸如机械强度和耐热性的性能。通常认为是热塑性塑料并且不可交联的聚合物还可以通过在聚合物中引入可交联基团而制成可交联的。其实例是包括聚烯烃(例如聚乙烯)的聚合物组合物,其中硅烷化合物作为可交联基团,例如通过将硅烷化合物接枝到制备的聚烯烃上,或通过烯烃与硅烷化合物的共聚合而被引入。这些技术例如从US4413066、US4297310、US4351876、US4397981、US4446283和US4456704中是已知的。
用催化剂交联包含可水解硅烷基团的聚合物组合物在本领域中是已知的,例如参见EP0736065。还已知交联方法可以在酸性硅烷醇缩合催化剂的存在下有利地进行。酸性硅烷醇缩合催化剂允许含硅烷的聚合物组合物已经在室温(大约20℃至25℃)下交联。这样的为有机磺酸、或这些酸的前体的酸性硅烷醇缩合催化剂的实例,例如,在WO95/17463、EP1309631、EP1309632和EP1849816中公开,这些文件及其内容通过引用方式并入本文。
还已知在聚合物组合物中使用各种添加剂。待使用的添加剂的特定的类型和用量取决于聚合物组合物被设计的特定用途。
此外,一些重要种类的添加剂是表面活性剂相互作用添加剂,其可以以,例如,颜料为代表,并且重要的颜料包含二氧化钛,即,TiO2,和/或碳酸钙,即,CaCO3作为主要成分的颜料。包含二氧化钛和/或碳酸钙的颜料用来改善加工制品的颜色覆盖范围。包含二氧化钛和/或碳酸钙的颜料,例如,用来使加工制品更加不透明。
此外,在本领域中还已知在包含含有可水解硅烷基团的聚烯烃和常规的硅烷醇缩合催化剂的聚合物组合物中使用包含二氧化钛和/或碳酸钙的颜料。而且,表面活性剂相互作用添加剂还已显示出,例如包含二氧化钛和/或碳酸钙的颜料,在某种程度上钝化布朗斯台德酸型的硅烷醇缩合催化剂的交联能力。因此,通常说来,包含二氧化钛和/或碳酸钙的颜料与用酸型的硅烷醇缩合催化剂交联含有可水解硅烷基团的聚烯烃的技术是不相容的。因此,需要一种聚合物组合物,其包含特定的硅烷醇缩合催化剂和表面活性剂相互作用添加剂,例如包含二氧化钛和/或碳酸钙的颜料,其中所述聚合物组合物有效地促进酸型的硅烷醇缩合催化剂的交联性能。
发明内容
现已惊奇地发现通过根据本发明的新的聚合物组合物,实现了提供有效地提高期望的交联性能的聚合物组合物的目的,其中所述聚合物组合物包含表面活性剂相互作用添加剂,以及特定的酸型的硅烷醇缩合催化剂,其中所述催化剂是:
i)式I化合物
ArSO3H(I)
或其前体,其中
Ar是1至4个烷基取代的芳基,其中所述芳基是苯基或萘基,并且其中各烷基独立地为含有10至30个碳的直链或支链烷基,其中在所述烷基中的碳的总数在20至80个碳的范围内;
ii)选自i)的酸酐、酯、乙酰化物、环氧封端酯和胺盐的i)的衍生物,其可水解为相应的式I化合物;以及
iii)i)的金属盐,其中金属离子选自铜、铝、锡和锌。
因此,本发明提供了一种聚合物组合物,其包含表面活性剂相互作用添加剂,其中所述聚合物组合物进一步包含至少一种硅烷醇缩合催化剂,并且每种催化剂选自:
i)式I化合物
ArSO3H(I)
或其前体,其中
Ar是1至4个烷基取代的芳基,其中所述芳基是苯基或萘基,并且其中各烷基独立地为含有10至30个碳的直链或支链烷基,其中在所述烷基中的碳的总数在20至80个碳的范围内;
ii)选自i)的酸酐、酯、乙酰化物、环氧封端酯和胺盐的i)的衍生物,其可水解为相应的式I化合物;以及
iii)i)的金属盐,其中金属离子选自铜、铝、锡和锌。
根据本发明,通过使用本文所述的包含表面活性剂相互作用添加剂,以及特定的酸型的硅烷醇缩合催化剂(该催化剂包含由一个或多个烷基取代的芳基)的聚合物组合物,现已惊奇地发现可以实现有效的交联反应,即,在表面活性剂相互作用添加剂的存在下,硅烷基团的水解和缩合。当聚合物制品在热水浴中交联时这种效果尤其显著。所述表面活性剂相互作用添加剂例如可以是色母料。包含二氧化钛和/或碳酸钙的色母料通常与酸相互作用。如果二氧化钛和/或碳酸钙的存在相对催化剂的浓度非常高,结果将是硅烷基团的无效交联。因此,本发明涉及使用特定的具有亲脂特性的酸型的硅烷醇缩合催化剂。所以,所述催化剂已显示与聚合物组合物的通常为非极性的聚合物基体具有改善的相容性。因此,相应地,所述催化剂还通过与添加剂表面相互作用而具有较小的驱动力以降低其能量。所以,所述催化剂在聚合物基体中保留更长时间并且对于催化硅烷水解和缩合反应来说更加可用。
根据本发明的聚合物组合物包含所述表面活性剂相互作用添加剂,该表面活性剂相互作用添加剂可以包括含有极性表面基团的固体物质,例如,选自填料、不同种类的颜料、TiO2、CaCO3、炭黑(例如“UV黑”,即,吸收紫外线辐射的炭黑)、碳酸钙镁石、云母、高岭土、氢氧化铝(ATH)、氢氧化镁(MDH)以及SiO2中一种或多种。
此外,根据本发明,表述“聚合物组合物包含表面活性剂相互作用添加剂,其中所述聚合物组合物进一步包含至少一种硅烷醇缩合催化剂”还将理解为包括这样聚合物组合物的实施方式,其中表面活性剂相互作用添加剂包含在表皮中,该表皮是外部,并且与包含所述“至少一种”硅烷醇缩合催化剂的内部聚合物组合物接触。因此,在这样的实施方式中,本发明的聚合物组合物包括所述表皮,其包含表面活性剂相互作用添加剂,以及所述的包含所述“至少一种”硅烷醇缩合催化剂的内部聚合物组合物。此外,所述内部聚合物组合物可以,任选地,还包含表面活性剂相互作用添加剂。
此外,根据本发明,表述“聚合物组合物包含表面活性剂相互作用添加剂,其中所述聚合物组合物进一步包含至少一种硅烷醇缩合催化剂”还将理解为包括包含表面活性剂相互作用添加剂的聚合物组合物的实施方式,其中所述聚合物组合物已用所述至少一种硅烷醇缩合催化剂喷洒。
本发明的聚合物组合物还包含所述“至少一种”硅烷醇缩合催化剂,其中每种催化剂选自:
i)式I化合物
ArSO3H(I)
或其前体,其中
Ar是1至4个烷基取代的芳基,其中所述芳基是苯基或萘基,并且其中各烷基独立地为含有10至30个碳的直链或支链烷基,其中在所述烷基中的碳的总数在20至80个碳的范围内;
ii)选自i)的酸酐、酯、乙酰化物、环氧封端酯和胺盐的i)的衍生物,其可水解为相应的式I化合物;以及
iii)i)的金属盐,其中金属离子选自铜、铝、锡和锌。
式I化合物的Ar,除了所述“1至4个烷基”-取代基,还可以,任选地,包含另外合适的取代基。
本发明的实施方式提供一种聚合物组合物,如在此所述,其中所述每种硅烷醇缩合催化剂选自a)C12-烷基化萘基磺酸;
b)选自a)的酸酐、酯、乙酰化物、环氧封端酯和胺盐的a)的衍生物,其可水解为相应的化合物a);和/或
c)a)的金属盐,其中金属离子选自铜、铝、锡和锌。
本发明的另一个实施方式提供一种聚合物组合物,如在此所述,其中所述每种硅烷醇缩合催化剂选自C12-烷基化萘基磺酸。
在本发明的另一个实施方式中,所述聚合物组合物是进一步包含聚合物基体的硅烷醇缩合催化剂母料。
当根据本发明的聚合物组合物是硅烷醇缩合催化剂母料时,所述硅烷醇缩合催化剂母料可以是一种混合物,其可以包含所述表面活性剂相互作用添加剂和所述“至少一种”硅烷醇缩合催化剂(即,式I化合物)两者,两者均以在所述聚合物基体中浓缩的形式。
此外,当根据本发明的聚合物组合物是硅烷醇缩合催化剂母料时,所述硅烷醇缩合催化剂母料可以通过使所述表面活性剂相互作用添加剂、所述“至少一种”硅烷醇缩合催化剂,以及,任选地,任何另外的添加剂与聚合物树脂(即,载体树脂)混合而产生,由此所述聚合物树脂形成所述聚合物基体。
任选地,所述另外的添加剂,例如可以是混溶性热塑性塑料、抗氧化剂、稳定剂、润滑剂、填料、过氧化物、硅烷和/或发泡剂。
根据本发明的硅烷醇缩合催化剂母料可以以液体形式或适合成形为,例如,粉末和/或颗粒状固体(如,丸粒或颗粒)的固体形式。
此外,在聚合物交联之前,当作为所述硅烷醇缩合催化剂母料以浓缩的形式添加时,可以有利于所述“至少一种”硅烷醇缩合催化剂,即,式I化合物,以及所述表面活性剂相互作用添加剂的处理。
所述聚合物基体可以包含,例如,聚烯烃,如聚乙烯,其可以是乙烯的均聚物或共聚物,例如低密度聚乙烯,或乙烯-丙烯酸酯共聚物,其中丙烯酸酯共聚单体选自丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和丙烯酸叔丁酯,或是含有1重量%至50重量%的所述丙烯酸酯共聚单体的共聚物,或它们的任意混合物。此外,所述聚合物基体可以包含高密度或中密度聚乙烯。此外,所述聚合物基体可以包含双峰聚合物。
在本发明的再一个实施方式中,所述聚合物组合物进一步包含含有可水解硅烷基团的可交联聚烯烃。
所述聚合物组合物的所述可交联聚烯烃,例如,可以包含含有可水解硅烷基团的聚乙烯,或所述可交联聚烯烃,例如,可以由含有可水解硅烷基团的聚乙烯组成。
所述可水解硅烷基团可以通过,例如,乙烯和含硅烷基团的共聚单体的共聚合,或通过接枝(即,大多数情况下通过在自由基间的反应中加入含硅烷的化合物化学改性聚烯烃)被引入所述聚烯烃中。在本领域中两种技术均为人熟知。
另外,所述含有可水解硅烷基团的可交联聚烯烃可以通过共聚合得到。例如在聚烯烃为聚乙烯的情况下,所述共聚合可以用由式II表示的不饱和硅烷化合物来进行
R1SiR2 qY3-q(II)
其中,
R1为烯键式不饱和烷基、烷氧基或(甲基)丙烯酰氧基烷基,
R2为脂肪族饱和烷基,
Y,可以相同或不同,为可水解有机基团,并且
q为0,1或2。
所述不饱和硅烷化合物的具体实例是其中R1为乙烯基、烯丙基、异丙烯基、丁烯基、环己基或γ-(甲基)丙烯酰氧基丙基;Y为甲氧基、乙氧基、甲酰氧基、乙酰氧基、丙酰氧基或烷基-或芳基氨基;并且R2,如果存在,为甲基、乙基、丙基、癸基或苯基的那些化合物。
在再一个实施方式中,所述不饱和硅烷化合物可以由式III表示
CH2=CHSi(OA)3(III)
其中A为具有1至8个碳原子,例如1至4个碳原子的烷基。
在本发明的另一个实施方式中,所述硅烷化合物,例如,可以是,乙烯基三甲氧基硅烷、乙烯基双甲氧基乙氧基硅烷、乙烯基三乙氧基硅烷、γ-(甲基)丙烯酰氧基丙基三甲氧基硅烷、γ-(甲基)丙烯酰氧基丙基三乙氧基硅烷、或乙烯基三乙酰氧基硅烷。
所述共聚合可以在引起两种单体共聚合的任何合适的条件下进行。
此外,所述共聚合可以在能够与所述两种单体共聚合的一种或多种其他共聚单体的存在下实施。这样的共聚单体包括,例如,羧酸乙烯基酯(如醋酸乙烯酯和新戊酸乙烯酯),α-烯烃(如丙烯、1-丁烯、1-己烯、1-辛烯和4-甲基-1-戊烯),(甲基)丙烯酸酯(如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯和(甲基)丙烯酸丁酯),烯属不饱和羧酸(如(甲基)丙烯酸、马来酸和富马酸),(甲基)丙烯酸衍生物(如(甲基)丙烯腈和(甲基)丙烯酰胺),乙烯基醚(如乙烯基甲基醚和乙烯基苯基醚),以及芳族乙烯基化合物(如苯乙烯和α-乙基苯乙烯)。
在本发明的再一个实施方式中,所述共聚单体可以是具有1-4个碳原子的单羧酸的乙烯酯,如醋酸乙烯酯,和/或具有1-4个碳原子的醇的(甲基)丙烯酸酯,如(甲基)-丙烯酸甲酯。
在本发明的又一个实施方式中,公开了所述共聚单体:丙烯酸丁酯、丙烯酸乙酯和/或丙烯酸甲酯。
在此公开的两种或更多种共聚单体,如任意的烯属不饱和化合物可以组合使用。术语“(甲基)丙烯酸”意图包括丙烯酸和甲基丙烯酸两者。所述共聚物的共聚单体的含量可以达到所述共聚物的70重量%,例如大约0.5重量%至35重量%,例如,大约1重量%至30重量%。
如果使用接枝聚合物,其可以通过分别在US3646155和US4117195中描述的两种方法的任意一种来制备。
所述含有可水解硅烷基团的聚烯烃,其包含在本发明的聚合物组合物中,可以包含0.001重量%至15重量%,例如,0.01重量%至5重量%,例如,0.1重量%至2重量%的硅烷化合物。
在本发明的另一个实施方式中,式I化合物的Ar是1、2、3或4个烷基取代的芳基,例如,2至3个烷基取代的芳基,或,例如,2个烷基取代的芳基。此外,所述芳基是苯基或萘基,例如萘基。
在本发明的实施方式中,Ar是被例如2个烷基取代的萘基。
此外,各烷基独立地为含有10至30个碳的直链或支链烷基,其中在所述烷基中的碳的总数在20至80个碳的范围内。
在本发明的另一个实施方式中,各烷基独立地为含有10至15个碳的直链烷基,其中在所述烷基中的碳的总数为20至60个碳的范围。
在本发明的再一个实施方式中,所述烷基中的任意两个可以经由桥联基团(如亚烷基)彼此连接。
所述硅烷醇缩合催化剂还可以是本文所述的式I化合物的衍生物,其中所述衍生物可以通过水解转化成式I化合物。所述衍生物例如可以是式I化合物的对应酸酐。或者,所述衍生物可以是已提供有可水解保护基团(例如乙酰基)的式I化合物。所述可水解保护基团可以通过水解除去。
在一个实施方式中,根据本发明的聚合物组合物包含,例如0.01重量%至5重量%,或,如0.01重量%至2重量%的量的所述表面活性剂相互作用添加剂。
在另一个实施方式中,根据本发明的聚合物组合物包含,例如,0.0001重量%至8重量%,0.0001重量%至6重量%,0.001重量%至2重量%,0.05重量%至1重量%,1重量%至8重量%或1重量%至6重量%的量的所述“至少一种”硅烷醇缩合催化剂。
在再一个实施方式中,其中所述聚合物组合物是根据本发明的硅烷醇缩合催化剂母料,所述硅烷醇缩合催化剂母料包含,例如0.2重量%至40重量%,或,如1重量%至35重量%的量的所述表面活性剂相互作用添加剂。
在又一个实施方式中,其中所述聚合物组合物是根据本发明的硅烷醇缩合催化剂母料,所述硅烷醇缩合催化剂母料包含,例如,0.7重量%至8重量%,0.7重量%至6重量%,1重量%至8重量%或1重量%至6重量%的量的所述“至少一种”硅烷醇缩合催化剂。
根据本发明的聚合物组合物可以进一步包含各种添加剂,例如,混溶性热塑性塑料、抗氧化剂、稳定剂、润滑剂、填料、过氧化物、硅烷和/或发泡剂。
例如,可以使用化合物或化合物的混合物作为抗氧化剂。所述抗氧化剂可以适当地为中性或酸性化合物,并且该化合物可以适当地包含空间位阻酚基团或脂肪族硫基团。在EP1254923中公开了这样的化合物并且这些化合物是用于稳定用硅烷醇缩合催化剂(例如,酸性硅烷醇缩合催化剂)交联的含有可水解硅烷基团的聚烯烃的合适的抗氧化剂。WO2005003199中公开了其他示例性的抗氧化剂。
此外,所述抗氧化剂可以以0.01重量%至3重量%,如0.05重量%至2重量%,或,如0.08重量%至1.5重量%的量存在于所述聚合物组合物中。
根据本发明,可以通过使可交联聚烯烃与一种或多种添加剂母料混合,将所述“至少一种”硅烷醇缩合催化剂、所述表面活性剂相互作用添加剂和所述可交联聚烯烃混合以制备本发明的聚合物组合物。所述一种或多种添加剂母料可以合适地包括本文所述的本发明的硅烷醇缩合催化剂母料。
所述混合可以通过任何已知的混合方法进行,包括用螺杆挤出机或捏合机挤出最终产品。
此外,所述一种或多种添加剂母料包含分别在其聚合物基体(例如聚烯烃基体)中浓缩形式的所述“至少一种”催化剂,所述表面活性剂相互作用添加剂和/或,任选地,另外的添加剂。
或者,所述“至少一种”催化剂,所述表面活性剂相互作用添加剂和所述,任选的,另外的添加剂中的一个或多个不需要以包含在母料中的形式被添加而是例如以液体形式被直接添加到用于制备本发明的聚合物组合物的体系中。
所述另外的,任选的,添加剂可以是如本文中已描述的那些。
所述一种或多种添加剂母料的聚合物基体或多种基体可以合适地作为本文中所述的硅烷醇缩合催化剂的聚合物基体。
此外,所述硅烷醇缩合催化剂母料、所述添加剂母料或多种母料包含浓缩形式的所述“至少一种”催化剂,所述表面活性剂相互作用添加剂和,任选地,另外的添加剂。用语“浓缩形式”在本文中是指所述“至少一种”催化剂,所述表面活性剂相互作用添加剂和所述任选的另外的添加剂,与在最终可交联聚合物组合物中它们的浓度相比,在所述母料中具有更高的浓度。
在本发明的另一个实施方式中,本文中所述的硅烷醇缩合催化剂母料或添加剂母料,例如,可以包含,例如,0.7重量%至8重量%,0.7重量%至6重量%,1重量%至8重量%或1重量%至6重量%的量的所述“至少一种”硅烷醇缩合催化剂。
进一步根据本发明,当本文中所述的硅烷醇缩合催化剂母料或添加剂母料与所述包含所述可交联聚烯烃的聚合物组合物混合时,所述硅烷醇缩合催化剂母料或所述添加剂母料可以以1重量%至10重量%,如2重量%至8重量%的量存在。
在本发明的再一个实施方式中,所述表面活性剂相互作用添加剂可以包含在作为色母料的添加剂母料中,或者,可选地,包含作为色母料的添加剂母料。
在本发明的另一个实施方式中,所述表面活性剂相互作用添加剂包括TiO2、CaCO3和/或炭黑(例如UV黑)。
在本发明的又一个实施方式中,所述表面活性剂相互作用添加剂包括受阻胺光稳定剂(HALS)。
本发明还涉及制备制品的方法,其中所述方法包括使用,例如挤出,本文所述的聚合物组合物。所述挤出可以在例如140℃至280℃的温度下进行。
在本发明的另一个实施方式中,公开了一种聚合物组合物,其中所述聚合物组合物包含交联的聚烯烃,其中所述交联的聚烯烃通过交联包含在本文所述的聚合物组合物中的可交联聚烯烃而制备。
在本发明的再一个实施方式中,公开了一种聚合物组合物,其中所述聚合物组合物包含在此所述的交联的聚烯烃,并且其中当根据EN60811-2-1:1999方法测定时,所述聚合物组合物具有小于175%的热固化伸长率(hotsetelongation)。
在本发明的又一个实施方式中,公开了一种聚合物组合物,其中所述聚合物组合物包含在此所述的交联的聚烯烃,并且其中所述聚合物组合物具有小于150%,130%或100%的热固化伸长率。
本发明的另一个实施方式涉及一种制品,例如涂层、导线或电缆,该制品包含本文所述的聚合物组合物。
本发明的又一个实施方式涉及本文所述的聚合物组合物的用途。
以下实施例举例说明本发明,但不意图限制本发明。
实施例
1.方法
a.熔体流动速率
根据ISO1133测定熔体流动速率(MFR)并以g/10min表示。在190℃下用2.16kg载荷测定乙烯聚合物的MFR(MFR2)。
b.热固化伸长率
根据IEC-60811-2-1(热固化方法和永久变形),在23℃和50%R.H交联几次之后,通过在200℃和0.2MPa的载荷下测定热变形来测定所述聚合物组合物的交联。
2.材料
基础树脂,其包含在所述聚合物组合物中,在本文的实施例中是乙烯乙烯基硅烷共聚物VisicoLE4423TM,即,含有可水解硅烷基团的可交联聚烯烃,由北欧化工股份公司(Borealis)提供,具有923kg/m3的密度和1.0g/10min的MFR2.16。
催化剂母料构成如下表1所示。DBSA(十二烷基苯磺酸),即,来自UngerFabrikker的UfacidK。CD-2180,即,C12-烷基化萘基磺酸的高疏水性混合物(即,选自本文所述的式I化合物中的硅烷醇缩合催化剂),来自KingIndustries,具有80%的活性含量。催化剂母料制备为具有等摩尔量的磺酸基团。用量以总催化剂母料的重量百分比给出。
催化剂载体是BAR717,即,乙烯丙烯酸丁酯共聚物,其由SpecialPolymersAntwerp提供。BAR717具有17重量%的丙烯酸丁酯含量和7.5g/10min的MFR2.16。
稳定剂是LowinoxCPL,来自科聚亚公司的酚类稳定剂,并且干燥剂是Dynasylan9116,HDTMS,Evonic生产的十六烷基三甲氧基硅烷。
在试验中使用的表面活性剂相互作用添加剂是2000-WT-50,一种由PolyOne提供的白色母料。2000-WT-50包含按重量计:30%-60%TiO2,10%-30%CaCO3,1%-5%无定形二氧化硅,1%-5%Al2O3,0.1%-1%石英。
表1
催化剂母料A | 催化剂母料B | |
BAR717(催化剂载体) | 86.1 | 83.3 |
DBSA | 3.5 | |
Nacure CD-2180 | 6.3 | |
稳定剂 | 6.4 | 6.4 |
干燥剂 | 3 | 3 |
3.样品制备
可以通过在130℃下在班伯里捏合机(Banburykneader)中使所述组分混合8分钟来制备催化剂母料。随后可以将混合物在布斯捏合机(Busskneader)上制粒。可以使用科林带挤出机(Collintapeextruder)挤出1.8mm的带,所述挤出机以50rpm,挤出区域150/160/170摄氏度的温度曲线运行。
表2.带的组成.
对比实施例1 | 对比实施例2 | 对比实施例3 | 发明实施例1 | |
LE4423 | 95 | 95 | 94 | 94 |
催化剂母料A | 5 | 5 | ||
催化剂母料B | 5 | 5 | ||
2000-WT-50 | 1 | 1 |
在90℃的水浴中或环境条件(23℃,50%RH)下处理所述带并且在施加0.2MPa的载荷15分钟后在200℃下测定热固化伸长率。用量以总组合物的重量百分比给出。
表3中给出热固化伸长试验的结果。如在例如IEC60502-1第2版和HD603A1中所给出,LV电缆绝缘的标准要求是<175%的热固化伸长率。
表3热固化伸长率
没有色母料的对比实施例1和2,满足所有热固化和交联要求。包含含有,可比较地,较少碳的高亲水性烷基苯磺酸催化剂和TiO2色母料的对比实施例3,样品在环境条件下交联而在热水浴中不交联(样品3在热固化炉中1分钟内断裂)。发明实施例1,其包含含有,可比较地,更多碳的烷基化萘基磺酸和TiO2色母料的高疏水性混合物,当样品在环境条件下和热水浴中交联时均满足所有的热固化要求。
Claims (16)
1.一种聚合物组合物,其包含表面活性剂相互作用添加剂,并且特征在于所述聚合物组合物进一步包含至少一种硅烷醇缩合催化剂,其中每种催化剂选自:
i)式I化合物
ArSO3H(I)
或其前体,其中
Ar是1至4个烷基取代的芳基,其中所述芳基是苯基或萘基,并且其中各烷基独立地为含有10至30个碳的直链或支链烷基,其中在所述烷基中的碳的总数在20至80个碳的范围内;
ii)选自i)的酸酐、酯、乙酰化物、环氧封端酯和胺盐的i)的衍生物,其可水解为相应的式I化合物;以及
iii)i)的金属盐,其中金属离子选自铜、铝、锡和锌。
2.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物是进一步包含聚合物基体的硅烷醇缩合催化剂母料。
3.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物进一步包含含有可水解硅烷基团的可交联聚烯烃。
4.根据权利要求1至3中任一项所述的聚合物组合物,其中式I化合物的Ar是萘基。
5.根据权利要求1至4中任一项所述的聚合物组合物,其中每种催化剂选自a)C12-烷基化萘基磺酸;
b)选自a)的酸酐、酯、乙酰化物、环氧封端酯和胺盐的a)的衍生物,其可水解为相应的化合物a);和/或
c)a)的金属盐,其中金属离子选自铜、铝、锡和锌。
6.根据权利要求1至5中任一项所述的聚合物组合物,其中所述聚合物组合物包含0.0001重量%至8重量%的量的所述“至少一种”硅烷醇缩合催化剂。
7.根据权利要求1至6中任一项所述的聚合物组合物,其中所述表面活性剂相互作用添加剂包括色母料。
8.根据权利要求1至7中任一项所述的聚合物组合物,其中所述表面活性剂相互作用添加剂包括TiO2、CaCO3和/或炭黑,例如UV黑。
9.根据权利要求1至8中任一项所述的聚合物组合物,其中所述表面活性剂相互作用添加剂包括受阻胺光稳定剂(HALS)。
10.根据权利要求1,3至9中任一项所述的聚合物组合物,其中所述含有可水解硅烷基团的可交联聚烯烃包括含有可水解硅烷基团的聚乙烯。
11.根据权利要求1,3至10中任一项所述的聚合物组合物,其中所述含有可水解硅烷基团的聚烯烃包含0.001重量%至15重量%的硅烷化合物。
12.根据权利要求1,3至11中任一项所述的聚合物组合物,其包含交联的聚烯烃,其中所述交联的聚烯烃通过交联包含在根据权利要求1,3至11中任一项所述的聚合物组合物中的所述可交联聚烯烃来制备。
13.根据权利要求12所述的聚合物组合物,当根据EN60811-2-1:1999方法测定时,所述聚合物组合物具有小于175%的热固化伸长率。
14.一种制品,例如,涂层、导线或电缆,其包含根据权利要求1至13中任一项所述的聚合物组合物。
15.一种制备制品的方法,其中所述方法包括使用,例如挤出,根据权利要求1至13中任一项所述的聚合物组合物。
16.根据权利要求1至13中任一项所述的聚合物组合物的用途。
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CN201480067492.4A Active CN105814134B (zh) | 2013-12-18 | 2014-12-17 | 包含含有可水解硅烷基团的可交联聚烯烃、催化剂和表面活性剂相互作用添加剂的聚合物组合物 |
Country Status (7)
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US (1) | US10233310B2 (zh) |
EP (1) | EP3083818B1 (zh) |
KR (2) | KR102194552B1 (zh) |
CN (1) | CN105814134B (zh) |
ES (1) | ES2947533T3 (zh) |
PL (1) | PL3083818T3 (zh) |
WO (1) | WO2015091702A1 (zh) |
Citations (3)
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WO2002012354A1 (en) * | 2000-08-03 | 2002-02-14 | King Industries, Inc. | Alkylaryl and arylalkyl monosulfonic acid catalysts for crosslinking polyethylene |
CN101548341A (zh) * | 2006-10-27 | 2009-09-30 | 北方技术股份有限公司 | 半导电性聚烯烃组合物 |
EP2657284A1 (en) * | 2012-04-27 | 2013-10-30 | Borealis AG | Additive masterbatch with a C3-C5 alpha-olefin homo- or copolymer comprised in the carrier |
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BE794718Q (fr) | 1968-12-20 | 1973-05-16 | Dow Corning Ltd | Procede de reticulation d'olefines |
GB1526398A (en) | 1974-12-06 | 1978-09-27 | Maillefer Sa | Manufacture of extruded products |
US4413066A (en) | 1978-07-05 | 1983-11-01 | Mitsubishi Petrochemical Company, Ltd. | Crosslinkable polyethylene resin compositions |
JPS5566809A (en) | 1978-11-13 | 1980-05-20 | Mitsubishi Petrochemical Co | Method of manufacturing crosslinked polyethylene resinncoated wire |
JPS5693542A (en) | 1979-12-27 | 1981-07-29 | Mitsubishi Petrochemical Co | Bridged polyethylene resin laminated film or sheet |
JPS5695940A (en) | 1979-12-28 | 1981-08-03 | Mitsubishi Petrochem Co Ltd | Ethylene polymer composition |
JPS57207632A (en) | 1981-06-16 | 1982-12-20 | Mitsubishi Petrochem Co Ltd | Crosslinkable polyethylene resin composition |
JPS5861129A (ja) | 1981-10-08 | 1983-04-12 | Sekisui Plastics Co Ltd | 発泡体の製造法 |
SE502171C2 (sv) | 1993-12-20 | 1995-09-04 | Borealis Holding As | Polyetenkompatibla sulfonsyror som silanförnätningskatalysatorer |
US6395837B1 (en) | 2000-08-03 | 2002-05-28 | King Industries, Inc. | Alkylated aryl disulfonic acid catalysts for crosslinking polyethylene |
US6538056B1 (en) * | 2000-10-10 | 2003-03-25 | Clariant International Ltd. | Polyolefin articles with long-term elevated temperature stability |
PT1433811E (pt) | 2001-05-02 | 2007-04-30 | Borealis Tech Oy | Utilização de compostos de polissulfureto para a estabilização de polímeros reticulados contendo grupos silano |
EP1641850A1 (en) | 2003-06-25 | 2006-04-05 | Union Carbide Chemicals & Plastics Technology Corporation | Moisture crosslinkable polymeric composition containing special antioxidants |
JP5415754B2 (ja) * | 2005-03-18 | 2014-02-12 | ダウ グローバル テクノロジーズ エルエルシー | 水分架橋性ポリマー組成物−改良された耐熱老化性能 |
ATE399187T1 (de) * | 2006-04-26 | 2008-07-15 | Borealis Tech Oy | Vernetzbare polyolefinzusammensetzung enthaltend hochmolekuaren silanolkondensationskatalysator |
-
2014
- 2014-12-14 US US15/105,506 patent/US10233310B2/en active Active
- 2014-12-17 WO PCT/EP2014/078321 patent/WO2015091702A1/en active Application Filing
- 2014-12-17 KR KR1020187018711A patent/KR102194552B1/ko active IP Right Grant
- 2014-12-17 CN CN201480067492.4A patent/CN105814134B/zh active Active
- 2014-12-17 ES ES14815345T patent/ES2947533T3/es active Active
- 2014-12-17 EP EP14815345.5A patent/EP3083818B1/en active Active
- 2014-12-17 KR KR1020167016174A patent/KR20160091928A/ko not_active Application Discontinuation
- 2014-12-17 PL PL14815345.5T patent/PL3083818T3/pl unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2002012354A1 (en) * | 2000-08-03 | 2002-02-14 | King Industries, Inc. | Alkylaryl and arylalkyl monosulfonic acid catalysts for crosslinking polyethylene |
CN101548341A (zh) * | 2006-10-27 | 2009-09-30 | 北方技术股份有限公司 | 半导电性聚烯烃组合物 |
EP2657284A1 (en) * | 2012-04-27 | 2013-10-30 | Borealis AG | Additive masterbatch with a C3-C5 alpha-olefin homo- or copolymer comprised in the carrier |
Also Published As
Publication number | Publication date |
---|---|
EP3083818A1 (en) | 2016-10-26 |
EP3083818B1 (en) | 2023-06-07 |
KR102194552B1 (ko) | 2020-12-24 |
US20160312012A1 (en) | 2016-10-27 |
WO2015091702A1 (en) | 2015-06-25 |
CN105814134B (zh) | 2019-03-26 |
KR20180077345A (ko) | 2018-07-06 |
KR20160091928A (ko) | 2016-08-03 |
PL3083818T3 (pl) | 2023-09-11 |
US10233310B2 (en) | 2019-03-19 |
ES2947533T3 (es) | 2023-08-11 |
US20170107356A2 (en) | 2017-04-20 |
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