CA2014005C - Process for stabilising polyolefins - Google Patents
Process for stabilising polyolefins Download PDFInfo
- Publication number
- CA2014005C CA2014005C CA002014005A CA2014005A CA2014005C CA 2014005 C CA2014005 C CA 2014005C CA 002014005 A CA002014005 A CA 002014005A CA 2014005 A CA2014005 A CA 2014005A CA 2014005 C CA2014005 C CA 2014005C
- Authority
- CA
- Canada
- Prior art keywords
- component
- stabiliser
- process according
- tert
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 23
- 230000003019 stabilising effect Effects 0.000 title claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000000155 melt Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- -1 glyceryl monocarboxylic acid ester Chemical class 0.000 claims description 40
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 229920001155 polypropylene Polymers 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 239000005662 Paraffin oil Substances 0.000 claims description 11
- 239000002530 phenolic antioxidant Substances 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000001993 wax Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 239000006078 metal deactivator Substances 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- AZSKHRTUXHLAHS-UHFFFAOYSA-N tris(2,4-di-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C AZSKHRTUXHLAHS-UHFFFAOYSA-N 0.000 claims 1
- 238000002844 melting Methods 0.000 description 56
- 230000008018 melting Effects 0.000 description 55
- 239000000306 component Substances 0.000 description 26
- 239000011777 magnesium Substances 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 3
- 229940116224 behenate Drugs 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WBSRIXCTCFFHEF-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinic acid Chemical compound CCOP(O)(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WBSRIXCTCFFHEF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 2
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 2
- 229940075507 glyceryl monostearate Drugs 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KJYSXRBJOSZLEL-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KJYSXRBJOSZLEL-UHFFFAOYSA-N 0.000 description 1
- MQQKTNDBASEZSD-UHFFFAOYSA-N 1-(octadecyldisulfanyl)octadecane Chemical compound CCCCCCCCCCCCCCCCCCSSCCCCCCCCCCCCCCCCCC MQQKTNDBASEZSD-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- NJEIFTCEBWBIEJ-UHFFFAOYSA-N 2-[2-[2-[2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound C(C)(C)(C)C=1C=C(C=C(C=1O)C(C)(C)C)CCC(=O)OCCOC1=C(C=CC=C1)C(C)(C)C1=C(C=CC=C1)OCCOC(CCC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)=O NJEIFTCEBWBIEJ-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003081 coactivator Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 239000011988 third-generation catalyst Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
A process for stabilising olefin polymers having a mean particle diameter of from 1 to 5 mm that have been polymerised on carrier catalysts, which comprises treating the polyolefins with a stabiliser mixture prepared by heating to from 120 to 260°C a mixture containing a) at least one carrier and/or b) at least one stabiliser that melts at from 20 to 120°C and c) at least one stabiliser that melts at from 120 to 260°C, and then cooling said mixture until solidified, components b) and c) being different.
Description
A process for stabilising polyolefins The present invention relates to a process for stabilising olefin polymers having a mean particle diameter of from 1 to 5 mm that have been polymerised on carrier catalysts.
JP-A-84/150 719 describes a process for stabilising polypropylene powder in which the polypropylene powder, the stabilisers and a carrier are homogenised in a mixer with the application of heat.
EP-A-281 189 describes a process for producing a hydrolysis-resistant stabiliser mixture consisting of a phosphate and a phenolic antioxidant, and the use of that stabiliser mixture for stabilising polypropylene powder. Pulverulent polyolefin has to be granulated in an extruder before being shaped. During the granulation, stabilisers and other processing auxiliaries are added to the polymer.
Unstabilised granular-type polyolefins that have been produced by polymerising olefins on solid carrier catalysts have been commercially available for some time. Since these polyolefins are obtained in granular form when manufactured, they do not need to be extruded in a subsequent processing step, unless incorporation of the stabilisers and the process-ing auxiliaries necessitates melting in order to ensure an adequate distribution of the additive in the polymer.
In many cases the addition of stabilisers during the olefin polymerisa-tion causes interference with the polymerisation and discolouration of the polymers.
JP-A-84/150 719 describes a process for stabilising polypropylene powder in which the polypropylene powder, the stabilisers and a carrier are homogenised in a mixer with the application of heat.
EP-A-281 189 describes a process for producing a hydrolysis-resistant stabiliser mixture consisting of a phosphate and a phenolic antioxidant, and the use of that stabiliser mixture for stabilising polypropylene powder. Pulverulent polyolefin has to be granulated in an extruder before being shaped. During the granulation, stabilisers and other processing auxiliaries are added to the polymer.
Unstabilised granular-type polyolefins that have been produced by polymerising olefins on solid carrier catalysts have been commercially available for some time. Since these polyolefins are obtained in granular form when manufactured, they do not need to be extruded in a subsequent processing step, unless incorporation of the stabilisers and the process-ing auxiliaries necessitates melting in order to ensure an adequate distribution of the additive in the polymer.
In many cases the addition of stabilisers during the olefin polymerisa-tion causes interference with the polymerisation and discolouration of the polymers.
The present invention relates to a process for stabilising olefin polymers having a mean particle diameter of from 1 to 5 mm that have been polymerised on carrier catalysts, which comprises treating the polyolefins with a stabiliser mixture prepared by heating to from 120 to 260°C a mixture containing components a), b) and c) or components b) and c) with component a) being at least one carrier, component b) being at least one stabiliser that melts at from 20 to 120°C, and component c) being at least one stabiliser that melts at from 120 to 260°C, and then cooling said mixture until solidified, components b) and c) being different.
Component b) can where appropriate assume the function of component a) as a carrier.
The ratio by weight of a:c is preferably from 0.1:1 to 4:1, especially from 0.5:1 to 2:1, and the ratio by weight of b:c is, for example, from 4:1 to 0.1:1 or from 2:1 to 0.1:1, preferably from 1:1 to 0.1:1.
A process in which the stabiliser mixture used contains components a), b) and c) is preferred.
The carrier is preferably a wax, paraffin oil or a glyceryl monocarboxylic acid ester. The following may be mentioned as examples of suitable carriers= polyethylene, polypropylene (for example atactic), olefinic copolymers (for example copolymers of propylene, such as propylene/ethylene copolymer or propylene/butene-1 copolymer), ethylene/vinyl acetate copolymers, ethylene/(unsaturated carboxylic acid 201 4flfl5 - 2a -ester) copolymers (for example ethylene/methyl methacrylate copolymer), ethylene/(unsaturated carboxylic acid metal salt) copolymers (for example ethylene/magnesium acrylate copolymer or ethylene/ainc acrylate copolymer), polyethylene or polypropylene each modified with unsaturated carboxylic acids, such as, for example, maleic acid anhydride, petroleum, paraffin oil, polyalkylene glycol, such as, for example, polyethylene glycol, polypropylene glycol etc., or glyceryl monocarboxylic acid ester, preferably glyceryl monostearate.
~f;
F
Component b) can where appropriate assume the function of component a) as a carrier.
The ratio by weight of a:c is preferably from 0.1:1 to 4:1, especially from 0.5:1 to 2:1, and the ratio by weight of b:c is, for example, from 4:1 to 0.1:1 or from 2:1 to 0.1:1, preferably from 1:1 to 0.1:1.
A process in which the stabiliser mixture used contains components a), b) and c) is preferred.
The carrier is preferably a wax, paraffin oil or a glyceryl monocarboxylic acid ester. The following may be mentioned as examples of suitable carriers= polyethylene, polypropylene (for example atactic), olefinic copolymers (for example copolymers of propylene, such as propylene/ethylene copolymer or propylene/butene-1 copolymer), ethylene/vinyl acetate copolymers, ethylene/(unsaturated carboxylic acid 201 4flfl5 - 2a -ester) copolymers (for example ethylene/methyl methacrylate copolymer), ethylene/(unsaturated carboxylic acid metal salt) copolymers (for example ethylene/magnesium acrylate copolymer or ethylene/ainc acrylate copolymer), polyethylene or polypropylene each modified with unsaturated carboxylic acids, such as, for example, maleic acid anhydride, petroleum, paraffin oil, polyalkylene glycol, such as, for example, polyethylene glycol, polypropylene glycol etc., or glyceryl monocarboxylic acid ester, preferably glyceryl monostearate.
~f;
F
Depending on the nature of the carrier, it melts, for example, at from 0 to 120°C, from 10 to 120°C or from 20 to 100°C. It is preferable to use a carrier that melts either at from 0 to 79°C (for example paraffin oil) or at from 80 to 105°C (for example wax).
Component b) is preferably a sterically hindered phenolic antioxidant, a phosphorus-containing stabiliser, a sterically hindered amine, a benzo-triazole, a benzophenone, a thiodicarboxylic acid diester and/or a dialkyl disulfide.
The following stabilisers are examples of component b):
Sterically hindered phenolic antioxidants:
A) 2,2-Bis(3',5'-di-tert-butyl-4'-hydroxyphenylpropionyloxyethoxyphenyl)-propane (H3C)3C~
HO-~\~ ~~~-CHZCHZ-~-0-CHZCHZ-0-~~~ ~j.
_. .-. ~H
(H3C)sC/~
melting point: 100-102°C
B) Tetrakis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl)methane (H3C)3C~
.-.
HO-~~ j~-CHZCHZ-~-0-CHz C
-.
(H3C)3C~.
Component b) is preferably a sterically hindered phenolic antioxidant, a phosphorus-containing stabiliser, a sterically hindered amine, a benzo-triazole, a benzophenone, a thiodicarboxylic acid diester and/or a dialkyl disulfide.
The following stabilisers are examples of component b):
Sterically hindered phenolic antioxidants:
A) 2,2-Bis(3',5'-di-tert-butyl-4'-hydroxyphenylpropionyloxyethoxyphenyl)-propane (H3C)3C~
HO-~\~ ~~~-CHZCHZ-~-0-CHZCHZ-0-~~~ ~j.
_. .-. ~H
(H3C)sC/~
melting point: 100-102°C
B) Tetrakis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl)methane (H3C)3C~
.-.
HO-~~ j~-CHZCHZ-~-0-CHz C
-.
(H3C)3C~.
melting point: 110-120°C
C) n-Octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate (H3C)3C~
HO-~\~ ~%~-CHZCHz-~-0-C1BH3~-n (H3C)aC~.-.
melting point: 50-55°C
D) Triethyleneglycol-bis(3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)-propionate) (H3C)3C\ /C(CH3)3 HO-~~~ ~j~-CHZCHz-~-0-(CHZCHz-O~~-CHzCHz-~~~ ~j~-OH
-. ._.
HaC/~ \CH3 melting point: 67-79°C
E) 1,5-Bis(3',5'-di-tert-butyl-4'-hydroxyphenylpropionyloxy~-3'-thia-pentane (HaC)aC\ /C(CH3)a HO-~~~ ~j~-CHzCHz-~-O-CHzCHz-S-CHZCHz-0-~-CHzCHz-~~~ ~j~-OH
(HaC)3C/.-. ~=~\C(CH3)a melting point: 63-68°C
Phosphorus-containing stabilisers:
F) Tetrakis(2,4-di-tert-butylphenylj-diphenylene diphosphonite j (CH3)a (H3C)aC\
(H3C)aC-~~. .~ P-~~.-.\ ~/~-~\ _P 0-~/. ~~ -C(CHa)s \ /~ \ /~ \ /~ \ /~
.-. ._. ._. .-.
z z melting point: 75-95°C
G) Distearylpentaerythritol diphosphite /0-CHz\ /CHz 0\ _ Ha~Cla-0-P\ /C\ /P 0-C18H3~
O-CH z CH z-0 melting point: 40-60°C
C) n-Octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate (H3C)3C~
HO-~\~ ~%~-CHZCHz-~-0-C1BH3~-n (H3C)aC~.-.
melting point: 50-55°C
D) Triethyleneglycol-bis(3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)-propionate) (H3C)3C\ /C(CH3)3 HO-~~~ ~j~-CHZCHz-~-0-(CHZCHz-O~~-CHzCHz-~~~ ~j~-OH
-. ._.
HaC/~ \CH3 melting point: 67-79°C
E) 1,5-Bis(3',5'-di-tert-butyl-4'-hydroxyphenylpropionyloxy~-3'-thia-pentane (HaC)aC\ /C(CH3)a HO-~~~ ~j~-CHzCHz-~-O-CHzCHz-S-CHZCHz-0-~-CHzCHz-~~~ ~j~-OH
(HaC)3C/.-. ~=~\C(CH3)a melting point: 63-68°C
Phosphorus-containing stabilisers:
F) Tetrakis(2,4-di-tert-butylphenylj-diphenylene diphosphonite j (CH3)a (H3C)aC\
(H3C)aC-~~. .~ P-~~.-.\ ~/~-~\ _P 0-~/. ~~ -C(CHa)s \ /~ \ /~ \ /~ \ /~
.-. ._. ._. .-.
z z melting point: 75-95°C
G) Distearylpentaerythritol diphosphite /0-CHz\ /CHz 0\ _ Ha~Cla-0-P\ /C\ /P 0-C18H3~
O-CH z CH z-0 melting point: 40-60°C
Stericallv hindered amines:
H) Bis(2,2,6,6-tetramethyl-4-piperidinyl]sebacate H3C~ /CH3 H3C~ /CH3 HN\~ ~ j~-0-~-(CHz ) s-~-0-.\. ~~H
H3C~~~CH3 H3C~~~~CH3 melting point: 82-86°C
I) Bis[1,2,2,6,6-pentamethyl-4-piperidinyl]sebacate H3C~ /CH3 H3C~ /CH3 H3C-N\. '~~-0-~-(CHz)s-~-0-.\.-.~-CH3 H3C~~~CH3 H3C~~~CH3 melting point: 20°C
J) Bis(2,2,6,6-tetramethyl-4-piperidinyl]succinate H3C~ /CH3 H3C~ /CH3 HN\~ ~ j~-0-~-( CHz ) z-~-0-.\. ~~H
H3C~~~CH3 H3C~~/~CH3 melting point: 120°C
K) Condensate of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid HaC~ j Ha ~/ H
HOCHZCHz-N\~ ~j~~ + HO-~-(CHz)z-~-OH
~ OH
H3C~~~CH3 melting point: 55-70°C
H) Bis(2,2,6,6-tetramethyl-4-piperidinyl]sebacate H3C~ /CH3 H3C~ /CH3 HN\~ ~ j~-0-~-(CHz ) s-~-0-.\. ~~H
H3C~~~CH3 H3C~~~~CH3 melting point: 82-86°C
I) Bis[1,2,2,6,6-pentamethyl-4-piperidinyl]sebacate H3C~ /CH3 H3C~ /CH3 H3C-N\. '~~-0-~-(CHz)s-~-0-.\.-.~-CH3 H3C~~~CH3 H3C~~~CH3 melting point: 20°C
J) Bis(2,2,6,6-tetramethyl-4-piperidinyl]succinate H3C~ /CH3 H3C~ /CH3 HN\~ ~ j~-0-~-( CHz ) z-~-0-.\. ~~H
H3C~~~CH3 H3C~~/~CH3 melting point: 120°C
K) Condensate of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid HaC~ j Ha ~/ H
HOCHZCHz-N\~ ~j~~ + HO-~-(CHz)z-~-OH
~ OH
H3C~~~CH3 melting point: 55-70°C
Benzotriazoles:
L) 2-(2'-Hydroxy-5'-tert-octyl)benzotriazolel ~~\
I I ~-.\./.\N .\.__ /
~\CeHl -t melting point: 103-104°C
M) 2-(2'-Hydroxy-3',5'-di-tert-pentyl)benzotriazole2 ./~\ QH j SH11-t I I ~- /~ ~\
~\CsHii-t melting point: 79-87°C
Benzophenone:
N) 2-Hydroxy-4-octyloxybenzophenone ~H
%.\ _ _ %.\
I II ~ I II
Hm C80/~~,/.
melting point: 47°C
Thiodicarboxvlic acid diesters:
0) Dilauryl thiodipropionate Hz5C1z00CCHzCHz-S-CHzCHZC00C1zHzs melting point: 40-45°C
1 tert-octyl = 1,1,3,3-tetramethyl-1-butyl tert-pentyl = 1,1-dimethyl-1-propyl P) Dimyristyl thiodipropionate Hz9C1400CCHZCHz-S-CHZCHZCOOC14Hz9 melting point: 44-48°C
Q) Distearyl thiodipropionate H37C1800CCHzCHz-S-CHZCHZCOOC18H37 melting point: 57-67°C
Dialkyl disulfides:
R) Distearyl disulfide H37C18-$$-C18H37 melting point: ~66°C
Component b) is especially preferably sterically hindered phenolic antioxidant.
Component c) is preferably a sterically hindered phenolic antioxidant, a metal deactivator, a sterically hindered amine, a benzotriazole, a phosphorus-containing stabiliser, a nickel-containing UV-absorber and/or a metal salt of a C16-Czz-fatty acid.
The following stabilisers are examples of component c):
_$_ Sterically hindered phenolic antioxidant:
a) 1,3,5-Trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene H3C ~ CH3 /C(CHa)s \ /.\ / -I II in which R = -CHz-~~~ ~j~-OH
R/'~ /'~ .-.\
1~ C(CH3)3 melting point: 242-245°C .
f3) 1,3,5-Tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)isocyanurate ~\ /R /C(CH3)a in which R = -CHz-~~1 ~j~-OH
._.\
C(CH3)3 melting point: 218-223°C
y) 1,3,5-Tris(2',6'-dimethyl-4'-tert-butyl-5'-hydroxybenzyl)isocyanurate /R H3C\ _ in which R = -CHz-~~~ ~j~-C(CH3)3 /'~~~ .-0 0 H3C/ ~\OH
melting point: 145-155°C
d) 1,2-Bis[3',3'-bis(4"-hydroxy-5"-tert-butylphenyl)butanoyloxy)ethane QH
/~\ /C(CH3)a I II
.\ /.
H3C-~-CHz-~-~CHz ~~\
I II
~\ /~\C(CHa)a ~H
z melting point: 170°C
e) Bis(3-tert-butyl-4-hydroxy-6-methylphenyl)sulfide (H3C)3C\ /C(CH3)3 HO-~\. .~.-S-,\._.~~-OH
._ ._.
melting point: 161°C
2-(2'-Hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-methyl-6-tert-butyl-phenyl acrylate QH CHZ ~OCCH=CHz (HaC)aC\ /~\ / ~ /~\ /C(CHa)a I II I II
.\ /. .\ /.
melting point: 130-132°C
n) 1,1,3-Tris[3'-tert-butyl-4'-hydroxy-6'-methylphenyl]butane (H3C)3C\ /C(CH3)3 HO-.\._.~~ H ~\. ~~._OH
._. HZ ._.
H3C HCH3 C~3 H3C\ ~~\
I II
~\ /~\C(CHa)s ~H
melting point: 182.5-190°C
B) 2,4-Di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate /C(CHs)s j (CHa)s (HaC)sC_~~._./~ ~~ ~\._~/~ OH
\C(CHs)a melting point: 190°C
Metal deactivators:
1) N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl]hydrazine (HaC)aC\ /C(CH3)a .-.
HO-~~ j~-(CHz)z-~-NHNH-~-(CHz)z-~~~ ~j~-OH
.-. ._ (H3C)3C/ ~\C(CH3)a melting point: 224-229°C
K) N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxyethyl]oxalic acid diamide (HaC)aC\
H~~~~ ~j~-(CHz)2-~-0-(CHz)z-~-(H3C)3C~~-.
melting point: 173°C
Sterically hindered amines:
Poly(2-(N,N-bis(2',2',6',6'-tetramethyl-4'-piperidinyl)hexamethylene-diamino-4-morpholino-1,3,5-triazin-6-yl]
(CHz)6 ~ ~N\
H3C\I/~\I% H3 H3C\I/~\I% H3 H3C~~~~\CH3 H3C~~~~\CH3 .\0/.
n melting point: 110-130°C
u) Poly[2-(N,N-bis(2',2',6',6'-tetramethyl-4'-piperidinyl)hexamethylene-diamino-4-tert-octyl-1,3,5-triazin-6-yl]
~T ( C H z ) s ~1 ~N\
H3C\I/~\I/CH3 H3C\I/~\I/CH3 \
HN-C8H1~-t H3C/~~~\CH3 H3C/~\~~\CH3 n melting point: 120-150°C
v) 1,5,8,12-Tetrakis[2',4'-bis(1",2",2",6",6"-pentamethyl-4"-piperidinyl-(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetraazadodecane H-~-(CHz)a-~-(CHz)zy-(CHz)a-yH
H3C\ /CH3 r4H9 /.-~NN' .~-CH
.
~ a \.
.
_ HaC/
~N .\ \CH3 R - . HaC\ /CH3 -.~-CHa H \.
9 \CH3 melting point: 150°C
Bis[1',2',2',6',6'-pentamethyl-4'-piperidinyl]-2-butyl-2-(3",5"-di-tert-butyl-4"-hydroxybenzyl)malonate HaC\ j H3 /
(H3C)aC\ ~~ ~\~- -CH3 /~\
HO-~~. ~~ -CHz- -C4H9 H3C CH3 \ -_~/~ H3C\ % Ha (HaC)aC/~ 00 /. .~-CH3 .\ _ H3C/~\CH3 melting point: 146-150°C
o) 1,2-Bis[3',3',5',5'-tetramethyl-2'-oxo-1',4'-diazinan-1'-yl]ethane HaC\ /CHa~% 0~ HaC\ j H3 HN\~ ~-(CHz)z-~~ ~/NH
H3C/~\CH3. .H3C/.\CH3 melting point: 136°C
~r ) HjC\ /CH3 0 - \~~
H3C CH3 \~ ~/~\~ ~\~ ~/NH
\ /_ / \ /~\~~ HjC/~\CH3 ~J ~\ _ _ HN\~ /~
~ ~ 0 H3C/~\CH3 melting point: 270°C
Benzotriazoles:
p) 2-(2'-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole ~ H C(CH3)3 \ ~_ /
I I ~-~j~ ~~
\~/.\N \~- /.
~\C(CH3)a melting point: 150-155°C
Q) 2-(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5'-chlorobenzotriazole C1\ /~\ QH /C(CH3)a I j - /~
~~ /~~ ~\ _ /
~ ~\CH3 melting point: 137-140°C
i) 2-(2'-Hydroxy-3',5'-di-tert-butylphenyl)-5'-chlorobenzotriazole C1\ /~\ QH /C(CH3)a I j .\ /.\,. .\ /
\C(CHs)a melting point: 154-158°C
Phosphorus-containing stabilisers:
v) Tris[2,4-di-tert-butylphenyl]phosphite (H3C)3C-~~~ ~j'- P
~ ~\C(CH3)a melting point: 180-185°C
Bis[2,4-di-tert-butylphenyl]pentaerythritol diphosphite C(CH3)a (HaC)aC
_ / 0-. -0 \ _ (HaC)aC-'/~ ~\ -0P/ \~/~ \P-C-~~. '~ -C(CH3)a \._./~ \~~/ \~-Q/ \._~/.
melting point: 160-175°C
X) Bis[2,6-di-tert-butyl-4-methylphenyl]pentaerythritol diphosphite /C(CHa)a (HsC)3C\
~ -' 0- ~ -0 H3C-~j ~ -0-P/ \ /~ \P-~~/._.\ -CH3 \~_- /~ \~~/~\~-0/ \ -~/~
~\C(CH3)a (H3C)3C/~
melting point: 235°C
V~ ) ~Ha (H3C)3C~ ~'~ ~ ~ ~'~ /C(CH3)3 I II ~ II
.\ /.\0 O/.\ /.
(H3C)3~ \~/ ~(CH3)3 melting point: 200-201°C
cu) Calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester (H3C)3C~
CzHs _ HO-'~~_./~ CHZ-~ 0 Ca2+
(H3C)3C/~-melting point: >150°C
A) Nickel salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester (H3C)jC~ _ CzHs _ HO-~~~ ~ j~-CH2- 0 Ni2+
(H3C)3C/~-.
melting point: >180°C
Nickel-containing UV-absorbers:
B) 2,2'-Thio-bis(4-tert-octylphenolato~-butylamino nickel (II) t-H17C8-.\._.~ 0 jS Ni-NHC4H9 t-H17C8-.\.-.~ 0 melting point: 258°C
Metal salts of C,s-C~~-fatty acids:
t) Ca palmitate, melting point: 150-155°C (decomposition) D) Mg palmitate, melting point: 121°C
E) Zn palmatate, melting point: 125°C
Z) Ca stearate, melting point: 180°C
H) Mg stearate, melting point: 145°C
A) Zn stearate, melting point: 130°C
I) Ca behenate, melting point: 150°C
K) Mg behenate, melting point: 150°C
A) Zn behenate, melting point: 125°C
A phosphorus-containing stabiliser, especially a phosphate, is of interest as component c).
The invention relates especially preferably to a process in which the stabiliser system used contains components a), b) and c) and in which component b) is a sterically hindered phenolic antioxidant and compo-nent c) is a phosphate.
According to another preference, component b) is n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate and/or tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]methane and component c) is tras[2,4-di-tert-butylphenyl]phosphate.
Also preferred is a process in which component b) is a stabiliser that melts at from 50 to 120°C and component c) is a stabiliser that melts at from 180 to 200°C and the stabiliser mixture as heated to from 180 to 200°C.
Components a), b) and c) are known and are for the most part commercially available products.
Olefins that can be polymerised on carrier catalysts are, for example, ethylene or a-olefins, especially propylene, 1-butene, 4-methylpentene-1 or 5-methylhexene-1, and mixtures of olefins, such as, for example, ethylene/propylene or propylene in admixture with smaller amounts of higher a-olefins.
Polyethylene, polypropylene, copolymers of ethylene and copolymers of propylene, especially polyethylene and polypropylene, each applied to carrier catalysts, are of interest.
The polymerisation catalysts used, which are frequently referred to as third generation catalysts, are advantageously solid catalysts of a particular particle size, such as, for example, those described in DE-A-29 33 997 and DE-A-26 41 960. They consist, for example, of an anhydrous magnesium dihalide in active form and a titanium compound.
Magnesium dihalide in active form denotes one in the X-ray spectrum of which the line of strongest reflection is broadened compared with the corresponding line in the spectrum of inactive magnesium halide.
Preferably, magnesium dichloride or magnesium dibromide is used as magnesium dihalide. The titanium compound contains preferably at least one titanium-halogen bond, the use of titanium tetrachloride being especially preferred.
The titanium compound can be used in combination with an electron donor, for example a carboxylic acid ester, such as that described in EP-A-45 977.
After reaction of the magnesium halide component with the titanium compound and, where appropriate, with the electron donor, the excess titanium compound and the excess electron donor are advantageously washed out with an inert solvent, for example with hexane or heptane.
The catalyst prepared in this manner is activated by reaction with an aluminium alkyl, which is preferably used in the form of a solution in an alkane. Examples of suitable aluminium alkyls are A1(CzHs)a or A1(CaH9)3.
There may be added as coactivator an electron donor such as, for example, an organic silicon compound that contains at least one Si-0-C bond, such as that described, for example, in EP-A-45 977. Examples of such silicon compounds are phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldi-methoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and ethyl-trimethoxysilane.
The polymerisation with these catalysts can be carried out according to known methods in liquid or gaseous phase. The liquid phase may be, for example, an aliphatic hydrocarbon, or the liquid monomer itself.
Spherical polymerised polyolefins are also described, for example, in P. Galli, P.C. Barbe and L. Noristi; "High Yield Catalysts in Olefin Polymerization", Die Angewandte Makromolekulare Chemie 120 (1984), p. 73-90 (No. 1935).
The diameter of the olefin polymers polymerised on carrier catalysts is preferably from 2 to 5 mm, especially from 2 to 3 mm.
The melting point of these granular-type polyolefins is, for example, from 140 to 165°C.
The concentration of the stabiliser mixtures in the polyolefin to be stabilised is preferably from 0.01 to 5 % by weight, especially from 0.05 to 1 % by weight.
Before incorporation into the polyolefin, it is advantageous to heat the stabiliser system until a milky solution has formed. This milky solution is a suspension of component c) in a) and/or b). For stabilisation, the polyolefin is stirred, for example for from 2 to 10 minutes, in a suitable device (preferably a mixer) with the stabiliser system, which has a temperature of, for example, from 60 to 120°C, preferably from 100 to 120°C, especially from 100 to 110°C, and then cooled.
Advantage-ously, the polyolefin is heated, for example to approximately from 60 to 120°C, before stabilisation.
The temperature of the polyolefin may be, for example, from 60 to 79°C if the stabiliser system contains as carrier a substance that melts at approximately from 0 to 79°C, such as, for example, paraffin oil, or if the stabilizer system has subsequently been treated with paraffin oil.
The ratio by weight of stabiliser system to paraffin oil is in the latter case, for example, from 1:1 to 3:1. In the case of subsequent treatment of the stabiliser system with paraffin oil, the stabiliser system is advantageously stirred into hot paraffin oil (from 100 to 120°C) and then stirred (for example for from 15 to 30 minutes) until a homogeneous mixture is obtained which can be used for the stabilisation of the polyolefin.
If a substance that melts at approximately from 80 to 110°C is used as carrier, such as, for example, wax, it is advantageous if the temperature of the polyolefin is, for example, from 80 to 120°C, preferably from 80 to 110°C.
The preparation of the stabiliser system is advantageously carried out by mixing components a) and/or b) and c). The mixture is heated, for example to from 120 to 260°C, preferably with stirring. The resulting melt is stirred, for example, for from 2 to 15 minutes, preferably from 8 to 12 minutes, and then cooled until it solidifies, which occurs, for example, at a temperature of from 0 to 30°C. The cooling can be effected, for example, with cold water or some other inert liquid, or with nitrogen or some other inert gas. It is also possible to cool the melt, for example, using a cold metal plate.
The preparation of the stabiliser system can also be effected, for example, in a kneader, in which case the stabiliser mixture is obtained in the form of a granulate.
The following Examples further illustrate the invention.
Example 1: Preparation of the stabiliser mixtures.
Stabiliser mixture I:
20 g of n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 50 g of tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]-methane and 100 g of tris[2,4-di-tert-butylphenyl]phosphite as well as 200 g of polyethylene wax (melting point according to ASTM D-3104:
102°C, hardness according to ASTM D-5: 7.0 dmm, density according to ASTM D-1505: 0.91 g/cc, viscosity according to Brookfield at 140°C:
180 cps) are mixed together and heated to 200°C. The molten material is stirred at that temperature for 10 minutes. The mixture is subsequently cooled, also with stirring, and solidifies.
Stabiliser mixture II:
II is prepared analogously to I using glyceryl monostearate instead of the wax.
Stabiliser mixture III:
III is prepared analogously to I using distearyl thiodipropionate instead of the polyethylene wax.
Stabiliser mixture IV:
IV is prepared analogously to I using 50 g of polyethylene wax instead of 200 g of polyethylene wax.
Stabiliser mixture V:
V is prepared analogously to IV, the mixing and heating being effected in an extruder ( BUSS-KO-KNETER) and the additive mixture being prepared in the form of a granulate.
Examples 2a-2c: Stabilisation of spherical polypropylene pellets.
a) 1000 g of spherical polypropylene ( Moplen SPL 12) are heated to 104°C
for 7 minutes in a~enschel mixer (capacity: 5000 ml). 3.7 g of the stabiliser mixture given in Table la, which have previously been melted at 104°C, are added. The mixture is stirred for 2 minutes and then cooled. The stabilised polypropylene pellets are subjected to oven ageing at 149°C for 30 h. The test results are given in Table la.
Discolouration of the polypropylene pellets indicates inadequate stabili-sation.
Table la:
Stabilizer 30 h oven ageing at 149C
mixture discolouration I no discolouration II no discolouration III no discolouration b) 1000 g of spherical polypropylene ( Moplen SPL 12) are heated to 65°C
for 3 minutes in ~Henschel mixer (capacity: 5000 ml). 3.7 g of the stabiliser mixture given in Table lb, which have previously been heated to 104°C, are added. Further processing and testing are carried out as in a). The test results are given in Table lb.
Table lb:
Stabilizer 30 h oven ageing at 149C
mixture discolouration III no discolouration c) 1000 g of sphe ~ al polypropylene ( Moplen SPL 12) are heated to 65°C
for 3 minutes in a Henschel mixer (capacity: 5000 ml).
2.2 g of the stabiliser mixture given in Table lc are added to 1 g of hot paraffin oil (110°C) and the resulting mixture is stirred at that temperature for 20 minutes. The mixture is then added to the poly-propylene (65°C) and the mixture is stirred for 2 minutes and then cooled. The polypropylene pellets are tested as in a). The test results are given in Table lc.
Table lc:
Stabilizer 30 h oven ageing at 149C
mixture discolouration IV no discolouration V no discolouration
L) 2-(2'-Hydroxy-5'-tert-octyl)benzotriazolel ~~\
I I ~-.\./.\N .\.__ /
~\CeHl -t melting point: 103-104°C
M) 2-(2'-Hydroxy-3',5'-di-tert-pentyl)benzotriazole2 ./~\ QH j SH11-t I I ~- /~ ~\
~\CsHii-t melting point: 79-87°C
Benzophenone:
N) 2-Hydroxy-4-octyloxybenzophenone ~H
%.\ _ _ %.\
I II ~ I II
Hm C80/~~,/.
melting point: 47°C
Thiodicarboxvlic acid diesters:
0) Dilauryl thiodipropionate Hz5C1z00CCHzCHz-S-CHzCHZC00C1zHzs melting point: 40-45°C
1 tert-octyl = 1,1,3,3-tetramethyl-1-butyl tert-pentyl = 1,1-dimethyl-1-propyl P) Dimyristyl thiodipropionate Hz9C1400CCHZCHz-S-CHZCHZCOOC14Hz9 melting point: 44-48°C
Q) Distearyl thiodipropionate H37C1800CCHzCHz-S-CHZCHZCOOC18H37 melting point: 57-67°C
Dialkyl disulfides:
R) Distearyl disulfide H37C18-$$-C18H37 melting point: ~66°C
Component b) is especially preferably sterically hindered phenolic antioxidant.
Component c) is preferably a sterically hindered phenolic antioxidant, a metal deactivator, a sterically hindered amine, a benzotriazole, a phosphorus-containing stabiliser, a nickel-containing UV-absorber and/or a metal salt of a C16-Czz-fatty acid.
The following stabilisers are examples of component c):
_$_ Sterically hindered phenolic antioxidant:
a) 1,3,5-Trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene H3C ~ CH3 /C(CHa)s \ /.\ / -I II in which R = -CHz-~~~ ~j~-OH
R/'~ /'~ .-.\
1~ C(CH3)3 melting point: 242-245°C .
f3) 1,3,5-Tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)isocyanurate ~\ /R /C(CH3)a in which R = -CHz-~~1 ~j~-OH
._.\
C(CH3)3 melting point: 218-223°C
y) 1,3,5-Tris(2',6'-dimethyl-4'-tert-butyl-5'-hydroxybenzyl)isocyanurate /R H3C\ _ in which R = -CHz-~~~ ~j~-C(CH3)3 /'~~~ .-0 0 H3C/ ~\OH
melting point: 145-155°C
d) 1,2-Bis[3',3'-bis(4"-hydroxy-5"-tert-butylphenyl)butanoyloxy)ethane QH
/~\ /C(CH3)a I II
.\ /.
H3C-~-CHz-~-~CHz ~~\
I II
~\ /~\C(CHa)a ~H
z melting point: 170°C
e) Bis(3-tert-butyl-4-hydroxy-6-methylphenyl)sulfide (H3C)3C\ /C(CH3)3 HO-~\. .~.-S-,\._.~~-OH
._ ._.
melting point: 161°C
2-(2'-Hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-methyl-6-tert-butyl-phenyl acrylate QH CHZ ~OCCH=CHz (HaC)aC\ /~\ / ~ /~\ /C(CHa)a I II I II
.\ /. .\ /.
melting point: 130-132°C
n) 1,1,3-Tris[3'-tert-butyl-4'-hydroxy-6'-methylphenyl]butane (H3C)3C\ /C(CH3)3 HO-.\._.~~ H ~\. ~~._OH
._. HZ ._.
H3C HCH3 C~3 H3C\ ~~\
I II
~\ /~\C(CHa)s ~H
melting point: 182.5-190°C
B) 2,4-Di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate /C(CHs)s j (CHa)s (HaC)sC_~~._./~ ~~ ~\._~/~ OH
\C(CHs)a melting point: 190°C
Metal deactivators:
1) N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl]hydrazine (HaC)aC\ /C(CH3)a .-.
HO-~~ j~-(CHz)z-~-NHNH-~-(CHz)z-~~~ ~j~-OH
.-. ._ (H3C)3C/ ~\C(CH3)a melting point: 224-229°C
K) N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxyethyl]oxalic acid diamide (HaC)aC\
H~~~~ ~j~-(CHz)2-~-0-(CHz)z-~-(H3C)3C~~-.
melting point: 173°C
Sterically hindered amines:
Poly(2-(N,N-bis(2',2',6',6'-tetramethyl-4'-piperidinyl)hexamethylene-diamino-4-morpholino-1,3,5-triazin-6-yl]
(CHz)6 ~ ~N\
H3C\I/~\I% H3 H3C\I/~\I% H3 H3C~~~~\CH3 H3C~~~~\CH3 .\0/.
n melting point: 110-130°C
u) Poly[2-(N,N-bis(2',2',6',6'-tetramethyl-4'-piperidinyl)hexamethylene-diamino-4-tert-octyl-1,3,5-triazin-6-yl]
~T ( C H z ) s ~1 ~N\
H3C\I/~\I/CH3 H3C\I/~\I/CH3 \
HN-C8H1~-t H3C/~~~\CH3 H3C/~\~~\CH3 n melting point: 120-150°C
v) 1,5,8,12-Tetrakis[2',4'-bis(1",2",2",6",6"-pentamethyl-4"-piperidinyl-(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetraazadodecane H-~-(CHz)a-~-(CHz)zy-(CHz)a-yH
H3C\ /CH3 r4H9 /.-~NN' .~-CH
.
~ a \.
.
_ HaC/
~N .\ \CH3 R - . HaC\ /CH3 -.~-CHa H \.
9 \CH3 melting point: 150°C
Bis[1',2',2',6',6'-pentamethyl-4'-piperidinyl]-2-butyl-2-(3",5"-di-tert-butyl-4"-hydroxybenzyl)malonate HaC\ j H3 /
(H3C)aC\ ~~ ~\~- -CH3 /~\
HO-~~. ~~ -CHz- -C4H9 H3C CH3 \ -_~/~ H3C\ % Ha (HaC)aC/~ 00 /. .~-CH3 .\ _ H3C/~\CH3 melting point: 146-150°C
o) 1,2-Bis[3',3',5',5'-tetramethyl-2'-oxo-1',4'-diazinan-1'-yl]ethane HaC\ /CHa~% 0~ HaC\ j H3 HN\~ ~-(CHz)z-~~ ~/NH
H3C/~\CH3. .H3C/.\CH3 melting point: 136°C
~r ) HjC\ /CH3 0 - \~~
H3C CH3 \~ ~/~\~ ~\~ ~/NH
\ /_ / \ /~\~~ HjC/~\CH3 ~J ~\ _ _ HN\~ /~
~ ~ 0 H3C/~\CH3 melting point: 270°C
Benzotriazoles:
p) 2-(2'-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole ~ H C(CH3)3 \ ~_ /
I I ~-~j~ ~~
\~/.\N \~- /.
~\C(CH3)a melting point: 150-155°C
Q) 2-(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5'-chlorobenzotriazole C1\ /~\ QH /C(CH3)a I j - /~
~~ /~~ ~\ _ /
~ ~\CH3 melting point: 137-140°C
i) 2-(2'-Hydroxy-3',5'-di-tert-butylphenyl)-5'-chlorobenzotriazole C1\ /~\ QH /C(CH3)a I j .\ /.\,. .\ /
\C(CHs)a melting point: 154-158°C
Phosphorus-containing stabilisers:
v) Tris[2,4-di-tert-butylphenyl]phosphite (H3C)3C-~~~ ~j'- P
~ ~\C(CH3)a melting point: 180-185°C
Bis[2,4-di-tert-butylphenyl]pentaerythritol diphosphite C(CH3)a (HaC)aC
_ / 0-. -0 \ _ (HaC)aC-'/~ ~\ -0P/ \~/~ \P-C-~~. '~ -C(CH3)a \._./~ \~~/ \~-Q/ \._~/.
melting point: 160-175°C
X) Bis[2,6-di-tert-butyl-4-methylphenyl]pentaerythritol diphosphite /C(CHa)a (HsC)3C\
~ -' 0- ~ -0 H3C-~j ~ -0-P/ \ /~ \P-~~/._.\ -CH3 \~_- /~ \~~/~\~-0/ \ -~/~
~\C(CH3)a (H3C)3C/~
melting point: 235°C
V~ ) ~Ha (H3C)3C~ ~'~ ~ ~ ~'~ /C(CH3)3 I II ~ II
.\ /.\0 O/.\ /.
(H3C)3~ \~/ ~(CH3)3 melting point: 200-201°C
cu) Calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester (H3C)3C~
CzHs _ HO-'~~_./~ CHZ-~ 0 Ca2+
(H3C)3C/~-melting point: >150°C
A) Nickel salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester (H3C)jC~ _ CzHs _ HO-~~~ ~ j~-CH2- 0 Ni2+
(H3C)3C/~-.
melting point: >180°C
Nickel-containing UV-absorbers:
B) 2,2'-Thio-bis(4-tert-octylphenolato~-butylamino nickel (II) t-H17C8-.\._.~ 0 jS Ni-NHC4H9 t-H17C8-.\.-.~ 0 melting point: 258°C
Metal salts of C,s-C~~-fatty acids:
t) Ca palmitate, melting point: 150-155°C (decomposition) D) Mg palmitate, melting point: 121°C
E) Zn palmatate, melting point: 125°C
Z) Ca stearate, melting point: 180°C
H) Mg stearate, melting point: 145°C
A) Zn stearate, melting point: 130°C
I) Ca behenate, melting point: 150°C
K) Mg behenate, melting point: 150°C
A) Zn behenate, melting point: 125°C
A phosphorus-containing stabiliser, especially a phosphate, is of interest as component c).
The invention relates especially preferably to a process in which the stabiliser system used contains components a), b) and c) and in which component b) is a sterically hindered phenolic antioxidant and compo-nent c) is a phosphate.
According to another preference, component b) is n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate and/or tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]methane and component c) is tras[2,4-di-tert-butylphenyl]phosphate.
Also preferred is a process in which component b) is a stabiliser that melts at from 50 to 120°C and component c) is a stabiliser that melts at from 180 to 200°C and the stabiliser mixture as heated to from 180 to 200°C.
Components a), b) and c) are known and are for the most part commercially available products.
Olefins that can be polymerised on carrier catalysts are, for example, ethylene or a-olefins, especially propylene, 1-butene, 4-methylpentene-1 or 5-methylhexene-1, and mixtures of olefins, such as, for example, ethylene/propylene or propylene in admixture with smaller amounts of higher a-olefins.
Polyethylene, polypropylene, copolymers of ethylene and copolymers of propylene, especially polyethylene and polypropylene, each applied to carrier catalysts, are of interest.
The polymerisation catalysts used, which are frequently referred to as third generation catalysts, are advantageously solid catalysts of a particular particle size, such as, for example, those described in DE-A-29 33 997 and DE-A-26 41 960. They consist, for example, of an anhydrous magnesium dihalide in active form and a titanium compound.
Magnesium dihalide in active form denotes one in the X-ray spectrum of which the line of strongest reflection is broadened compared with the corresponding line in the spectrum of inactive magnesium halide.
Preferably, magnesium dichloride or magnesium dibromide is used as magnesium dihalide. The titanium compound contains preferably at least one titanium-halogen bond, the use of titanium tetrachloride being especially preferred.
The titanium compound can be used in combination with an electron donor, for example a carboxylic acid ester, such as that described in EP-A-45 977.
After reaction of the magnesium halide component with the titanium compound and, where appropriate, with the electron donor, the excess titanium compound and the excess electron donor are advantageously washed out with an inert solvent, for example with hexane or heptane.
The catalyst prepared in this manner is activated by reaction with an aluminium alkyl, which is preferably used in the form of a solution in an alkane. Examples of suitable aluminium alkyls are A1(CzHs)a or A1(CaH9)3.
There may be added as coactivator an electron donor such as, for example, an organic silicon compound that contains at least one Si-0-C bond, such as that described, for example, in EP-A-45 977. Examples of such silicon compounds are phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldi-methoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and ethyl-trimethoxysilane.
The polymerisation with these catalysts can be carried out according to known methods in liquid or gaseous phase. The liquid phase may be, for example, an aliphatic hydrocarbon, or the liquid monomer itself.
Spherical polymerised polyolefins are also described, for example, in P. Galli, P.C. Barbe and L. Noristi; "High Yield Catalysts in Olefin Polymerization", Die Angewandte Makromolekulare Chemie 120 (1984), p. 73-90 (No. 1935).
The diameter of the olefin polymers polymerised on carrier catalysts is preferably from 2 to 5 mm, especially from 2 to 3 mm.
The melting point of these granular-type polyolefins is, for example, from 140 to 165°C.
The concentration of the stabiliser mixtures in the polyolefin to be stabilised is preferably from 0.01 to 5 % by weight, especially from 0.05 to 1 % by weight.
Before incorporation into the polyolefin, it is advantageous to heat the stabiliser system until a milky solution has formed. This milky solution is a suspension of component c) in a) and/or b). For stabilisation, the polyolefin is stirred, for example for from 2 to 10 minutes, in a suitable device (preferably a mixer) with the stabiliser system, which has a temperature of, for example, from 60 to 120°C, preferably from 100 to 120°C, especially from 100 to 110°C, and then cooled.
Advantage-ously, the polyolefin is heated, for example to approximately from 60 to 120°C, before stabilisation.
The temperature of the polyolefin may be, for example, from 60 to 79°C if the stabiliser system contains as carrier a substance that melts at approximately from 0 to 79°C, such as, for example, paraffin oil, or if the stabilizer system has subsequently been treated with paraffin oil.
The ratio by weight of stabiliser system to paraffin oil is in the latter case, for example, from 1:1 to 3:1. In the case of subsequent treatment of the stabiliser system with paraffin oil, the stabiliser system is advantageously stirred into hot paraffin oil (from 100 to 120°C) and then stirred (for example for from 15 to 30 minutes) until a homogeneous mixture is obtained which can be used for the stabilisation of the polyolefin.
If a substance that melts at approximately from 80 to 110°C is used as carrier, such as, for example, wax, it is advantageous if the temperature of the polyolefin is, for example, from 80 to 120°C, preferably from 80 to 110°C.
The preparation of the stabiliser system is advantageously carried out by mixing components a) and/or b) and c). The mixture is heated, for example to from 120 to 260°C, preferably with stirring. The resulting melt is stirred, for example, for from 2 to 15 minutes, preferably from 8 to 12 minutes, and then cooled until it solidifies, which occurs, for example, at a temperature of from 0 to 30°C. The cooling can be effected, for example, with cold water or some other inert liquid, or with nitrogen or some other inert gas. It is also possible to cool the melt, for example, using a cold metal plate.
The preparation of the stabiliser system can also be effected, for example, in a kneader, in which case the stabiliser mixture is obtained in the form of a granulate.
The following Examples further illustrate the invention.
Example 1: Preparation of the stabiliser mixtures.
Stabiliser mixture I:
20 g of n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 50 g of tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]-methane and 100 g of tris[2,4-di-tert-butylphenyl]phosphite as well as 200 g of polyethylene wax (melting point according to ASTM D-3104:
102°C, hardness according to ASTM D-5: 7.0 dmm, density according to ASTM D-1505: 0.91 g/cc, viscosity according to Brookfield at 140°C:
180 cps) are mixed together and heated to 200°C. The molten material is stirred at that temperature for 10 minutes. The mixture is subsequently cooled, also with stirring, and solidifies.
Stabiliser mixture II:
II is prepared analogously to I using glyceryl monostearate instead of the wax.
Stabiliser mixture III:
III is prepared analogously to I using distearyl thiodipropionate instead of the polyethylene wax.
Stabiliser mixture IV:
IV is prepared analogously to I using 50 g of polyethylene wax instead of 200 g of polyethylene wax.
Stabiliser mixture V:
V is prepared analogously to IV, the mixing and heating being effected in an extruder ( BUSS-KO-KNETER) and the additive mixture being prepared in the form of a granulate.
Examples 2a-2c: Stabilisation of spherical polypropylene pellets.
a) 1000 g of spherical polypropylene ( Moplen SPL 12) are heated to 104°C
for 7 minutes in a~enschel mixer (capacity: 5000 ml). 3.7 g of the stabiliser mixture given in Table la, which have previously been melted at 104°C, are added. The mixture is stirred for 2 minutes and then cooled. The stabilised polypropylene pellets are subjected to oven ageing at 149°C for 30 h. The test results are given in Table la.
Discolouration of the polypropylene pellets indicates inadequate stabili-sation.
Table la:
Stabilizer 30 h oven ageing at 149C
mixture discolouration I no discolouration II no discolouration III no discolouration b) 1000 g of spherical polypropylene ( Moplen SPL 12) are heated to 65°C
for 3 minutes in ~Henschel mixer (capacity: 5000 ml). 3.7 g of the stabiliser mixture given in Table lb, which have previously been heated to 104°C, are added. Further processing and testing are carried out as in a). The test results are given in Table lb.
Table lb:
Stabilizer 30 h oven ageing at 149C
mixture discolouration III no discolouration c) 1000 g of sphe ~ al polypropylene ( Moplen SPL 12) are heated to 65°C
for 3 minutes in a Henschel mixer (capacity: 5000 ml).
2.2 g of the stabiliser mixture given in Table lc are added to 1 g of hot paraffin oil (110°C) and the resulting mixture is stirred at that temperature for 20 minutes. The mixture is then added to the poly-propylene (65°C) and the mixture is stirred for 2 minutes and then cooled. The polypropylene pellets are tested as in a). The test results are given in Table lc.
Table lc:
Stabilizer 30 h oven ageing at 149C
mixture discolouration IV no discolouration V no discolouration
Claims (13)
1. A process for stabilising olefin polymers having a mean particle diameter of from 1 to 5 mm that have been polymerised on carrier catalysts, which comprises treating the polyolefins with a stabiliser mixture prepared by heating to from 120 to 260°C a mixture containing components a), b) and c) or components b) and c) with component a) being at least one carrier, component b) being at least one stabiliser that melts at from 20 to 120°C, and component c) being at least one stabiliser that melts at from 120 to 260°C, and then cooling said mixture until solidified, components b) and c) being different.
2. A process according to claim 1, wherein the stabiliser mixture contains components a), b) and c).
3. A process according to claim 1, wherein component a) is a wax, paraffin oil or a glyceryl monocarboxylic acid ester.
4. A process according to claim 3, wherein component a) is a polyethylene, a polypropylene, an olefinic copolymer, an ethylene/vinyl acetate copolymer, an ethylene/(unsaturated carboxylic acid ester) copolymer, an ethylene/(unsaturated carboxylic acid metal salt) copolymer, a polyethylene or polypropylene each modified with unsaturated carboxylic acids, petroleum, paraffin oil, a polyalkylene glycol or a glyceryl monocarboxylic acid ester.
5. A process according to claim 1, wherein component b) is a sterically hindered phenolic antioxidant, a phosphorus-containing stabiliser, a sterically hindered amine, a benzotriazole, a benzophenone, a thiodicarboxylic acid diester or a dialkyl disulfide.
6. A process according to claim 1, wherein component b) is a sterically hindered phenolic antioxidant.
7. A process according to claim 1, wherein component c) is a sterically hindered phenolic antioxidant, a metal deactivator, a sterically hindered amine, a benzotriazole, a phosphorus-containing stabiliser, a nickel-containing UV-absorber or a metal salt of a C16-C22 fatty acid.
8. A process according to claim 1, wherein component c) is a phosphorus-containing stabiliser.
9. A process according to claim 1, wherein component c) is a phosphite.
10. A process according to claim 2, wherein component b) is a sterically hindered phenolic antioxidant and component c) is a phosphite.
11. A process according to claim 10, wherein component b) is n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxy-phenyl)propionate or tetrakis[3,5-di-tert-butyl-4-hydroxy-phenylpropionyloxymethyl]methane, and component c) is tris[2,4-di-tert-butylphenyl]phosphate.
12. A process according to claim 1, wherein component b) is a stabiliser that melts at from 50 to 120°C and component c) is a stabiliser that melts at from 180 to 200°C and the stabiliser mixture is heated to from 180 to 200°C.
13. A process according to claim 1, wherein the polyolefins have a mean diameter of from 2 to 5 mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1351/89-3 | 1989-04-10 | ||
| CH135189 | 1989-04-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2014005A1 CA2014005A1 (en) | 1990-10-10 |
| CA2014005C true CA2014005C (en) | 2001-05-15 |
Family
ID=4208441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002014005A Expired - Fee Related CA2014005C (en) | 1989-04-10 | 1990-04-06 | Process for stabilising polyolefins |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0392392B1 (en) |
| JP (1) | JP2942997B2 (en) |
| KR (1) | KR0156249B1 (en) |
| CN (1) | CN1038595C (en) |
| AR (1) | AR246976A1 (en) |
| AT (1) | ATE131189T1 (en) |
| AU (1) | AU632553B2 (en) |
| BR (1) | BR9001671A (en) |
| CA (1) | CA2014005C (en) |
| DD (1) | DD294035A5 (en) |
| DE (1) | DE59009938D1 (en) |
| ES (1) | ES2081313T3 (en) |
| FI (1) | FI101806B (en) |
| MX (1) | MX171591B (en) |
| NO (1) | NO301021B1 (en) |
| ZA (1) | ZA902698B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU630179B2 (en) * | 1989-04-06 | 1992-10-22 | Montell North America Inc. | Polyolefins suitable for spinning and thermoweldable fibers obtained from them |
| IT1231769B (en) * | 1989-08-02 | 1991-12-21 | Himont Inc | PROCEDURE FOR THE STABILIZATION OF POLYOLEFINS AND PRODUCTS OBTAINED FROM IT. |
| IT1247941B (en) * | 1991-05-17 | 1995-01-05 | Enichem Sintesi | PROCESS FOR OBTAINING GRANULAR FORMS OF ADDITIVES FOR ORGANIC POLYMERS |
| IT1258271B (en) * | 1992-04-06 | 1996-02-22 | Enichem Sintesi | PROCESS FOR OBTAINING GRANULAR FORMS OF ADDITIVES FOR ORGANIC POLYMERS. |
| US5844042A (en) * | 1993-04-06 | 1998-12-01 | Great Lakes Chemical Italia S.R.L. | Process for obtaining granular forms of additives for organic polymers |
| EP0635514B1 (en) * | 1993-07-22 | 1999-05-12 | General Electric Company | Neo-diol phosphites as polymer stabilizers |
| US5605947A (en) * | 1993-07-22 | 1997-02-25 | General Electric Company | Amorphous neo-diol phosphite compositions |
| US5614571A (en) * | 1994-09-16 | 1997-03-25 | General Electric Company | Stabilizer blend containing phosphite |
| AU7043298A (en) | 1997-04-15 | 1998-11-11 | Ciba Specialty Chemicals Holding Inc. | Preparation of low-dust stabilisers |
| DE19817257A1 (en) | 1998-04-19 | 1999-12-09 | Grace Gmbh | Granulate composition of antiblocking agents and additives for polymer production |
| WO2008033410A1 (en) | 2006-09-14 | 2008-03-20 | Ingenia Polymers Inc. | High concentration pelletized additive concentrates for polymer |
| CN104114616B (en) * | 2012-02-01 | 2016-05-18 | 株式会社Adeka | Resin Additive Masterbatch |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA695633B (en) * | 1968-08-08 | 1971-03-31 | Ici Ltd | Polymer stabilisers |
| US4647608A (en) * | 1986-03-21 | 1987-03-03 | The Dow Chemical Company | Process for the production of polyolefin resins containing an amide and a zinc compound |
| DE3876110T2 (en) * | 1987-02-13 | 1993-05-27 | Enichem Sintesi | SOLID STABILIZER MIXTURE FOR ORGANIC POLYMERS AND METHOD FOR THEIR PRODUCTION. |
| IT1202611B (en) * | 1987-03-03 | 1989-02-09 | Enichem Sintesi | SOLID STABILIZING COMPOSITION FOR SYNTHETIC POLYMERS |
-
1990
- 1990-04-06 CA CA002014005A patent/CA2014005C/en not_active Expired - Fee Related
- 1990-04-06 EP EP90106660A patent/EP0392392B1/en not_active Expired - Lifetime
- 1990-04-06 DE DE59009938T patent/DE59009938D1/en not_active Expired - Fee Related
- 1990-04-06 AR AR90316580A patent/AR246976A1/en active
- 1990-04-06 ES ES90106660T patent/ES2081313T3/en not_active Expired - Lifetime
- 1990-04-06 MX MX020221A patent/MX171591B/en unknown
- 1990-04-06 AU AU53031/90A patent/AU632553B2/en not_active Ceased
- 1990-04-06 FI FI901772A patent/FI101806B/en not_active IP Right Cessation
- 1990-04-06 AT AT90106660T patent/ATE131189T1/en active
- 1990-04-09 DD DD90339599A patent/DD294035A5/en not_active IP Right Cessation
- 1990-04-09 ZA ZA902698A patent/ZA902698B/en unknown
- 1990-04-09 NO NO901605A patent/NO301021B1/en not_active IP Right Cessation
- 1990-04-09 BR BR909001671A patent/BR9001671A/en not_active IP Right Cessation
- 1990-04-10 CN CN90101989A patent/CN1038595C/en not_active Expired - Fee Related
- 1990-04-10 KR KR1019900004889A patent/KR0156249B1/en not_active Expired - Fee Related
- 1990-04-10 JP JP2094911A patent/JP2942997B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AR246976A1 (en) | 1994-10-31 |
| DD294035A5 (en) | 1991-09-19 |
| NO301021B1 (en) | 1997-09-01 |
| AU5303190A (en) | 1990-10-11 |
| KR900016347A (en) | 1990-11-13 |
| JPH02294345A (en) | 1990-12-05 |
| BR9001671A (en) | 1991-05-14 |
| ATE131189T1 (en) | 1995-12-15 |
| AU632553B2 (en) | 1993-01-07 |
| NO901605L (en) | 1990-10-11 |
| EP0392392A1 (en) | 1990-10-17 |
| CN1046537A (en) | 1990-10-31 |
| JP2942997B2 (en) | 1999-08-30 |
| FI101806B1 (en) | 1998-08-31 |
| NO901605D0 (en) | 1990-04-09 |
| ZA902698B (en) | 1991-01-30 |
| CN1038595C (en) | 1998-06-03 |
| EP0392392B1 (en) | 1995-12-06 |
| FI901772A0 (en) | 1990-04-06 |
| CA2014005A1 (en) | 1990-10-10 |
| DE59009938D1 (en) | 1996-01-18 |
| ES2081313T3 (en) | 1996-03-01 |
| FI101806B (en) | 1998-08-31 |
| KR0156249B1 (en) | 1998-12-01 |
| MX171591B (en) | 1993-11-08 |
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| EEER | Examination request | ||
| MKLA | Lapsed |