WO2025021515A1 - Composition for increased stability of recycled polyethylene - Google Patents
Composition for increased stability of recycled polyethylene Download PDFInfo
- Publication number
- WO2025021515A1 WO2025021515A1 PCT/EP2024/069487 EP2024069487W WO2025021515A1 WO 2025021515 A1 WO2025021515 A1 WO 2025021515A1 EP 2024069487 W EP2024069487 W EP 2024069487W WO 2025021515 A1 WO2025021515 A1 WO 2025021515A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethylene
- composition according
- recycled polyethylene
- polymer
- composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- -1 polyethylene Polymers 0.000 title claims abstract description 39
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 32
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 35
- 239000005977 Ethylene Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229930003427 Vitamin E Natural products 0.000 claims abstract description 16
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019165 vitamin E Nutrition 0.000 claims abstract description 16
- 239000011709 vitamin E Substances 0.000 claims abstract description 16
- 229940046009 vitamin E Drugs 0.000 claims abstract description 16
- 239000012748 slip agent Substances 0.000 claims abstract description 7
- 238000009472 formulation Methods 0.000 claims description 22
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 14
- 239000011732 tocopherol Substances 0.000 claims description 10
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 7
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 7
- 229920001684 low density polyethylene Polymers 0.000 claims description 7
- 239000004702 low-density polyethylene Substances 0.000 claims description 7
- 229940099514 low-density polyethylene Drugs 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- 229930003799 tocopherol Natural products 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 229960001295 tocopherol Drugs 0.000 claims description 6
- 229930003802 tocotrienol Natural products 0.000 claims description 6
- 239000011731 tocotrienol Substances 0.000 claims description 6
- 235000019148 tocotrienols Nutrition 0.000 claims description 6
- 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 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920001038 ethylene copolymer Polymers 0.000 claims description 3
- 235000010384 tocopherol Nutrition 0.000 claims description 3
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 3
- GJJVAFUKOBZPCB-UHFFFAOYSA-N 2-methyl-2-(4,8,12-trimethyltrideca-3,7,11-trienyl)-3,4-dihydrochromen-6-ol Chemical compound OC1=CC=C2OC(CCC=C(C)CCC=C(C)CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-UHFFFAOYSA-N 0.000 claims description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 2
- 239000000499 gel Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 21
- 239000002861 polymer material Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- GJJVAFUKOBZPCB-ZGRPYONQSA-N (r)-3,4-dihydro-2-methyl-2-(4,8,12-trimethyl-3,7,11-tridecatrienyl)-2h-1-benzopyran-6-ol Chemical class OC1=CC=C2OC(CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-ZGRPYONQSA-N 0.000 description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 125000002640 tocopherol group Chemical class 0.000 description 4
- 235000019149 tocopherols Nutrition 0.000 description 4
- 229940068778 tocotrienols Drugs 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 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 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- XZZWOTQMUOIIFX-UHFFFAOYSA-N 1-(2-diphenoxyphosphanyloxypropoxy)propan-2-yl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC(C)COCC(C)OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 XZZWOTQMUOIIFX-UHFFFAOYSA-N 0.000 description 1
- HPLQLQQLRLADHV-UHFFFAOYSA-N 1-[bis(6-methylheptoxy)phosphoryl]-4-octylbenzene Chemical compound CCCCCCCCC1=CC=C(P(=O)(OCCCCCC(C)C)OCCCCCC(C)C)C=C1 HPLQLQQLRLADHV-UHFFFAOYSA-N 0.000 description 1
- VKCMZEUOQWUNAR-UHFFFAOYSA-N 2,2-bis(2,4-ditert-butyl-6-methylphenyl)ethyl dihydrogen phosphite Chemical compound CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1C(COP(O)O)C1=C(C)C=C(C(C)(C)C)C=C1C(C)(C)C VKCMZEUOQWUNAR-UHFFFAOYSA-N 0.000 description 1
- NOXZWNDBNWJGFX-UHFFFAOYSA-N 2,3-dicyclopentyl-4-methylphenol Chemical compound C1CCCC1C=1C(C)=CC=C(O)C=1C1CCCC1 NOXZWNDBNWJGFX-UHFFFAOYSA-N 0.000 description 1
- HUYSCRCIPIWDPL-UHFFFAOYSA-N 2,3-dipentylbenzene-1,4-diol Chemical compound CCCCCC1=C(O)C=CC(O)=C1CCCCC HUYSCRCIPIWDPL-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- MXSKJYLPNPYQHH-UHFFFAOYSA-N 2,4-dimethyl-6-(1-methylcyclohexyl)phenol Chemical compound CC1=CC(C)=C(O)C(C2(C)CCCCC2)=C1 MXSKJYLPNPYQHH-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- VQQLTEBUMLSLFJ-UHFFFAOYSA-N 2,6-ditert-butyl-4-nonylphenol Chemical compound CCCCCCCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VQQLTEBUMLSLFJ-UHFFFAOYSA-N 0.000 description 1
- QABUQFYJORNZBW-UHFFFAOYSA-N 2-(2-hydroxypropoxy)propan-1-ol;phosphorous acid Chemical compound OP(O)O.CC(O)COC(C)CO QABUQFYJORNZBW-UHFFFAOYSA-N 0.000 description 1
- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 1
- PHXLONCQBNATSL-UHFFFAOYSA-N 2-[[2-hydroxy-5-methyl-3-(1-methylcyclohexyl)phenyl]methyl]-4-methyl-6-(1-methylcyclohexyl)phenol Chemical compound OC=1C(C2(C)CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1(C)CCCCC1 PHXLONCQBNATSL-UHFFFAOYSA-N 0.000 description 1
- ZJYVOSGUICQZHC-UHFFFAOYSA-N 2-butyl-2-ethyl-1-(2,4,6-tritert-butylphenyl)propane-1,3-diol;phosphorous acid Chemical compound OP(O)O.CCCCC(CC)(CO)C(O)C1=C(C(C)(C)C)C=C(C(C)(C)C)C=C1C(C)(C)C ZJYVOSGUICQZHC-UHFFFAOYSA-N 0.000 description 1
- XKZGIJICHCVXFV-UHFFFAOYSA-N 2-ethylhexyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCC(CC)CCCC)OC1=CC=CC=C1 XKZGIJICHCVXFV-UHFFFAOYSA-N 0.000 description 1
- TVWGHFVGFWIHFN-UHFFFAOYSA-N 2-hexadecan-2-yl-4,6-dimethylphenol Chemical compound CCCCCCCCCCCCCCC(C)C1=CC(C)=CC(C)=C1O TVWGHFVGFWIHFN-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- SEBPXHSZHLFWRL-UHFFFAOYSA-N 3,4-dihydro-2,2,5,7,8-pentamethyl-2h-1-benzopyran-6-ol Chemical group O1C(C)(C)CCC2=C1C(C)=C(C)C(O)=C2C SEBPXHSZHLFWRL-UHFFFAOYSA-N 0.000 description 1
- YLUZWKKWWSCRSR-UHFFFAOYSA-N 3,9-bis(8-methylnonoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCC(C)C)OCC21COP(OCCCCCCCC(C)C)OC2 YLUZWKKWWSCRSR-UHFFFAOYSA-N 0.000 description 1
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-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
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- FJDLQLIRZFKEKJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound CC(C)(C)C1=CC(CCC(N)=O)=CC(C(C)(C)C)=C1O FJDLQLIRZFKEKJ-UHFFFAOYSA-N 0.000 description 1
- KMWIPXLIKIAZMT-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanehydrazide Chemical compound CC(C)(C)C1=CC(CCC(=O)NN)=CC(C(C)(C)C)=C1O KMWIPXLIKIAZMT-UHFFFAOYSA-N 0.000 description 1
- VYIBCOSBNVFEIW-UHFFFAOYSA-N 3-phenylpropanamide Chemical compound NC(=O)CCC1=CC=CC=C1 VYIBCOSBNVFEIW-UHFFFAOYSA-N 0.000 description 1
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-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
- BFZOTKYPSZSDEV-UHFFFAOYSA-N 4-butan-2-yl-2,6-ditert-butylphenol Chemical compound CCC(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BFZOTKYPSZSDEV-UHFFFAOYSA-N 0.000 description 1
- WTWGHNZAQVTLSQ-UHFFFAOYSA-N 4-butyl-2,6-ditert-butylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WTWGHNZAQVTLSQ-UHFFFAOYSA-N 0.000 description 1
- JSVDMQKVGLGYCM-UHFFFAOYSA-N 5,5-dimethyl-2-phenoxy-1,3,2-dioxaphosphinane Chemical compound O1CC(C)(C)COP1OC1=CC=CC=C1 JSVDMQKVGLGYCM-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- NBPOOCGXISZKSX-UHFFFAOYSA-N 6-methylheptyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)CCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NBPOOCGXISZKSX-UHFFFAOYSA-N 0.000 description 1
- PMRUPHDYGYPYQC-UHFFFAOYSA-N 6-methylheptyl phenyl hydrogen phosphite Chemical compound CC(C)CCCCCOP(O)OC1=CC=CC=C1 PMRUPHDYGYPYQC-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 101100041688 Caenorhabditis elegans sao-1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- RCZRMCMDNRCJSE-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C(C)(C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C(C)(C)C)C(C)(C)C RCZRMCMDNRCJSE-UHFFFAOYSA-N 0.000 description 1
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 1
- FRCLQKLLFQYUJJ-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FRCLQKLLFQYUJJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OZFFDSIESCRZEA-UHFFFAOYSA-N [2,3-di(nonyl)phenyl] bis(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=C(CCCCCCCCC)C=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OZFFDSIESCRZEA-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- OGVJEUDMQQIAPV-UHFFFAOYSA-N diphenyl tridecyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCCCCC)OC1=CC=CC=C1 OGVJEUDMQQIAPV-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 229940113120 dipropylene glycol Drugs 0.000 description 1
- IIRVGTWONXBBAW-UHFFFAOYSA-M disodium;dioxido(oxo)phosphanium Chemical compound [Na+].[Na+].[O-][P+]([O-])=O IIRVGTWONXBBAW-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003749 fatty amide group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- LTXMJHWSYUANCC-UHFFFAOYSA-N tris(2,4-ditert-butyl-5-methylphenyl) phosphite Chemical compound C1=C(C(C)(C)C)C(C)=CC(OP(OC=2C(=CC(=C(C)C=2)C(C)(C)C)C(C)(C)C)OC=2C(=CC(=C(C)C=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C LTXMJHWSYUANCC-UHFFFAOYSA-N 0.000 description 1
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- PEXOFOFLXOCMDX-UHFFFAOYSA-N tritridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC PEXOFOFLXOCMDX-UHFFFAOYSA-N 0.000 description 1
- 235000020942 vitamer Nutrition 0.000 description 1
- 239000011608 vitamer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
Definitions
- the present invention relates to a composition comprising an ethylene-based polymer having increased stability, and in particular to a polymer composition comprising a recycled polyethylene formulation having increased stability.
- Polymer materials are ubiquitously used in a wide variety of applications, including in durable and single-use goods, and in rigid and flexible applications. It is well-known that polymer materials may suffer from oxidative and thermal degradation. A particular phenomenon that may occur as a result of degradation is the generation of long chain branches. In particular, such generation of long chain branches is believed to occur due to chain scissions or hydrogen abstraction in the polymer chains, resulting in the formation of certain radicals, which may join to form a polymer chain with increased long chain branches. This phenomenon is particularly known to occur in polyethylene materials. It may be induced thermally and/or mechanically and may be initiated during processing of polymers into a product, as well as during the use of the product.
- Such long chain branch formation can typically be observed as gel formation, wherein the term “gel” refers to a small defect that distorts the appearance and strength of a polymer product.
- gel refers to a small defect that distorts the appearance and strength of a polymer product.
- the formation of gels is preferably avoided as much as possible. Therefore, typically stabilizers are added to polymer materials. Such stabilizers prevent gel formation upon processing of polymers and also prevent degradation during the life span of the polymer material.
- a recycling process may for example involve compiling a suitable polymer composition comprising the polymer material and further additives, and subjecting the polymer composition to a re-shaping process to create a new product that again may find its way to e.g. consumers.
- a post-consumer recycle stream is likely to have been exposed to outdoor conditions (oxygen, moisture, elevated temperatures, etc.) and as such may have suffered from thermo-oxidative degradation.
- additives present in post-consumer recycle streams may have been depleted partially or in full, further decreasing its resistance against thermo-oxidative degradation.
- polymer materials are recycled after use, they typically are subjected to melt-shaping processes in order to convert the polymer materials from the form in which they were obtained as waste into a form that is suitable for renewed use.
- Such exposure to high temperatures, such as in extrusion or injection molding processes, is particularly believed to contribute to long chain branch formation.
- the present invention provides a composition
- a composition comprising: a) at least one ethylene-based polymer; b) vitamin E, the vitamin E being at least one tocopherol or tocotrienol; c) a secondary antioxidant; and d) optionally a slip-agent.
- Such a composition is appropriately stable and sufficiently stable to use also in recycling applications.
- the composition can stabilize post-consumer recycled polyethylene.
- Vitamin E is a group of eight fat soluble compounds that include four tocopherols and four tocotrienols. Tocopherols and tocotrienols both occur in a (alpha), p (beta), y (gamma) and 5 (delta) forms, as determined by the number and position of methyl groups on the chromanol ring. All eight of these vitamers feature a chromane double ring, with a hydroxyl group that can donate a hydrogen atom to reduce free radicals.
- each of the three "R” sites has a methyl group (CH 3 ) attached.
- the combination of a secondary antioxidant with vitamin E is particularly effective in reducing the gel count of a composition with ethylene-based polymer as compared to combinations with other primary antioxidants, notably in combination with PCR materials.
- This is particularly attractive as vitamin E is non-toxic, which poses additional advantages in case of migration of the antioxidant to the surface and subsequent human contact.
- PCR materials are often deficient in secondary anti-oxidant concentration originally introduced during production.
- the role of secondary anti-oxidants is to reduce peroxides - formed through the interaction of the polymer with oxygen during use - into non-radical forming species (alcohols). Though efficient, these secondary anti-oxidants convert into inactive species themselves upon exhibiting their function. As a result, the concentration of intact secondary anti-oxidant reduces over time, while the concentration of peroxides attached to the polymer backbone increases. If these peroxides are not reduced prior to melting, they rapidly decompose into radical based species, effectively inducing unwanted chemical reactions in the polyolefin (related to gel formation).
- Vitamin E is a highly reactive primary antioxidant which rapidly scavenges any radical formed during processing (i.e. formed by the high temperatures, shear or decomposition of peroxides). The higher the reactivity of the phenolic anti-oxidant, the lower the life-time of a radical and hence the lower number of chemical reactions it can undergo. [0017] The combination of a secondary antioxidant with vitamin E is capable of rapidly suppressing radical formation during processing and reducing peroxides formed in the plastic upon contact with oxygen during its use.
- the secondary antioxidant may for example be a phosphite.
- the secondary antioxidant may be a monophosphite, a diphosphite or a polyphosphite.
- Suitable monophosphites that may be used as secondary antioxidant can be selected from trisnonylphenyl phosphite, trilauryl phosphite, tris (2,4-di-t-butyl phenyl) phosphite, diisooctyl phosphite, triisodecyl phosphite, diisodecylphenyl phosphite, diphenyl isodecyl phosphite, triphenyl phosphite, tris(tridecyl) phosphite, diphenyl isooctyl phosphite, 2,2- methylene-bis(4,6-di-t-butyl-phenyl)-octyl-phosphite, 2,2’-ethylenebis(4,6-di-t-butyl- phenyl)fluorophosphonite, disodium hydrogen
- Suitable diphosphites that may be used as secondary antioxidant can be selected from distearyl pentaerythritol diphosphite, tetrakis-(2,4-di-t-butyl-phenyl)-4,4’-bi-phenylene-di- phosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis-(2,6-di-t-butyl-4-methyl- phenyl)-pentaerythritol-di-phosphite, bis(2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, tetrakis isodecyl 4,4’-isopropylidene diphosphite, bis-(2,4-dicumylphenyl)-pentaerythritol diphosphite, tetrapheny
- Suitable polyphosphites that may be used as secondary antioxidant can be selected from poly(dipropyleneglyocol)phenyl phosphite, 2,2’,2”-nitrilo triethyl-tris(3,3’,5,5’-tetra-t-butyl- 1 ,1 ’-biphenyl-2,2’-diyl) phosphite, dipropyleneglycol phosphite, and 1 ,1 ,3-tris(2-methyl-4- (ditridecyl phosphite)-5-t-butylphenyl)butane.
- the secondary antioxidant is a monophosphite.
- a particularly preferable monophosphate is tris (2,4-di-t-butyl phenyl) phosphite.
- the composition may optionally comprise a further primary antioxidant.
- the further primary antioxidant may for example be selected from methylhydroquinone; 2-t-butyl-hydro- quinonone; diamylhydroquinone; 2-t-butyl-4-methylphenol; styrenated phenol; 3-t-butyl-4- hydroxyanisole; 2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-4-ethyl-phenol; 2,6-di-t-butyl-a- (di-methyl-amino)-p-cresol; 2,6-di-t-butyl-4-sec-butyl-phenol; 2,6-di-t-butyl-4-nonyl-phenol; 2,4-di-methyl-6-(1-methyl-cyclohexyl) phenol; 2,4-dimethyl-6-(1-methyl-pentadecyl)-phenol; 3- (3,5-di-d
- the further primary antioxidant is benzenepropanoic acid, 3,5-bis(1 ,1-dimethylethyl)-4-hydroxy-, 1 , 1 [2 ,2-bi s[[3- [3 , 5- bis ( 1 , 1 -dimethylethyl)-4-hydroxyphenyl]-1 -oxopropoxy]methyl]- 1 ,3- propanediyl] ester.
- the composition comprises > 100 and ⁇ 4000 ppm by weight of the further primary antioxidant, with regard to the total weight of the ethylene-based polymer, more preferably > 400 and ⁇ 2000 ppm, most preferably > 500 and ⁇ 1000 ppm.
- the ethylene-based polymer is a low-density polyethylene (LDPE), a linear low-density polyethylene (LLDPE), a high-density polyethylene (HDPE), or a mixture thereof.
- LDPE low-density polyethylene
- LLDPE linear low-density polyethylene
- HDPE high-density polyethylene
- the ethylene-based polymer is a LLDPE.
- Such LDPE may for example have a density of > 900 and ⁇ 935 kg/m 3 , preferably of > 910 and ⁇ 925 kg/m 3 .
- An LDPE may for example an ethylene-based homopolymer or copolymer produced via free radical polymerisation, such as high-pressure free-radical polymerisation.
- such LDPE may be produced via high-pressure tubular reactor processes or via high-pressure autoclave reactor processes.
- An LLDPE may for example be an ethylene-based copolymer having a density of > 850 and ⁇ 940 kg/m 3 , preferably of > 890 and ⁇ 925 kg/m 3 , more preferably of > 905 and ⁇ 925 kg/m 3 .
- the LLDPE may comprise moieties derived from one of more C3-C10 a-olefins, preferably moieties derived from an a-olefin selected from propylene, 1 -butene, 4-methyl-1- pentene, 1 -hexene, or 1 -octene.
- the LLDPE may comprise > 5.0 and ⁇ 25.0 wt%, preferably > 5.0 and ⁇ 20.0 wt%, of moieties derived from an a-olefin selected from propylene, 1 -butene, 4-methyl-1 -pentene, 1 -hexene, or 1 -octene, with regard to the total weight of the LLDPE.
- an a-olefin selected from propylene, 1 -butene, 4-methyl-1 -pentene, 1 -hexene, or 1 -octene
- An HDPE may for example be an ethylene-based copolymer or homopolymer having a density of > 940 and ⁇ 975 kg/m 3 , preferably of > 945 and ⁇ 970 kg/m 3 , more preferably of > 945 and ⁇ 965 kg/m 3 .
- the HDPE may comprise moieties derived from one of more C3-C10 a- olefins, preferably moieties derived from an a-olefin selected from propylene, 1 -butene, 4- methyl-1 -pentene, 1-hexene, or 1-octene.
- the HDPE may comprise > 0.2 and ⁇ 5.0 wt%, preferably > 0.5 and ⁇ 3.0 wt%, of moieties derived from an a-olefin selected from propylene, 1 -butene, 4-methyl-1 -pentene, 1-hexene, or 1-octene, with regard to the total weight of the HDPE.
- the density of the polyethylenes may be determined in accordance with ASTM D792 (2008).
- the ethylene-based polymer has a density of > 900 and ⁇ 940 kg/m 3 , more preferably of > 910 and ⁇ 930 kg/m 3 , most preferably of > 915 and ⁇ 925 kg/m 3 , as determined in accordance with ASTM D792; and/or a melt mass-flow rate (MFR2) of > 0.1 and ⁇ 5.0 g/10 min, more preferably of > 0.1 and ⁇ 3.0 g/10 min, most preferably of > 0.5 and ⁇ 1.5 g/10 min, as determined in accordance with ASTM D1238, at 190°C at a load of 2.16 kg.
- MFR2 melt mass-flow rate
- the ethylene-based polymer is an ethylene homopolymer or an ethylene copolymer comprising ⁇ 25.0 wt%, preferably ⁇ 20.0 wt%, of moieties derived from a comonomer selected from 1-butene, 1-hexene and 1-octene.
- the ethylenebased polymer is an ethylene copolymer comprising > 5.0 and ⁇ 25.0 wt%, preferably > 5.0 and ⁇ 20.0 wt%, of moieties derived from a comonomer selected from 1-butene, 1-hexene and 1-octene.
- the composition comprises > 600 and ⁇ 4000 ppm by weight of the secondary antioxidant, with regard to the total weight of the ethylene-based polymer, more preferably > 700 and ⁇ 3000 ppm, most preferably > 800 and ⁇ 2500 ppm.
- the composition may comprise > 800 and ⁇ 1200 ppm or > 2000 and ⁇ 2500 ppm by weight of the secondary antioxidant.
- the composition comprises > 40 and ⁇ 400 ppm by weight of vitamin E, with regard to the total weight of the ethylene-based polymer, preferably > 45 and ⁇ 300 ppm, most preferably > 50 and ⁇ 150 ppm.
- the optional slip-agent reduces the viscosity during processing, thereby decreasing the number of radicals (or their lifetime) formed by shear of the polymer chains.
- the slip-agent is a fatty amide, preferably erucamide or oleamide, most preferably erucamide.
- the composition comprises > 0.1 and ⁇ 5 wt% of the slip-agent, with regard to the total weight of the ethylene-based polymer, more preferably > 0.2 and ⁇ 2.5, most preferably > 0.5 and ⁇ 1 .5 wt%.
- the composition may further comprise an acid-scavenger such as calcium stearate or zinc stearate to negate the effect of any residual catalyst.
- an acid-scavenger such as calcium stearate or zinc stearate to negate the effect of any residual catalyst.
- the composition may comprise > 100 and ⁇ 2500 ppm by weight, preferably > 150 and ⁇ 750 ppm by weight, more preferably > 200 and ⁇ 600 ppm by weight of calcium stearate or zinc stearate, with regard to the total weight of the ethylene-based polymer, preferably calcium stearate.
- the invention further provides a polymer composition comprising the composition of the invention, and further comprising a recycled polyethylene formulation, preferably a postconsumer recycled polyethylene formulation, more preferably a post-consumer recycled polyethylene formulation having: a density of > 900 and ⁇ 970 kg/m3, preferably of > 910 and ⁇ 960 kg/m3, more preferably of > 910 and ⁇ 930 kg/m3, as determined in accordance with ISO 1183-1 (2019); and/or a melt mass-flow rate (MFR2) of > 0.1 and ⁇ 5.0 g/10 min, preferably of > 0.1 and ⁇ 2.0 g/10 min, more preferably of > 0.1 and ⁇ 1.0 g/10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 2.16 kg.
- a recycled polyethylene formulation preferably a postconsumer recycled polyethylene formulation, more preferably a post-consumer recycled polyethylene formulation having: a density of > 900 and ⁇ 970 kg/
- the recycled polyethylene formulation comprises > 90.0 wt% of ethylenebased polymers, more preferably > 95.0 wt%, with regard to the total weight of the recycled polyethylene formulation.
- the recycled polyethylene formulation comprises ⁇ 10.0 wt% of propylene- based polymers, or > 0.1 and ⁇ 10.0 wt%, preferably ⁇ 5.0 wt%, for example > 1.0 and ⁇ 5.0 wt%, with regard to the total weight of the recycled polyethylene formulation.
- the recycled polyethylene formulation comprises polyethylene-based polymers and polypropylene-based polymers, for example the recycled polyethylene formulation may comprise ethylene-based polymers and > 1.0 and ⁇ 10.0 wt% of propylene-based polymers, preferably the recycled polyethylene formulation may comprise > 90.0 wt% of ethylene-based polymers and > 1 .0 and ⁇ 10.0 wt% of propylene-based polymers.
- the polymer composition comprises 10 - 60 wt% of the composition of the invention and 40 - 90 wt% of the post-consumer recycled polyethylene formulation.
- the invention further provides use of a composition according to the invention to reduce the gel content (also: gel count) of polymer compositions comprising recycled polyethylene.
- Gels are to be understood to be distinct polymeric domains in the polymer material that do not show thermoplastic properties, for example wherein individual polymer molecules are chemically bound to each other as a result of crosslinking, or for example wherein polymer molecules of a high molecular weight form physical bonds which are not reversible by exposing the material to a heat processing step such as is the case in thermoplastic processing, for example by forming entanglements and/or dense crystalline domains.
- the gel content may for example be determined via on-line measurement of a film produced in the cast film system using an FSA-100 optical film surface analyser equipped with software version 6.3.4.2 obtainable from Optical Control Systems GmbH, in which the surface analyser is positioned between the chill roll system and the nip rolls.
- the film surface analyser may comprise a CCD line scan camera with a resolution of 50 pqq, enabling the identification of gels having a dimension of at least 50 pqq length and 50 pqq width.
- the film surface analyser may comprise a halogen based illumination system. A continuous image of the film surface may be produced.
- the determination of gels may be performed using image recognition software provided by Optical Control Systems GmbH integrated with the FSA-100 film surface analyser.
- a film sample with a total surface size of > 1 .0 m 2 may be tested, alternatively > 5.0 m 2 , alternatively > 1 .0 and ⁇ 10.0 m 2 , alternatively > 5.0 and ⁇ 8.0 m 2 .
- the film thickness may be 40 - 60 pm, such as 50 pm.
- the equivalent diameter of a gel is to be understood to be the average of the length and the width of the surface area of the gel as determined via on-line measurement as described above.
- the equivalent diameter may be the average of the largest diameter of a gel and the largest diameter of said gel in a direction perpendicular direction to said largest diameter of said gel.
- the resulting compounds were processed into cast films, followed by the assessment of the gelcount.
- the cast film extrusion was performed using an OCS extruder running at a maximum set temperature of 230 °C (melt temperature 226 - 227 °C), followed by cooling of the film on chilled rollers (25 °C) at a take up speed of 3.2 m/min.
- the gel content was determined via on-line measurement of the film in the cast film system using an FSA-100 film surface analyser obtainable from Optical Control Systems GmbH software version 6.3.4.2, wherein surface analyser is the positioned between the chill roll system and the nip rolls.
- the film surface analyser comprised a CCD line scan camera with a resolution of 50 pqq.
- the smallest defects that could be identified accordingly had a dimension of 50 pqq length and 50 pqq width.
- the film surface analyser comprised halogen based illumination system. A continuous image of the film surface was thus produced.
- the determination of defects was performed using image recognition software provided by Optical Control Systems GmbH integrated with the FSA-100 film surface analyser. A film sample with a total surface size of 6.0 m ⁇ 2>was tested.
- SEI 0.28 - 0.29 KWh/kg & melt temperature of 250 - 260 °C
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Abstract
The invention relates to a composition comprising at least one ethylene-based polymer; vitamin E, a secondary antioxidant; and optionally a slip-agent. The composition is particularly suitable to reduce the gel content of polymer compositions comprising recycled polyethylene.
Description
Composition for increased stability of recycled polyethylene
[0001] The present invention relates to a composition comprising an ethylene-based polymer having increased stability, and in particular to a polymer composition comprising a recycled polyethylene formulation having increased stability.
[0002] Polymer materials are ubiquitously used in a wide variety of applications, including in durable and single-use goods, and in rigid and flexible applications. It is well-known that polymer materials may suffer from oxidative and thermal degradation. A particular phenomenon that may occur as a result of degradation is the generation of long chain branches. In particular, such generation of long chain branches is believed to occur due to chain scissions or hydrogen abstraction in the polymer chains, resulting in the formation of certain radicals, which may join to form a polymer chain with increased long chain branches. This phenomenon is particularly known to occur in polyethylene materials. It may be induced thermally and/or mechanically and may be initiated during processing of polymers into a product, as well as during the use of the product.
[0003] Such long chain branch formation can typically be observed as gel formation, wherein the term “gel” refers to a small defect that distorts the appearance and strength of a polymer product. In order to provide a material with adequate appearance and strength, the formation of gels is preferably avoided as much as possible. Therefore, typically stabilizers are added to polymer materials. Such stabilizers prevent gel formation upon processing of polymers and also prevent degradation during the life span of the polymer material.
[0004] Presently, there is an increased emphasis on extending the service life of polymer materials by recycling, thereby reducing their environmental impact. A recycling process may for example involve compiling a suitable polymer composition comprising the polymer material and further additives, and subjecting the polymer composition to a re-shaping process to create a new product that again may find its way to e.g. consumers.
[0005] However, a post-consumer recycle stream is likely to have been exposed to outdoor conditions (oxygen, moisture, elevated temperatures, etc.) and as such may have suffered from thermo-oxidative degradation. In addition, additives present in post-consumer recycle streams may have been depleted partially or in full, further decreasing its resistance against thermo-oxidative degradation. When polymer materials are recycled after use, they typically are subjected to melt-shaping processes in order to convert the polymer materials from the form in which they were obtained as waste into a form that is suitable for renewed use. Such
exposure to high temperatures, such as in extrusion or injection molding processes, is particularly believed to contribute to long chain branch formation.
[0006] It is an objective of the present invention to provide a composition comprising ethylene-based polymer material, that is sufficiently stable to prevent gel formation. It is a further objective of the present invention to provide a composition comprising ethylene-based polymer material, that is sufficiently stable to use also in recycling applications. It is a particular objective of the present invention to provide a composition that can stabilize postconsumer recycled polyethylene, in order to enable recycling of the polyethylene into new products.
[0007] Thereto, the present invention provides a composition comprising: a) at least one ethylene-based polymer; b) vitamin E, the vitamin E being at least one tocopherol or tocotrienol; c) a secondary antioxidant; and d) optionally a slip-agent.
[0008] Such a composition is appropriately stable and sufficiently stable to use also in recycling applications. In particular, the composition can stabilize post-consumer recycled polyethylene.
[0009] Vitamin E is a group of eight fat soluble compounds that include four tocopherols and four tocotrienols. Tocopherols and tocotrienols both occur in a (alpha), p (beta), y (gamma) and 5 (delta) forms, as determined by the number and position of methyl groups on the chromanol ring. All eight of these vitamers feature a chromane double ring, with a hydroxyl group that can donate a hydrogen atom to reduce free radicals.
[0011] For alpha (a)-tocopherol each of the three "R" sites has a methyl group (CH3) attached.
For beta (p)-tocopherol: R1 = methyl group, R2 = H, R3 = methyl group. For gamma (y)- tocopherol: R1 = H, R2 = methyl group, R3 = methyl group. For delta (b)-tocopherol: R1 = H, R2 =
H, R3 = methyl group. The same configurations exist for the tocotrienols, except that the hydrophobic side chain has three carbon-carbon double bonds whereas the tocopherols have a saturated side chain.
[0013] Any one of these 8 identified compounds as well as any combination thereof is understood to be vitamin E in the present invention.
[0014] Surprisingly, the combination of a secondary antioxidant with vitamin E is particularly effective in reducing the gel count of a composition with ethylene-based polymer as compared to combinations with other primary antioxidants, notably in combination with PCR materials. This is particularly attractive as vitamin E is non-toxic, which poses additional advantages in case of migration of the antioxidant to the surface and subsequent human contact.
[0015] PCR materials are often deficient in secondary anti-oxidant concentration originally introduced during production. The role of secondary anti-oxidants is to reduce peroxides - formed through the interaction of the polymer with oxygen during use - into non-radical forming species (alcohols). Though efficient, these secondary anti-oxidants convert into inactive species themselves upon exhibiting their function. As a result, the concentration of intact secondary anti-oxidant reduces over time, while the concentration of peroxides attached to the polymer backbone increases. If these peroxides are not reduced prior to melting, they rapidly decompose into radical based species, effectively inducing unwanted chemical reactions in the polyolefin (related to gel formation).
[0016] Vitamin E is a highly reactive primary antioxidant which rapidly scavenges any radical formed during processing (i.e. formed by the high temperatures, shear or decomposition of peroxides). The higher the reactivity of the phenolic anti-oxidant, the lower the life-time of a radical and hence the lower number of chemical reactions it can undergo.
[0017] The combination of a secondary antioxidant with vitamin E is capable of rapidly suppressing radical formation during processing and reducing peroxides formed in the plastic upon contact with oxygen during its use.
[0018] The secondary antioxidant may for example be a phosphite. For example, the secondary antioxidant may be a monophosphite, a diphosphite or a polyphosphite.
[0019] Suitable monophosphites that may be used as secondary antioxidant can be selected from trisnonylphenyl phosphite, trilauryl phosphite, tris (2,4-di-t-butyl phenyl) phosphite, diisooctyl phosphite, triisodecyl phosphite, diisodecylphenyl phosphite, diphenyl isodecyl phosphite, triphenyl phosphite, tris(tridecyl) phosphite, diphenyl isooctyl phosphite, 2,2- methylene-bis(4,6-di-t-butyl-phenyl)-octyl-phosphite, 2,2’-ethylenebis(4,6-di-t-butyl- phenyl)fluorophosphonite, disodium hydrogen phosphite, bis(2,4-di-t-butyl-6- methylphenyl)ethyl phosphite, 2,4,6-tri-t-butylphenyl-2-butyl-2-ethyl- 1 ,3-propanediol phosphite, triisooctyl phosphite, tris(dipropyleneglycol) phosphite, diisooctyl octylphenyl phosphite, tris(2,4-di-t-butyl-5-methylphenyl) phosphite, diphenyl phosphite, phenyl neopentyleneglycol phosphite, tristearyl phosphite, dinonylphenyl bis(nonylphenyl) phosphite, isooctyl phenyl phosphite, 2-ethylhexyl diphenyl phosphite, and diphenyl tridecyl phosphite.
[0020] Suitable diphosphites that may be used as secondary antioxidant can be selected from distearyl pentaerythritol diphosphite, tetrakis-(2,4-di-t-butyl-phenyl)-4,4’-bi-phenylene-di- phosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis-(2,6-di-t-butyl-4-methyl- phenyl)-pentaerythritol-di-phosphite, bis(2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, tetrakis isodecyl 4,4’-isopropylidene diphosphite, bis-(2,4-dicumylphenyl)-pentaerythritol diphosphite, tetraphenyl dipropyleneglycol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, tetra(tridecyl)-4,4’-butylidene-bis(6-t-butyl- 2-methyldiphenyl) diphosphite, and tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4’-bi-phenylene diphosphonite.
[0021] Suitable polyphosphites that may be used as secondary antioxidant can be selected from poly(dipropyleneglyocol)phenyl phosphite, 2,2’,2”-nitrilo triethyl-tris(3,3’,5,5’-tetra-t-butyl- 1 ,1 ’-biphenyl-2,2’-diyl) phosphite, dipropyleneglycol phosphite, and 1 ,1 ,3-tris(2-methyl-4- (ditridecyl phosphite)-5-t-butylphenyl)butane.
[0022] Preferably, the secondary antioxidant is a monophosphite. A particularly preferable monophosphate is tris (2,4-di-t-butyl phenyl) phosphite. Also preferred is a compound of formula I:
wherein each R is individually selected from 1 ,1 -dimethylpropyl or hydrogen. The latter compound is an FDA approved additive, and as such would render the composition non-toxic if used as the sole secondary antioxidant.
[0023] The composition may optionally comprise a further primary antioxidant. The further primary antioxidant may for example be selected from methylhydroquinone; 2-t-butyl-hydro- quinonone; diamylhydroquinone; 2-t-butyl-4-methylphenol; styrenated phenol; 3-t-butyl-4- hydroxyanisole; 2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-4-ethyl-phenol; 2,6-di-t-butyl-a- (di-methyl-amino)-p-cresol; 2,6-di-t-butyl-4-sec-butyl-phenol; 2,6-di-t-butyl-4-nonyl-phenol; 2,4-di-methyl-6-(1-methyl-cyclohexyl) phenol; 2,4-dimethyl-6-(1-methyl-pentadecyl)-phenol; 3- (3,5-di-tert.-butyl-4-hydroxyphenyl)propionic acid-methyl-ester; octadecyl 3-(3,5-di-t-butyl-4- hydroxyphenyl) propionate; 2,6-di-phenyl-4-octadecyl-cyclo-oxy-phenol; a-tocopherol; n- propyl 3,4,5-trihydroxybenzoate; phenol, 4-methyl-2,6-bis(2-phenylethenyl)-2,6-distyryryl-p- cresol;, 2(2-phenylethenyl)-4-methyl-6-(1 ,1-dimethylethyl)-phenol; isooctyl 3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate; 6-t-butyl-2,4-dimethyl-phenol; dicyclopentyl-p-cresol; 2,6-di-t- butyl-4-n-butylphenol; 4-hydroxymethyl-2,6-di-t-butyl-phenol; 2,6-di-t-butyl-phenol; 3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionic acid hydrazide; 3-(3,5-di-tert.-butyl-4- hydroxyphenyl)propionic acid; 2,4,6 tris t-butyl phenol; 2,5-di-t-butyl-hydroquinone; p- benzoquinone; hydroquinone; hydroquinone-mono-methyl-ether; 2,2'-bis(6-t-butyl-p- cresyl)methane; 2,2'-methylenebis (6-tert-butyl-4-ethylphenol); 2,2'-methylenebis 6-(1- methylcyclohexyl)-p-cresol; 4,4’-butylidene-bis-(6-t-butyl-m-cresol); 2,2'-ethylidenebis (4,6-di- t-butylphenol); phenol, 4,4'-methylenebis[2,6-bis(1 ,1-dimethylethyl)-4,4'-methylenebis (2,6-di- t-butylphenol); 2,2'-ilsobutylidenebis (4,6-dimethylphenol); bisphenol A; 3,9-bis(2-(3-(3-(tert- butyl-4-hydroxy-5-methyl-phenyl)-propionyl-oxy)-1 ,1-dimethylethyl]-2,4,8,10- tetraoxospiro(5,5)undecane; tri-ethylene-glycol-bis-3-(t-butyl-4-hydroxy-5-methyl-phenyl)- propionate; hexamethylenebis (3,5-di-t-butyl-4-hydroxycinnamate); benzenepropanamide, N,N'-1 ,3-propanediylbis[3,5-bis(1 ,1-dimethylethyl)-4-hydroxy-]N,N'-1 ,3-Propanediylbis(3,5-di-
t-butyl-4-hydroxyhydrocinnamamide); 2,2'-methylenebis(6-nonyl-p-cresol); 1 ,1 ,3-tris(2-methyl- 4-hydroxy-5-t-butyl phenyl)butane; 1 ,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene; butyric acid, 3,3-bis(3-t-butyl-4-hydroxyphenyl) ethylene ester; tris(3,5-di-t-butyl-4- hydroxy benzyl) isocyanurate; 1 ,3,5-tris (4-t-butyl-2,6-dimethyl-3-hydroxy-benzyl)-iso- cyanurate; 3-(3,5-di-t-butyl-4-hydroxy-phenyl) propion acid ester with 1 ,3,5-tris (2- hydroxyethyl)-iso-cyanurate; pentaerythritol tetrakis(3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate; 2,6-bis(2’-bis-hydroxy-3’-t-butyl-5’-methyl-phenyl-4-methyl-phenol) or benzenepropanoic acid, 3 , 5- bis ( 1 , 1 -dimethylethyl)-4-hydroxy-, 1 , 1 [2 ,2- bis [[3- [3 , 5- b is( 1 , 1 - dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1 ,3-propanediyl] ester. Preferably, the further primary antioxidant is benzenepropanoic acid, 3,5-bis(1 ,1-dimethylethyl)-4-hydroxy-, 1 , 1 [2 ,2-bi s[[3- [3 , 5- bis ( 1 , 1 -dimethylethyl)-4-hydroxyphenyl]-1 -oxopropoxy]methyl]- 1 ,3- propanediyl] ester.
[0024] Preferably, the composition comprises > 100 and < 4000 ppm by weight of the further primary antioxidant, with regard to the total weight of the ethylene-based polymer, more preferably > 400 and < 2000 ppm, most preferably > 500 and < 1000 ppm.
[0025] Preferably, the ethylene-based polymer is a low-density polyethylene (LDPE), a linear low-density polyethylene (LLDPE), a high-density polyethylene (HDPE), or a mixture thereof. Most preferably, the ethylene-based polymer is a LLDPE.
[0026] Such LDPE may for example have a density of > 900 and < 935 kg/m3, preferably of > 910 and < 925 kg/m3. An LDPE may for example an ethylene-based homopolymer or copolymer produced via free radical polymerisation, such as high-pressure free-radical polymerisation. For example, such LDPE may be produced via high-pressure tubular reactor processes or via high-pressure autoclave reactor processes.
[0027] An LLDPE may for example be an ethylene-based copolymer having a density of > 850 and < 940 kg/m3, preferably of > 890 and < 925 kg/m3, more preferably of > 905 and < 925 kg/m3. The LLDPE may comprise moieties derived from one of more C3-C10 a-olefins, preferably moieties derived from an a-olefin selected from propylene, 1 -butene, 4-methyl-1- pentene, 1 -hexene, or 1 -octene. For example, the LLDPE may comprise > 5.0 and < 25.0 wt%, preferably > 5.0 and < 20.0 wt%, of moieties derived from an a-olefin selected from propylene, 1 -butene, 4-methyl-1 -pentene, 1 -hexene, or 1 -octene, with regard to the total weight of the LLDPE.
[0028] An HDPE may for example be an ethylene-based copolymer or homopolymer having a density of > 940 and < 975 kg/m3, preferably of > 945 and < 970 kg/m3, more preferably of >
945 and < 965 kg/m3. The HDPE may comprise moieties derived from one of more C3-C10 a- olefins, preferably moieties derived from an a-olefin selected from propylene, 1 -butene, 4- methyl-1 -pentene, 1-hexene, or 1-octene. For example, the HDPE may comprise > 0.2 and < 5.0 wt%, preferably > 0.5 and < 3.0 wt%, of moieties derived from an a-olefin selected from propylene, 1 -butene, 4-methyl-1 -pentene, 1-hexene, or 1-octene, with regard to the total weight of the HDPE.
[0029] The density of the polyethylenes may be determined in accordance with ASTM D792 (2008).
[0030] Preferably, the ethylene-based polymer has a density of > 900 and < 940 kg/m3, more preferably of > 910 and < 930 kg/m3, most preferably of > 915 and < 925 kg/m3, as determined in accordance with ASTM D792; and/or a melt mass-flow rate (MFR2) of > 0.1 and < 5.0 g/10 min, more preferably of > 0.1 and < 3.0 g/10 min, most preferably of > 0.5 and < 1.5 g/10 min, as determined in accordance with ASTM D1238, at 190°C at a load of 2.16 kg.
[0031] Preferably, the ethylene-based polymer is an ethylene homopolymer or an ethylene copolymer comprising < 25.0 wt%, preferably < 20.0 wt%, of moieties derived from a comonomer selected from 1-butene, 1-hexene and 1-octene. For example, the ethylenebased polymer is an ethylene copolymer comprising > 5.0 and < 25.0 wt%, preferably > 5.0 and < 20.0 wt%, of moieties derived from a comonomer selected from 1-butene, 1-hexene and 1-octene.
[0032] Preferably, the composition comprises > 600 and < 4000 ppm by weight of the secondary antioxidant, with regard to the total weight of the ethylene-based polymer, more preferably > 700 and < 3000 ppm, most preferably > 800 and < 2500 ppm. For example, the composition may comprise > 800 and < 1200 ppm or > 2000 and < 2500 ppm by weight of the secondary antioxidant.
[0033] Preferably, the composition comprises > 40 and < 400 ppm by weight of vitamin E, with regard to the total weight of the ethylene-based polymer, preferably > 45 and < 300 ppm, most preferably > 50 and < 150 ppm.
[0034] The optional slip-agent reduces the viscosity during processing, thereby decreasing the number of radicals (or their lifetime) formed by shear of the polymer chains. Preferably, the slip-agent is a fatty amide, preferably erucamide or oleamide, most preferably erucamide.
[0035] Preferably, the composition comprises > 0.1 and < 5 wt% of the slip-agent, with regard to the total weight of the ethylene-based polymer, more preferably > 0.2 and < 2.5, most preferably > 0.5 and < 1 .5 wt%.
[0036] The composition may further comprise an acid-scavenger such as calcium stearate or zinc stearate to negate the effect of any residual catalyst. For example the composition may comprise > 100 and < 2500 ppm by weight, preferably > 150 and < 750 ppm by weight, more preferably > 200 and < 600 ppm by weight of calcium stearate or zinc stearate, with regard to the total weight of the ethylene-based polymer, preferably calcium stearate.
[0037] The invention further provides a polymer composition comprising the composition of the invention, and further comprising a recycled polyethylene formulation, preferably a postconsumer recycled polyethylene formulation, more preferably a post-consumer recycled polyethylene formulation having: a density of > 900 and < 970 kg/m3, preferably of > 910 and < 960 kg/m3, more preferably of > 910 and < 930 kg/m3, as determined in accordance with ISO 1183-1 (2019); and/or a melt mass-flow rate (MFR2) of > 0.1 and < 5.0 g/10 min, preferably of > 0.1 and < 2.0 g/10 min, more preferably of > 0.1 and < 1.0 g/10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 2.16 kg.
[0038] Preferably, the recycled polyethylene formulation comprises > 90.0 wt% of ethylenebased polymers, more preferably > 95.0 wt%, with regard to the total weight of the recycled polyethylene formulation.
[0039] Preferably, the recycled polyethylene formulation comprises < 10.0 wt% of propylene- based polymers, or > 0.1 and < 10.0 wt%, preferably < 5.0 wt%, for example > 1.0 and < 5.0 wt%, with regard to the total weight of the recycled polyethylene formulation.
[0040] In a certain embodiment, the recycled polyethylene formulation comprises polyethylene-based polymers and polypropylene-based polymers, for example the recycled polyethylene formulation may comprise ethylene-based polymers and > 1.0 and < 10.0 wt% of propylene-based polymers, preferably the recycled polyethylene formulation may comprise > 90.0 wt% of ethylene-based polymers and > 1 .0 and < 10.0 wt% of propylene-based polymers.
[0041] Preferably, the polymer composition comprises 10 - 60 wt% of the composition of the invention and 40 - 90 wt% of the post-consumer recycled polyethylene formulation.
[0042] The invention further provides use of a composition according to the invention to reduce the gel content (also: gel count) of polymer compositions comprising recycled polyethylene.
[0043] Gels are to be understood to be distinct polymeric domains in the polymer material that do not show thermoplastic properties, for example wherein individual polymer molecules are chemically bound to each other as a result of crosslinking, or for example wherein polymer molecules of a high molecular weight form physical bonds which are not reversible by exposing the material to a heat processing step such as is the case in thermoplastic processing, for example by forming entanglements and/or dense crystalline domains.
[0044] The gel content may for example be determined via on-line measurement of a film produced in the cast film system using an FSA-100 optical film surface analyser equipped with software version 6.3.4.2 obtainable from Optical Control Systems GmbH, in which the surface analyser is positioned between the chill roll system and the nip rolls. The film surface analyser may comprise a CCD line scan camera with a resolution of 50 pqq, enabling the identification of gels having a dimension of at least 50 pqq length and 50 pqq width. The film surface analyser may comprise a halogen based illumination system. A continuous image of the film surface may be produced. The determination of gels may be performed using image recognition software provided by Optical Control Systems GmbH integrated with the FSA-100 film surface analyser. A film sample with a total surface size of > 1 .0 m2 may be tested, alternatively > 5.0 m2, alternatively > 1 .0 and < 10.0 m2, alternatively > 5.0 and < 8.0 m2. The film thickness may be 40 - 60 pm, such as 50 pm.
[0045] The equivalent diameter of a gel is to be understood to be the average of the length and the width of the surface area of the gel as determined via on-line measurement as described above. For example, the equivalent diameter may be the average of the largest diameter of a gel and the largest diameter of said gel in a direction perpendicular direction to said largest diameter of said gel.
[0046] The invention will now be illustrated by the following non-limiting examples.
[0047] A number of compositions (see Table 2) were subjected to extrusion compounding using a twin screw extruder (Krauss-Maffei Berstorff ZE25 UTXi twin-screw extruder with L/D 48, SEI = 0.31-0.33 kWh/kg). The resulting compounds were processed into cast films, followed by the assessment of the gelcount. The cast film extrusion was performed using an OCS extruder running at a maximum set temperature of 230 °C (melt temperature 226 - 227 °C), followed by cooling of the film on chilled rollers (25 °C) at a take up speed of 3.2 m/min.
[0048] The gel content was determined via on-line measurement of the film in the cast film system using an FSA-100 film surface analyser obtainable from Optical Control Systems GmbH software version 6.3.4.2, wherein surface analyser is the positioned between the chill roll system and the nip rolls. The film surface analyser comprised a CCD line scan camera with a resolution of 50 pqq. The smallest defects that could be identified accordingly had a
dimension of 50 pqq length and 50 pqq width. The film surface analyser comprised halogen based illumination system. A continuous image of the film surface was thus produced. The determination of defects was performed using image recognition software provided by Optical Control Systems GmbH integrated with the FSA-100 film surface analyser. A film sample with a total surface size of 6.0 m<2>was tested.
[0049] It should be noted that the recipes highlight the additional additives (on top of the 750 ppm Irganox 1010 and 1250 ppm Irgafos 168 already present in the commercial material). Table 2.
[0050] In parallel, the compositions of examples 1 - 7 were compounded together with LLDPE PCR material in 50/50 wt/wt ratio (SEI = 0.28 - 0.29 KWh/kg & melt temperature of 250 - 260 °C) resulting in the formulations of Table 3. The resulting PCR containing compounds were again subjected to cast film extrusion and gel-count assessment as described above. No significant changes in MFI were observed.
[0051] It can be observed that the gel count of reference example 1 is relatively high, which is thought to be related to the harsh processing conditions the sample was subjected to to enforce degradation. Various additives combinations were evaluated, including the introduction of Irganox MD1024 (primary antioxidant; pAO1), Vitamin E (primary antioxidant; pAO3), Irgafos 168 (secondary antioxidant; sAO1) or Weston 705 (secondary antioxidant; sAO2). A composition with slip-agent erucamide was tested as well. Clearly, the best results are obtained upon the introduction of Vitamine E and a secondary antioxidant (examples 5 and 6). Noteworthy, the addition of 1 wt% erucamide improves the gelcount, but results in a sticky film. This may be less desired.
[0052] Taking the same 7 samples after compounding with the 50% PCR phase results in halving the overall concentration of the additives. Though the gelcount is still high (also due to the presence of gels which are not related to polymer degradation), it can be observed that the presence of additional vitamin E and a secondary antioxidant results in a 10 - 20% reduction in gelcount compared to the reference or the samples with only secondary antioxidant. Clearly, as observed for the virgin material, also in mixtures with PCR the presence of additional vitamin E and a secondary anti-oxidant is boosting the resistance of the material against gel formation during extrusion.
Claims
1. Composition comprising: a) at least one ethylene-based polymer; b) vitamin E, the vitamin E being at least one tocopherol or tocotrienol; c) a secondary antioxidant; and d) optionally a slip-agent.
3. Composition according to claim 1 or 2, wherein the ethylene-based polymer is a low- density polyethylene (LDPE), a linear low-density polyethylene (LLDPE), a high-density polyethylene (HDPE), or a mixture thereof, preferably wherein the ethylene-based polymer is a LLDPE.
4. Composition according to any one of the preceding claims, wherein the ethylene-based polymer has:
• a density of > 900 and < 940 kg/m3, preferably of > 910 and < 930 kg/m3, more preferably of > 915 and < 925 kg/m3, as determined in accordance with ASTM D792; and/or
• a melt mass-flow rate (MFR2) of > 0.1 and < 5.0 g/10 min, preferably of > 0.1 and < 3.0 g/10 min, more preferably of > 0.5 and < 1 .5 g/10 min, as determined in accordance with ASTM D1238, at 190°C at a load of 2.16 kg.
5. Composition according to any one of the preceding claims, wherein the ethylene-based polymer is an ethylene homopolymer or an ethylene copolymer comprising < 25.0 wt%, preferably < 20.0 wt%, of moieties derived from a comonomer selected from 1 -butene,
1 -hexene and 1 -octene.
6. Composition according to any one of the preceding claims, wherein the composition comprises > 600 and < 4000 ppm by weight of the secondary antioxidant, with regard to the total weight of the ethylene-based polymer, preferably > 700 and < 3000 ppm, most preferably > 800 and < 2500 ppm.
7. Composition according to any one of the preceding claims, wherein the composition comprises > 40 and < 400 ppm by weight of vitamin E, with regard to the total weight of the ethylene-based polymer, preferably > 45 and < 300 ppm, most preferably > 50 and < 150 ppm.
8. Polymer composition comprising the composition according to any one of the preceding claims, and further comprising a recycled polyethylene formulation, preferably a postconsumer recycled polyethylene formulation, more preferably a post-consumer recycled polyethylene formulation having:
• a density of > 900 and < 970 kg/m3, preferably of > 910 and < 960 kg/m3, more preferably of > 910 and < 930 kg/m3, as determined in accordance with ISO 1183-1 (2019); and/or
• a melt mass-flow rate (MFR2) of > 0.1 and < 5.0 g/10 min, preferably of > 0.1 and < 2.0 g/10 min, more preferably of > 0.1 and < 1.0 g/10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 2.16 kg; preferably wherein the recycled polyethylene formulation comprises > 90.0 wt% of ethylene-based polymers and > 1.0 and < 10.0 wt% of propylene-based polymers..
9. Polymer composition according to claim 8, wherein
• the recycled polyethylene formulation comprises > 90.0 wt% of ethylene-based polymers, preferably > 95.0 wt%, with regard to the total weight of the recycled polyethylene formulation; and/or
• the recycled polyethylene formulation comprises < 10.0 wt% of propylene-based polymers, preferably < 5.0 wt%, with regard to the total weight of the recycled polyethylene formulation.
10. Polymer composition according to claim 8 or 9, comprising 10 - 60 wt% of the composition according to claim 1 and 40 - 90 wt% of the post-consumer recycled polyethylene formulation.
11. Use of a composition according to any one of claims 1 - 7 to reduce the gel content of polymer compositions comprising recycled polyethylene.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0542108A2 (en) * | 1991-11-12 | 1993-05-19 | F. Hoffmann-La Roche Ag | Stabilizers for plastic materials |
EP0730001A1 (en) * | 1995-02-22 | 1996-09-04 | F. Hoffmann-La Roche Ag | Stabilizers for plastic materials |
WO2011049728A1 (en) * | 2009-10-23 | 2011-04-28 | Chemtura Corporation | Polymers with low gel content and enhanced gas-fading |
WO2014108382A1 (en) * | 2013-01-10 | 2014-07-17 | Saudi Basic Industries Corporation | Polyethylene composition |
WO2021074140A1 (en) * | 2019-10-15 | 2021-04-22 | Sabic Global Technologies B.V. | Polyethylene composition for use with recycled polyethylene |
EP4331800A1 (en) * | 2022-08-30 | 2024-03-06 | Basell Poliolefine Italia S.r.l. | Process for recycling propylene based polymers |
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2024
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Publication number | Priority date | Publication date | Assignee | Title |
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EP0542108A2 (en) * | 1991-11-12 | 1993-05-19 | F. Hoffmann-La Roche Ag | Stabilizers for plastic materials |
EP0730001A1 (en) * | 1995-02-22 | 1996-09-04 | F. Hoffmann-La Roche Ag | Stabilizers for plastic materials |
WO2011049728A1 (en) * | 2009-10-23 | 2011-04-28 | Chemtura Corporation | Polymers with low gel content and enhanced gas-fading |
WO2014108382A1 (en) * | 2013-01-10 | 2014-07-17 | Saudi Basic Industries Corporation | Polyethylene composition |
WO2021074140A1 (en) * | 2019-10-15 | 2021-04-22 | Sabic Global Technologies B.V. | Polyethylene composition for use with recycled polyethylene |
EP4331800A1 (en) * | 2022-08-30 | 2024-03-06 | Basell Poliolefine Italia S.r.l. | Process for recycling propylene based polymers |
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